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High speed selective jet

electrodeposition of gold and
gold alloys using single
circular jets
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by the/an author.
Additional Information:

A Doctoral Thesis. Submitted in partial fulllment of the requirements

for the award of Doctor of Philosophy of Loughborough University.

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c C. Bocking

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HIGH SPEED SELECTIVE JET ELECTRODEPOSITION OF GOLD AND GOLD

ALLOYS USING SINGLE CIRCULAR JETS

by

C. E. BOCKING FIMF, Grad. IMF (Poly. South Bank)

A Doctoral Thesis

Submitted in fulfilment of the requirements

for the award of the degree of Doctor of Philosophy
Technology
University
Loughborough
the
of
of

Supervisor: Dr D. R. Gabe
Institute of Polymer and Materials Engineering
Loughborough University of Technology

m by C. Bocking 1994

ABSTRACT

High SpeedSelectiveJetElectrodeposition
(HSSJE)is a processin which metalsandalloysmay
be electrodeposited
at high ratesand in a selectivefashionwithout the needfor masking.Ile
jet of electrolyteat the surfaceto be
methodconsistsof directinga high velocitynon-submerged
platedandpassinga currentbetweenthe nozzleandthe substrate.Due to the natureof the flow
and the currentdistributioftwithin the jet, depositiontakesplaceat high ratesbut only in the
impingementand immediatelysurroundingregion. This techniquehas seenlittle commercial
withdeveloping
onlyasmallnumberofpapersonthesubject.7besewereconcerned
exploitationand
mathematicalmodelsfor the system.The purposeof this work was to examinethe structural,
produced
morphologicalandmetallurgicalcharacteristics
of bothgoldandgoldalloyelectrodeposits
undervariedconditionsofhighelectrolyteflow usingsmallgeometry(< Imm) nozzles.By relating
factorssuchaselectrolytevelocity, currentdensity,temperatureandmetalion concentrationetc
to the morphologyof the depositsproduced,an understanding
of the limiting conditionsfor
Resultsobtainedfrom depositsproducedby HSSJE
maximumdepositionrateswas ascertained.
As
those
to
made
under
conditions.
well as examiningthe
compared
more
conventional
were
deposits,attemptswere madeto gain informationon the electrochemicalfactors controlling
deposition.71ese factors, such as masstransfer characteristics,required the productionof
polarisationcurvesidentifyingthe limiting current densitiesof the systemunder study. Some
potentialapplicationsof the techniquearealsodiscussed.

ACKNOWLEDGEMENTS

The authorwould like to thankthe following peoplefor the invaluablecontributionto the work
carriedoutintheexperimental
phaseofthisTbesis.First,DrDavid Gabe,my AcademicSupervisor,
thatI undertakethis7"hesis
whooriginallysuggested
andwithoutwhom,it wouldneverhavebeen
Centre.Dr Brian Cameron,my GroupLeader
written. Also, my colleagues
at theHirst Research
and Mr Ian Christie, LaboratoryManagerof the MaterialsScienceLaboratoryas well as my
IndustrialSupervisor, for the freedomgiven to me in the pursuit of the aims of the BRITE
programmefrom whichthiswork wasderived.In addition,I wouldlike to thankDr BrianCameron
for carryingout the wear testingof connectorsin this study. Mr Alan Vale, for the chemical
analysisof theelectrolytesanddepositsproduced.Mr IanGunterfor thecomputercontrolprogram
that controlledthejet platingequipmentaswell asadviceandback-upon the electroniccontrol
systemsused.Mr Colin Dineen,who operatedthe X-Ray Diffraction equipmentand provided
enormousexpertisein the analysisand interpretationof the results.Mr David Prichardwho
producedsomeof the ScanningElectronMicrographsshownhere.Mr Chris Fisherfor themany
thatwe hadin trying to fathomthecomplexitiesof
varied,interestingandmostusefuldiscussions
the electrochemistry
of the system.
At Loughborough University my thanks go to Mr Frank Page, who produced some stunning and
prize winning Scanning Electron Micrographs of the more visually interesting deposits. Additionally, Dr Geoff Wilcox for the assistancehe provided concerningconventional electrochemical
procedures.
Finally, I would like to thank my wife Sueand children Laura and Lewis for their patienceduring
the writing of this Thesis.

inIndustrial
Theexperimental
workdescribedinthis thesiswastakenfrom aBRITE(BasicResearch
Technology)programmeNo. RI I B-304, "The improvementin the control andattainmentof high
processes".It was undertakenwith partnersCentro Svillupo Materiali,
speedelectrodeposition
Universityof Technology.Thework
GEC-MarconiHirst ResearchCentreandtheLoughborough
on HSSJEwascarriedout solelyat the Hirst ResearchCentreby the authorexceptwherestated
above.The other partnersworked on different aspectsof high speeddeposition.As such,the
its
For this reason,certainavenuesof
to
prior
commencement.
was
predetermined
programme
interestcouldnot be pursueddueto the needto obtaindefinitemilestoneswithin pre-determined
time periods.

11

Table of Contents
CHAPTER 1 INTRODUCTION
..........................................................
1.1 GENERAL BACKGROUND
.........................................................
1.2 SCOPE OF THIS STUDY
.............................................................
CHAPTER 2 GOLD ELECTRODEPOSITION
.......................................
2.1 GOLD PLATING IN THE ELECTRONICS INDUSTRY
.....................
2.2 ELECTROLYTE TYPES
.
.............................................................
2.2.1 Alkaline cyanideelectrolytes
.
...................................................
2.2.2 Acid gold electrolytes
.............................................................
2.2.2.1 Pure acid golds
..............................................................
2.2.2.2 Alloy acid golds
.............................................................
2.2.3 Structural characteristicsof gold deposits
.
.....................................
2.2.4 Ile influence of pulsed current on gold electrodeposition
. .................
CHAPTER 3 SELECTIVE PLATING TECHNIQUES
.............................
3.1 DIELECTRIC MASKING
00
...
................................................
00
......
3.1.1 Solvent based lacquers
..................................
o
.........................
3.1.2 Thick film inks
....................................................................
3.1.3 Photo-resists
........................................................................
3.1.3.1 Photoresistchemistry
.......................................................
3.1.3.1.1 Positive working resists
.............................................
3.1.3.1.2 Negative working resists
............................................
3.1.3.2 Outline of Printed Circuit Board Production Methods
..........
3.1.4 Pre-formed masks
...........................................
o
......................
3.1.5 Controlled depth immersion
......................................................
3.2 BRUSH PLATING
....................................................
$00
...............
3.3 ANODE PLACEMENT AND GEOMETRY
o
.................
.......
o
............
3.4 AUTOCATALYTIC (ELECTROLESS) DEPOSITION
........................
CHAPTER 4 HIGH SPEED ELECTRODEPOSITION PROCESSES
...........
4.1 THEORETICAL ASPECTS
..........................................................
4.1.1 Transport mechanismsand the diffusion layer
.
...............................
4.1.2 Realistic limiting current densities
.............................................
4.2 MEASUREMENT OF THE LIMITING CURRENT DENSITY
.............
4.2.1 Limiting current density measurementmethods
.
.............................
4.2.1.1 Galvanodynamicmethods
; .....................................
.
...........
4.2.1.2 Potentiodynamicmethods
.
................................................
4.2.1.3 Convective control methods
.
..............................................
4.3 PRODUCTION PROCESSES
........................................................

1
1
4
6
6
8
8
9
9
10
12
13
15
15
16
17
17
18
18
20
21
23
25
25
27
29
30
30
30
32
32
33
34
34
35
36

39
CHAPTER 5 ELECTROCRYSTALLISATION AND MORPHOLOGY
.......
5.1 SOME FUNDAMENTAL ASPECTSOF ELECTROCRYSTALLISATION
*... *0.........................
00*00
*.
0
...
.....
00*0
.....
9009*
*
0....
*00#0
0
.....
0
............
....
....
...
5.1.1 Electrocrystallisation at low current densities
.
...............................
5.1.2 Electrocrystallisation at high current densities
...............................
.
5.1.3 Mechanismsof surface irregularity amplification
...........................
.
5.1.4 Stability theories for roughnessdevelopment
.
.................................
5.1.5 Theories of needle, dendritic, densebranching morphology (DBM) and

fractal growth
. ..........................................................................
...
I
CHAPTER 6 HIGH SPEEDJET ELECTRODEPOSITION .......................
6.1 CHARACTERISTICS OF FLUID FLOW WITHIN JETS
....................
6.1.1 Flow within the freejet region
....................................................
6.1.2 Flow within the impingementregion
...........................................
6.1.3 Flow within the wall jet
..........................................................
.
6.2 MASS TRANSFER CHARACTERISTICS OF IMPINGING JETS
.........

lll

39
42
43
44
45

46
53
53
54
54
55
55

6.2.1 Mass transfer in submergedjets

. ................................................
6.2.2 Mass transfer in the non-submerged
jet
........................................

55
56

CHAPTER 7 EXPERIMENTAL STUDIES OF HIGH SPEED SELECTIVE

JET ELECTRODEPOSITION
63
...............................................................
7.1. EQUIPMENT USED IN THIS
STUDY
63
.
7.1.1. Computer controlled X-Y drive system..........................................
63
.......................................
7.1.1.1 The nozzle and substratemount
64
. .........................................
7.1.1.2 The pump system
65
.
..........................................................
7.1.1.3 The X-Y Table
65
...............................................................
7.1.1.4 Motion control system
66
. .....................................................
7.1.1.5 The plating current power
66
supply. .......................................
7.1.1.6 The computer and control program
67
......................................
7.1.2 Additional equipment
68
..............................................................
7.2 EQUIPMENT AND METHODS USED FOR DEPOSIT EVALUATION
68
.. 68
7.2.1 Deposit Morphology
...............................................................
7.2.2 Deposit thickness
69
7.2.3 Deposit structure ...................................................................
69
...................................................................
7.2.4 Deposit hardness
74
...................................................................
7.2.5 Chemical analysis
74
.
.................................................................
7.2.6 Types of substrateused
74
.
..........................................................
7.3 METHODS USED FOR THE PRODUCTION OF EVALUATION
SAMPLES
75
.....................................................................................
.
7.3.1 Pure gold deposits
75
.
.................................................................
7.3.1.1 Electrolyte composition
76
....................................................
7.3.1.2 Experimental method
76
.......................................................
7.3.2 Gold alloy deposits
77
.................................................................
7.3.2.1 Initial trials for electrolyte selection
78
. ....................................
7.3.2.2 Optimising the gold/nickel electrolyte
78
. ..................................
7.3.2.3 Experimental method
79
.
......................................................
7.4 MASS TRANSFER STUDIES
80
.
.......................................................
7.4.1 Principles of SCPV and SVPA
80
. .................................................
7.4.2 The working electrode/reference
81
electrodeassembly. .......................
7.4.3 The equipmentused
83
.
...............................................................
7.4.4 Experimental technique
83
. ..........................................................
CHAPTER 8 RESULTS
85
........................................
*.. *........................
8.1 PURE GOLD DEPOSITS
85
.
.............................................................
8.1.1 The effect of nozzle to substratedistance
85
.......................................
8.1.2 The effect of current density
86
.
....................................................
8.1.2.1 General observations
86
8.1.2.2 Deposit topography .......................................................
88
.
........................................................
8.1.2.3 Deposition rate
94
...............................................................
8.1.2.4 Cathodic current efficiency
94
................................................
8.1.2.5 Hardnessof deposits
95
........................................................
8.1.2.6 Selectivity of the deposit
96
...................................................
8.1.2.7 Crystal structure and residual
97
strain. ....................................
8.1.3 The effect of electrolyte velocity
101
................................................
8.1.4 Temperatureeffects
101
.
...............................................................
8.1.5 The influence of the gold concentration
101
. ......................................
8.1.6 The effect of pH
102
....................................................................
8.1.7 The role of electrolyte conductivity
102
.
............................................
8.1.8 The influence of nozzle size
103
8.1.8.1 Increasednozzle size . ......................................................
103
.
......................................................
8.1.8.2 Decreasednozzle size
103
.
.....................................................
8.1.9 Pure gold deposition using pulsed current
104
. ....................................
8.1.9.1 Variation of the averagecurrent density
106
. ...............................
8.1.9.2 Variation of the on-time
106
.
..................................................
8.1.9.3 The effect of increasing the duty cycle
106
. .................................

IV

8.1.9.4 The influence of pulsed deposition on selectivity

.
.....................
8.1.10 Examination of the limiting factors controlling maximum deposition
rates. .........................................................................................
8.1.10.1 Mass transfer studies
.....................................................
.
8.1.10.1.1 SampledVoltage Pulse Amperometry
.
.........................
8.1.10.1.2 SampledCurrent Pulse Voltametry
.
.............................
8.2 GOLD ALLOY DEPOSITS
.
..........................................................
8.2.1 The influence of deposition parametersfor the Ronovel N electrolyte
with no nickel. .............................................................................
8.2.2 The effect of the addition of nickel to the basic Ronovel N electrolyte.
..
8.2.2.1 Relationship betweennickel in the deposit, nickel in the electrolyte
and current density. ...................................................................
8.2.2.2 Deposit topography
.
.......................................................
8.2.2.3 Deposition rate
.
..............................................................
8.2.2.4 Current efficienc
8.2.2.5 Hardnessof the
8.2.2.6 Selectivity of the deposits
.
.................................................
8.2.2.7 Crystal structure
.
............................................................
8.2.3 Sampledcurrent pulse voltammetry of the Ronovel N electrolyte. ........
CHAPTER 9 THE APPLICATIONS OF HIGH SPEED SELECTIVE JET
ELECTRODEPOSITION .......................................................................
9.1 APPLICATIONS WITHIN THE ELECTRONICS INDUSTRY . ............
9.1.1 The direct writing of Microwave IntegratedCircuit Substrates(MICS).
'
*****'*.**...
5.*i'i*Ee"s*el*ecti*ve*pl*at'i*ng*of*reel"t'o*re*el"co*mpone*n*ts***.
9.1.3 Bump plating
.......................................................................
.
9.1.4 The direct writing of etch resist for printed circuit boards. .................
9.2 DEMONSTRATIONS OF THE USE OF HSSJE ..........................
9.2.1 Microwave circuit test samples- 50 ohm lines. ........................
9.2.2 The plating of connectorswith alloy gold
.
.....................................
9.2.3 Thermocompressionbonding properties of HSSJE pure gold . .............
9.2.4 The direct writing of printed circuit boards
. ..................................
CHAPTER 10 ANALYSIS AND DISCUSSION ....................................
#...
10.1 GENERAL ..............................................................................
10.2 MASS TRANSFER MEASUREMENTS ..........................................
10.3 THE INFLUENCE OF DEPOSITION CONDITIONS
.......................
10.3.1. Nozzle to substratedistance. ............. : .....................................
10.3.2. Current density ..................................................................
.
10.3.3. Electrolyte velocity . ...........................................................
:..
10.3.4. Temperature. ...................................................................
10.3.5. Electrolyte composition .........................................................
10.3.6. The influence of nozzle size ..................................................
.
10.3.7. The effects of pulsed current .................................................
.
10.4 SOME PHYSICAL AND STRUCTURAL PROPERTIES OF PURE
GOLD HSSJE DEPOSITS ..........................................
*0-0
..........
so*.
*-*...
10.5 SOME PHYSICAL AND STRUCTURAL PROPERTIES OF GOLD
ALLOY HSSJE DEPOSITS .....................................................
0.*o.... so.
10.6 FLUID FLOW AND ITS INTERACTION WITH THE DEPOSIT ........
10.6.1 Interaction of the flow below the maximum useful current density ......
10.6.2 Interaction of the flow above the maximum useful cuff ent density.
10.6.2.1 Nodular deposits. .....................................
10.6.2.2 Needle-ypedeposits
....
.................................
10.6.2.3 Field oriented jet core structures. .................................
10.7 THE GROWTH OF NODULAR DEPOSITS . ............................
10.7.1. Inhibition versus diffusion mechanisms ......................................
10.8. SUMMARY OF FACTORS CONTROLLING THE MAXIMUM DEPOSITION RATE . ...............................................................................

106
107
107
108
109
ill
112
113
113
115
116
117
117
120
122
131
132
132
132
133
134
134
135
135
136
137
137
139
139
140
146
146
146
149
149
150
151
153
153
155
157
158
161
161
161
163
164
165
167

REFERENCES
...........................................................................................
PHOTOGRAPHS 1-39
.................................................................................
TABLES 1-27
............................................................................................

VI

169
174
198

NOMENCLATURE

Amps

Lattice parameter,A

Constant as defined in equation(2 1)

Specific area, CM2 CM-3

a,.
C
&
CO
C
Cf

Concentration, mol crrr3

Concentration in the bulk electrolyte, mol cm-3
Concentrationat the electrodesurface, Mol Cm-3
Coulombs, A sec-1.
Local coeffficient of friction defined as
-C.
pU2X12

d
d'
D
Deff
Dvw
E

diameter of the nozzle, cm.

Radial distancefrom centre of impingementzone, cm
Diffusion coefficient, mol cm-2sec-I
The effective crystallite size uncorrected for faulting,
A
True crystallite size,

Electrical potential, volts

Faraday's constant, 96,480 C

Hydrodynamic constantsec-I

Distance of the nozzle from the substrate, cm.

Cuff ent density, A CM-2

io

Limiting current density, A Cm-2

Exchange current density, A Cm-2

JD

Diffusion flux,

k
KL

Local masstransfer coefficient, cm sec-I

Mass transfer coefficient, cm sec-I
Mass transfer coefficient at the limiting current density, cm.sec-I

Litres

I
M
n

Order of reflection, as in hkI

Molar
Number of electrons involved in an electrochemicalreaction.

nozzle radius, cm,

r
R

radius of cathode, cm,

Gas constant, 8.314 Joules K-1mol-I

Dimensionless distanceratio, d/r

Re

Reynolds number defined as Ud/v

Re,

Local Reynolds number defined as Ud'/v

Mol

CM-2sec-I

Vii

SC

Schmidt number defined as v/D

Sh

Sherwood number defined as KdID

Sh.
t

Local Sherwoodnumber defined as kd'ID

Time, seconds

to

Transport number

t.
T

Time to achievesteadystatecondition, seconds

Temperature, -Kelvin

Average fluid velocity at the nozzle exit, cm sec-I

Average local velocity over the impinged surface, cm sec-I
Cartesian coordinate

Cartesian coordinate

Cartesian coordinate

U.

Greekletters
Stackingfault probability,dimensionless
Twin fault probability,dimensionless
Symmetryfactor, oftentakenas0.5

a
P,
P
6

Diffusion layer thickness,cm

11
0

Overpotential,volts
Braggangle,degrees

1C
I-C

Specificconductivity
Kinematicviscosity,CM2sec-1
Viscosity, g cm-1sec

Density, g cm-1

Time to the steadystate during a transient current pulse, seconds

Local wall shear stress, N CM-2

Angular velocity, radianssec-I

Superscripts
b
e'
c

Power of Re as defined in equation (22)

Power of H/d
Power of Sc as defined in equation (22)

Note: In the graphs presentedin this Thesis, the terms A/cm sq and kg/mm sq

in
limitations
is
due
This
the graphplotting software.The sq in
to
are used.

these terms should be read as "squared" and represent, for example A

CM-2.

viii

CHAPTER 1

INTRODUCTION

1.1 GENERAL BACKGROUND

is a processwherebymetalsare electrodeposited
Selectiveelectrodeposition
in discreteareas
of a substrate,preciselywherethat metalis requiredfor functionalor decorativepurposes.It is
widely practisedin boththe electronicsandengineeringindustries.Therearemanyreasonswhy
to alterthesurfacepropertiesof thesubstrate
a metalis depositedselectively.It maybe necessary
metal in a particularareain order to conferwear resistance,hardness,electricalconductivity,
in
somecases,to providea local form of corrosionresistance.In
and
solderabilityor weldability
materialssuchasgold, a considerable
costsavingcanbe achieved
addition,with certainexpensive
by platingthe minimumquantityof metaljust whereit is needed.
Examplesof selectivelyplatedmetals in the engineeringindustry can be seenin the re-building
of worn componentssuchas drive shafts,bearing surfaces,crankshaftsand piston sleeves.As part
of a manufacturing process, bearings are usually plated with the bearing material on the wear
surface only. Chromium is often plated selectively onto piston sleevesto confer wear resistance.
The electronics industry makesgreat use of selectiveplating. The printed circuit board (PCB)
industry usesselectively plated metals to act as etch resists. Thesemetals are plated onto regions
where tracks etc are required so that when the rest of the copper clad board is etched away, the
tracks remain. Electrical connectorsare usually plated with a gold alloy to confer wear resistance
and low electrical resistance.In order to minimise costs, only the region where contact is made is
plated with the gold. Another example is where componentsthat cannot easily be soldered are
given a tin or tin alloy coating to confer solderability. To minimise the spread of solder, these
componentsare plated selectively.
Many techniquesare available to produce selectiveelectrodepositionand theseare detailed in
subsequentChapters.However, aswith any process,they havetheir advantagesand disadvantages.
Most require the use of some form of dielectric mask to provide the edge definition which can
lead to cost penalties. Those that do not use masking are generally of poor definition but tend to
be lower cost processescomparedwith masking systems.Therefore there is a trade-off. Recently,
in
developed
has
been
that
technique
offers
overcoming the limitations of existing
some
promise
a
processes.This method will be referred to as High SpeedSelectiveJet Electrodeposition.

High SpeedSelectiveJet Electrodeposition(HSSJE)is an electrodepositiontechniquewhereby

metals are electrodepositedin a selectivemanner without the needfor masking. The principle is
that a non-submersed,free standing electrolytejet impinges, at a high velocity, onto a substrate
and with the application of a suitable potential, deposition occurs within the impingement region
and to a minor extent, the immediately surrounding region. Due to the resistive nature of the
electrolyte and the properties of the hydrodynamic flow surrounding the impingementregion, the
spread of the deposit is limited. Figure 1. shows a schematicview of the electrolyte jet and its
interaction with the substrate.It is a combinedschematicbasedon the work of two authors.1.2.

ZONE I

Free

ZONE II
ZONE III

Impingement
Wall jet

jet

zone

-NOZZLE
JET

III
II

SUBSTRATE
HYDRAULIC JUMP
Figure

Figure 1. Schematicof the electrolyte jet interaction with a substrate

Region I is the free jet region where flow continues in a similar fashion to that within the tube
is
known
II
Region
the
as the stagnation region. Close to the point of impingement, the
nozzle.
of
flow changes speed and direction from that of the free jet to that of region III, which is known as
the wall jet (after Glauert3. ). Finally, there occurs what is known as the hydraulic jump where the
flow
description
jet
increases
Further
the
thickness
and
changes.
momentum
of the flow will
wall
be given in Chapter 6.

Most electrochen-dcalprocessesbenefit from agitation of the electrolyte. This is becausethe

reaction ratesof theseprocessesare often governedby the rate of masstransfer of the active species
from the bulk of the electrolyte to the surface. In the caseof electrodeposition, the active species

is the metal ion. The maximum current density obtainableis therefore controlled by the situation
where the concentrationof metal ions at the surfaceapproacheszero. In other words, as soon as
a metal ion reachesthe surface, it is discharged.This situation is known as the limiting current
density, 'L. The limiting current density is given by;

nFDcb

(1)

= b(1-t')

It can be seenthat the thicknessof the diffusion layer 6 has a strong influence on the limiting
layer
is,
Migration
higher
limiting
density.
The
this
the
the
thinner
under the
current.
current
is
by
its
influence
dependent
for
(1
The
is
field
t').
on the total
magnitude
of
accounted
electric
ie
If
is
indifferent
there
a supporting
carriers,
an
charge
excess
of
carriers.
number of charge
insignificant.
be
Electrolyte agitation reducesthe thickness of the
term
then
this
will
electrolyte,
diffusion layer, the strongerthe agitation, the thinner the layer andthe higher the maximum current
density will be. By using a high electrolyte jetting rate, the interfacial agitation will be high and
the diffusion layer thicknesswill be low. It is very difficult to measurethe thicknessof the diffusion
layer directly but it can be measuredindirectly by meansof either a masstransfer coefficient, KLq
defined as

Kj

(2)

nFc

Sh,
dimensionless
Sherwood
the
by
the
masstransfer coefficient;
number,
or

Sh - KcD

(3)

In the electrodeposition
of metals,the limiting current densitycannotusually be achieved
form
is
deterioration
This
deteriorating
before
deposit
takes
the
this
the
reached.
quality
without
been
deterioration
has
S.
It
that
this
dendritic,
reported4.5.6.7.
or
powdery
growth.
nodular
of
for
0.9
'/'L
between
0.4
manyof the commonplatingelectrolytes.
of
and
at a ratio of
commences
However,little is knownaboutthe effectsof very high electrolytevelocitieson the ratio of "'L or
the metallurgicalstructureof depositsproducedundertheseconditions.

1.2 SCOPE OF THIS STUDY

The purpose of this work was to examine the structural, morphological and metallurgical
characteristics of both gold and gold alloy deposits produced under varied conditions of high
electrolyte flow using small geometry (< Inim) nozzleswith a constantcurrent DC supply. By
relating factorssuchaselectrolytevelocity, currentdensity,temperatureandmetal ion concentration
for
deposits
limiting
the
the
to
the
of
of
conditions
produced,
an
understanding
etc
morphology
maximum deposition rates could be ascertained.Propertiesof depositsproduced by HSSJEwere
compared to those from deposits produced under more conventional conditions. As well as
factors
information
deposits,
the
to
the
on
attempts
were
made
gain
electrochemical
examining
controlling deposition.Thesefactors, suchasmasstransfer characteristics,required the production
identify
limiting
Whilst
densities
to
the
the
under
study.
of
system
current
curves
of polarisation
dilute
be
"ideal"
information
using
electrolytesusing conditions
or
obtained
ran
redox
couples
such
for
it
information
the systemsunder
to
this
was
necessary
agitation,
establish
of rapid electrolyte
study to be effective. Suchinformation is difficult to obtain for relatively concentratedand agitated
disc
For
defined
the
electrode.
rotating
measurement
such
as
well
systems
using
even
electrolytes
this reason, more conventional techniqueswere modified and used in an attempt to obtain this
information. In order to confirm the effectivenessof thesemodified methods,trials were additionally
carried out using a dilute copper sulphateelectrolyte.

After optimumdepositshadbeenproducedusingDC, furthertrials werecarriedout to observe

the effectivenessof pulsedcurrent in improvingthe depositionrate and/or the quality of such
deposits.
A number of different acid and neutral gold electrolytes were used in this study. Pure gold
depositswere produced from acid cyanide/citrate and cyanide/phosphateelectrolytes. In the case
for
briefly
their effectiveness
commercial
examined
the
several
electrolytes
were
alloys,
gold
of
for
further
jet
the
study.
most
promising
and
was
chosen
conditions
under
Once the conditions for maximum deposition rates had been established,sample components
in
for
The
trials
trials.
these
are
of
reported
separately
some
evaluation
results
were prepared
Chapter 9.

Becausethe techniqueof HSSJEencompasses

manydifferent disciplinesand aspectsof the
it
is
necessaryto review a wide rangeof subjectareasto provide a
process,
electrodeposition
6
Chapters
2
Therefore,
for
to
examinethevariousaspectsrelevant
the
work.
current
point
starting

to this process. Chapter 2 details gold electrodeposition,the electrolytes used and the electrochemistry of the process. Chapter 3 examinesthe current methodsof selectiveelectrodeposition.
Chapter 4 deals with the mass transport mechanismsas applicable to high speed deposition
processes.Chapter 5 looks at electrocrystallisationand morphology and how the structure of the
deposit is related to the deposition conditions. Chapter 6 revues the current knowledge of jet
deposition theory and examinesthe characteristicsof fluid flow within jets. Chapters 7 onward
describe the experimentalresearchwork carried out for this thesis.
A number of papershavealready beenpublishedon work connectedwith this Thesis and these
have been addedas an Addendum.

CHAPTER 2

GOLD ELECTRODEPOSITION

The unique properties of gold are highly desirable in many spheresof life. Its chemical and
aesthetic properties have meant that gold has acquired a special position in society. The most
famous of theseare a function of the surface- its colour as well as its resistanceto corrosion and
tarnishing. In many respects,thin layers depositedonto basemetalscan function in the sameway
as if the whole article was madeof gold. Applying gold onto basemetalshas its roots in antiquity,
with gold leaf being applied ornamentally as far back as Egyptian times. In the 18th and 19th
deposited
items
by the application of a gold/mercury amalgam,the
onto
gold
was
metal
centuries,
mercury subsequentlybeing evaporatedoff. However, it did not escapethe attention of those
involved that the life of a gilder was not a long one as mercury poisoning took its toll. The first
in
V.
1802
by
Luigi
Brugnatelli,9.a colleagueof Allisandro
the
of
gold
was
of
electroplating
record
Volta. His work was not widely publicisedthough. Volta was invited with Brugnatelli to the French
Academyof Sciencesto discusstheir work. Unfortunately, whenVolta introducedhim to Napoleon,
the Academy President, as "the great Italian chemist, Brugnatelli", Napoleon insulted him by
Pavia
Italian
With
Brugnatelli
"there
10.
to
this,
chemists".
andpublished
returned
great
are
no
saying
his work there, which was not widely seen.It was not until 1840that Henry and George Richard
Elkington patented"- the forerunner of the modem gold electroplating solution, based on gold
potassiumcyanide. From 1845the processwas commercially available and was popular up to the
d'art
In
Russia
During
Victorian
this
time,
the
were
gold
plated.
grand
objets
period.
many
of
end
bases
large
For
the
a
very
out
on
and capitals of the
scale.
example,
carried
was
gold plating
interior columns of St Isaac's cathedral in St Petersburgwere gold plated, using 280 kg of gold.
However, becauseof a poor understandingof the chemistry of the process, successdependingon
"black book" recipes known only to a few, it fell into disrepute. Thereafter, gold plating was
largely relegated to the production of inexpensivenovelties or trinkets until its re-emergenceas
in
industry
1940's.
the
the
early
electronics
of
part

2.1 GOLD PLATING IN THE ELECTRONICS INDUSTRY

With the advent of the electronics industry, a specialinterest in the technology emerged. Gold
becamepopularbecauseof its inert nature, its high electrical conductivityand low contactresistance.
The modem electronics industry is one of the largest users of gold plating. In 1990 in Europe
deposited
kg
13,482
been
it
has
that
of
gold
was
out of a total electronics usage
estimated'2alone,

of 18,097 kg. For the sameyear, the world electronics consumptionof gold was 142,800 kg. 13.
This would indicate that approximately 110,000kg was electroplatedwith a value of just over $1.3
billion.
Within the electronics industry, the two major scale applications of gold are for electrical
connectors and printed circuit boards. It is estimatedthat in 1990,6,869 kg was plated onto
kg
deposited
2,440
was
onto printed circuit boards in Europe. The satisfactory
connectorswhilst
performanceof a connectoris crucial to the overall performanceof anypieceof electrical equipment.
It has to have a low contactresistance,as well as good corrosion and wear resistance.This latter
property is necessarybecauseconnectorsare frequently mated and un-matedduring the courseof
the equipment lifetime. Many specificationsrequire a connectorto remain functional through up
to 500 insertion/withdrawal cycles. In order to achieve this wear resistance, small quantities
(approximately 0.1 - 1.0 % by weight) of a transition group metal, such as nickel or cobalt, are
increases
This
the hardnessfrom about 80 Hv (Vickers Pyramidal
the
gold.
co-depositedwith
Hardness)for pure gold up to about 150 Hv with very little increasein the contact resistance.
Printed circuit boards (PCB's) are plated with gold in order to suppresscorrosion of the
improve
to
solderability. Many boardsstill usegold plated edgeconnectors.
underlying copperand
Theseare areasat one end of the board that act as connectingpadsthat can be mated with external
connectors. They are plated with the gold alloy to confer wear resistance.With the advent of
for
has
been
the
to
the production
use
systems,
gold
preferred
metal
communications
microwave
for
boards
high
frequency
needed
applications.The glassreinforced plastic
the
circuit
specialised
of
that is used for conventionalPCB's hasbeen replacedby either sintered alumina, quartz or PTFE
based materials for these applications. These are metallised using sputtering techniquesand the
tracks are built up using a combinationof photolithography and electroplatedgold. The remaining
metallisation is then removed.

Gold plating is particularlyimportantin spaceapplications.The uniquepropertiesof gold,

infra
in
it
its
high
tarnish
terrestrial
red
reflectivity
and
atmospheres,
resistance
make
especially
invaluablefor thermalradiationcontrol. In addition,gold resistssublimationin the high vacuum
lead
in
This
to
can
short
circuits
phenomenon
electronicequipmentif other "electronic
space.
of
due
to vaporisationandcondensation
of the metal.
are
used,
metals"
Beside these applications, gold is plated onto semiconductorlead frames for the purposes of
bonding gold wire interconnectsfrom the chip to the frame. Becausegold is ductile, soft and when
be
joined
by
forms
bonding.
thermo-compression
components
can
cold
welds,
easily
readily
pure,
Die attachmentis facilitated by the use of gold plating, again due to its tarnish resistance. There

are numerousminor electronicsapplicationsof gold plating that cannotbe mentionedhere which

together ensure that electronics is the secondlargest fabrication consumer of gold next to the
jewellery trade.

2.2 ELECTROLYTE TYPES.

Gold, being a noble metal, requiresonly a very small overpotentialfor reduction from the ionic
to the metallic state. Therefore, in electrolytes containing free metal ions, immersion deposits
readily form. In addition, electrodepositsfrom such an electrolyte are coarsegrained and tend to
form nodules and dendrites. It is therefore essentialthat the gold ions are complexed in order to
2
for
There
this
are
only
suitable
of
general commercial use. The
complexes
gold
effect.
reduce
in
form
is
the
of potassiumgold cyanide, KAu(CN)2, In the caseof the
produced
complex
cyanide
in
is
the form of sodium gold sulphite, NaAu(S03). However, the
the
gold
sulphite complex,
cyanide complex may be used in a number of different electrolytes over a wide pH range.
2.2.1 Alkaline cyanide electrolytes.
Alkaline cyanide electrolytes use the gold potassiumcyanide together with excesspotassium
cyanide at a pH in excessof 12. A typical formulation is shown below;
Au as KAu(CN)2
Potassiumcyanide

4-12 g 1-'

Potassiumorthophosphate
Potassiumcarbonate

30 g 1-'

pH
Temperature

> 12
50 - 65 oC

Current density

1 -8 mA cm-2

30 g 1-'
30 g 1-1

The free cyanide is usually maintained at above 15 g 1-1.Due to their alkaline nature, these
in
been
have
the electronics industry particularly in the gold plating of
used
rarely
electrolytes
PCB's. As a result of the increasedrequirement for such applications during the 1950's, acid to
developed.
based
gold
on
potassium
cyanide
were
electrolytes
neutral

2.2.2 Acid gold electrolytes

2.2.2.1 Pure acid golds

In 1959, Ehrhardt14.found that potassiumdicyanauratewas stablein acid media down to a pH
formulations
Subsequently,
3.0.
a
number
of
were developedbasedon a carboxylic acid/carof
boxylic salt mixtures with potassiumdicyanaurate.The first electrolytesemployedcitric acid and
sodium citrate and operatedat a pH between3.0 and 5.0. The citrate mixture was presentto buffer
the electrolyte. In addition, citrate was found to be capableof complexing transition metals such
as nickel, cobalt and iron. This allowed the electrolyte to be used for both pure gold deposits as
Because
deposits.
of this ability, it is important that when depositingpure gold from
alloy
well as
such an electrolyte that stronger complexing agents be addedso that codepositionwith impurity
transition metals is avoided. Ammonium citrates are used in modem formulations of this type of
electrolyte thus eliminating the possibility of contaminatingelectronic deviceswith sodium, which
device
be
deleterious
to
the
performance.
could

A typical pureacid gold is shownbelow;

8.0 g 1-'

Au as KAu(CN)2
Citric acid
Ammonium citrate

40 g 1-'
40 g 1-'

EDTA

1-2g1-'

pH
Temperature

3.0-6.0
25-30oC

Current density

5- 10 mA cm-2

With the developmentof transistorsand integratedcircuits the needfor gold plating the device
for
barrel
The
the
electrolytes
were
suitable
acid
not
very
plating applications that
grew.
packages
these devices required and thus neutral electrolytes were developed. The acid electrolytes were
subject to metallic contamination and were able to co-deposit the contaminants. Nobel and
Thomson". demonstratedthe superiority of neutral electrolytes in a study of the barrel plating of
transistor headers. Subsequently,numerousproprietary formulations were developed, based on
mixtures of phosphatesand citrates, phosphateonly and pyrophosphates.To reducethe danger of
derivatives
Many
acid
such
organic
phosphonic
were
used.
agents
as
complexing
co-deposition,
of theseelectrolytesusedvarious addition agentssuchasorganic thio compoundsaswell astrivalent

arsenic to act as grain refiners and brighteners. Due to the wide variety of formulations for neutral
electrolytes, there is no "typical" formulation and the reader is referred to the literature for ftirther
information. 16-17.18.

In the early 1970's, it was discoveredthat the additive free acid and neutral baths worked quite
well when freshly made up but on use and with ageing, the deposit quality deteriorated, giving
rise to brownish deposits. Reinheimer'9-was one of the first to discover that the reasonfor this
was that freshly made electrolytes often containedsmall quantities of lead as a contaminant. As
the bath was used, so the lead was removed by co-deposition. It was only when more lead was
addedthat the quality of the depositwas returned. The addition of lead at a level of about 0.5 ppm
was patentedby him. At about the same time, it was found that thalliurn and arsenic were also
carried out a study on the depolarising effect of heavy
effective brighteners. McIntyre and Peck2Ometal ions including arsenic, lead, thallium bismuth and mercury. They demonstratedthat lead
and thallium depolarisedthe gold electrode. The proposedmechanismwas of adsorption of the
trace metal followed by an electrochemicaldisplacementreaction betweenthe adsorbedmetal and
Au(CN), This displacementwasthoughtto modify the crystallisationof gold allowing well formed
-.
fine crystals with a strong preferred orientation. This resulted in a bright appearance.However,
they discovered no depolarisationeffects with arsenic. Eisenman2l.examinedthe kinetics of the
reduction of dicyanaurateboth with and without lead. He explainedthat the effect of lead was to
lower the activation energy of the electrontransfer which gaverise to the acceleratedestablishment
of a preferred orientation. Rao andWeil22-and more recently Dinan and Cheh:73-studiedthe effects
Rao
to
electrolytes.
gold
and Weil thought that arsenicadsorbedonto the gold
additions
of arsenic
and acted as nucleation sitesbut at the sametime inhibited the lateral growth of the gold crystals.
As a consequence,the grain size was considerably reduced and this was responsible for the
brightening effect. Dinan and Cheh examinedthe effect of arsenicon the hardnessof gold. They
led
to an increase of hardness and that this was due to the
that
additions
arsenic
concluded
incorporation of the trace metal in the deposit.
One disadvantageof using these trace metals as brightening agents has been due to their
incorporation into the deposit and their subsequentinfluence on the performance of the gold. It
both
been
the thermocompressionand ultrasonic bondability was reduced in
that
shown24-25was
the presence of such incorporated additives, particularly when the gold was deposited at high
current densities. These workers concluded that low additive concentrations and low current
densities should be used for such applications.
2.2.2.2 Alloy acid golds

independently
discoveredtheacidstability
At thesametimeasEhrhardt'sdisclosure,Rinker26introducing
He
found
by
dicyanaurate.
that
also
suitablycomplexedbasemetals,the
of potassium

10

depositsproducedwere much hardeF.With as little as0.1 % basemetal incorporation, the hardness

of the gold deposit could be doubled. As well as increasingthe hardness,the wear resistanceof
the deposit was drastically improved. Complexing agentssuch as EDTA (ethylenediaminetetraacetic acid (disodium.salt) and NTA (Nitro triacetic acid) were necessaryto facilitate the slow
releaseof the metal for codeposition.Without someform of additional complexing, the basemetals
are in fact more noble than the complexedgold ions and will depositpreferentially. Thus an alloy
would be depositedwith a high basemetal content for very low concentrationsof basemetal in
the electrolyte. Modem formulations make use of a wider range of carboxylic acid buffers and
often, phosphatesor phosphonatesare used.
A typical acid hard gold formulation is describedbelow that usesnickel asthe alloying element.
The tetraethylenepentamineis used to complex the nickel in this case.

Au as KAu(CN)Z
Citric acid

4.0 g 1-'
120 g 1-'

Tetraethylenepentamine
Nickel (as nickel citrate)

20 g 1-'
2.5 g 1-'

pH
Temperature

4.0

Current density

20 mA cm-2

40 C

The most widely usedand studiedhard gold is one that usescobalt as an additive. In this case,
the bath formulations are similar to the abovebut the cobalt is addedasthe EDTA complex. There
have beenmany studiescarried out on the mechanismof hardeningand wear resistanceproperties
of this electrolyte. The addition of cobalt has been shown to increasethe hardnessfrom a value
200
kg
hardness
increase
It
150
kg
brought
80
100
to
thought
that
the
mm-2.
was
was
nun-1
of
in
Lo
by
the
reduction
grain
size.
et aP7. concluded that the hardnesswas a
a
significant
about
in
from
2
down
the
to 20 -30 nm. Eisenmann,21.in his
the
grain
size
about
of
reduction
itm
result
study of the kinetics of the reduction of gold concluded that the cobalt increasedthe activation
energy of the electron transfer reaction and gave rise to a high nucleation rate leading to a small
crystallite size. However, a high hardnessalone doesnot accountfor the good wear resistanceof
the cobalt and nickel hardened golds. Koch et aln. developed an additive free hard gold that
deposits.
itwas
However,
to
these
shownthatthe slidingwear resistance
similarhardness
exhibiteda
of the additive free depositswas not as good as thosecontaining cobalt in the absenceof a suitable
lubricant. Munier29-found an organic material co-depositedwith the cobalt gold and described it
as a "polymer". It was thought for sometime that this was responsiblefor both the increasedwear
increased
deposits
the
these
contactresistanceassociatedwith them.
as
well
as
slightly
of
resistance

11

However, there were many studies carried out subsequently and in one of them, 30.it was concluded
that the "polymer" discovered by Munier was in fact cobalt II hexacyanocobaltate III,
C03[Co(CN)J2. xH20. By using extraction with mercury instead of aqua regia as Munier had, it
was found that potassium cobalticyanide, K3Co(CN)6 was co-deposited. Of this, only 25 % of the
cobalt was in this state, the rest being in the form of metallic cobalt. In addition, only 21 % of the
carbon and 41 % of the potassium could be attributed to the K3CO(CN)6. The rest was later found
to be from incorporated AuCN. Later studies by Antler3l. showed that in addition to high hardness,
good wear resistance required a low ductility. Another study by DeDoncker et aP2. showed that
good wear resistance could only be obtained if the deposit contained at least 0.08 wt% of the cobalt
complex together with between 0.06 - 0.2 wt% of metallic cobalt. If the complexed cobalt was
below this value, then the wear resistance was poor. High levels of cobalt in the electrolyte tended
to suppress the co-deposition of the complex leading to high metallic cobalt contents. This resulted
in abrasive wear characteristics.

The useof cobalt asan additive hasa major disadvantagewhenusedfor high speeddeposition.33.
The CoII is readily oxidised to the inert CoHI complex, Co(CN)63-at the anode. However, nickel
does not suffer from this problem.
There are many reviews of gold electrodeposition technology in the literature and further
information can be obtained from them. 10.33.34.

2.2.3 Structural characteristics of gold deposits.

The structure of any metal deposit is highly dependent on the deposition conditions, the electrolyte formulation, the temperature and the substrate. The substrate exercises its influence during
the early stages of deposition and ceases to exert a significant influence once the thickness of the
deposit has exceeded about 5 lim. A number of studies have been carried out on the initial stages
of deposition of gold. 35.36.It was found in these studies that the greatest influence on deposit
structure was due to the lattice mismatch between the gold and the substrate. The current density
influence
little
have
found
to
on the initial stages of deposition. However, additives in the
was
electrolyte were found to significantly influence the structure and the coverage. Lin et aP7. examined
the crystal structure, using Transmission Electron Microscopy (TEM), of thicker deposits from a
citrate electrolyte both with and without additives over a current density range of 4 to 12 mA CM-2.
They found that the deposits grew mainly as the (I 11) planes, this trend being greater at lower
temperatures and higher current densities. The next major plane was the (311), the growth of
increasing
by
the current density. Certain surfactant additives were found
suppressed
which was
to suppress the growth of the (I 11) planes allowing the emergence of a (220) and (311) structure.

12

The changesin the preferred orientation were reflected in the changeof morphology. The deposits
with a preferred (111) orientation exhibited a plate-like structure whilst those with the (220) and
(311) orientations showedwhat was describedas a "shell-like" morphology.
Wakabayashi25
reported that the presenceof lead or thallium favoured the growth of the (311)
planeswhilst the addition of arsenicleadsto a (111) preferred orientation. They also reportedthat
in the absenceof additives, the (111) plane was predominant.
DeBonteet a138.describedthe influence of current density on the structure of both the additive
free hard gold and a cobalt hardenedgold. In the caseof the additive free hard gold, low current
densities favoured a mixed (200) and (311) texture, the deposits having what they term as a
polyhedrical morphology. With increasingcurrent density, a (I 11) texture becamepredominant,
associatedwith a fine grained structure. With increasing current density, the deposits adopteda
mixed (200) and (211) texture which showedas a lenticular or plate-like morphology. Before the
onset of burning, a slightly nodular structure was observedthat exhibited a (200) texture. In the
caseof the cobalt hardenedgold, the structure at low current densitieswas a mixed (220) and (311)
texture. With increasing current density, this becamea (I 11) preferred orientation.
Antler39- reported a (311) major preferred orientation for a pure acid gold using XRD. In
addition, he reporteda (111) preferred orientation for a nickel hardenedalloy gold. The electrolyte
nickel content was 0.15 %. However, for cobalt hardenedgold, he reportedan un-oriented deposit.

2.2.4 The influence of pulsed current on gold electrodeposition.

It has long been known that the use of either pulsed current or pulsed voltage can influence
deposit characteristics. Reducedporosity, smaller grain size, improved distribution and higher
deposition rateshave all beenclaimed asbenefitsto the useof pulseddeposition. The use of pulsed
current on pure gold electrolytes was first studied by Cheh.40- He found that although the
instantaneousapplied current, ip, could be considerably higher than under DC conditions, the
overall plating rate was generally lower. He concludedthat the main advantageto the use of pulsed
current was not in increasingthe deposition rate but the ability to increasethe rate of nucleation,
leading to a finer grain structure and a reducedporosity. Rehrig4l. confirmed this by finding that
at high peak current densities and duty cycles less than 50%, the grain diameter was inversely
proportional to the peak current and the duration of the pulse. This effect has been observed in
other investigations.42.

13

It hasbeenpointed out42.that using very high peakcurrent densitiescan leadto grain refinement
and thus greater deposition rates than under DC conditions. However the rate can never exceed
the DC limiting current density. Therefore, whilst peak current densities can approachthe peak
limiting current densities with no degradationof deposit quality, the average limiting current
density cannot be surpassedwithout deposit deterioration. This meansthat for such high peak
current densities,there has to be an appropriateoff-time to allow recovery of the metal ions in the
diffusion layer so that the averagelimiting current density is not exceeded. One advantageof
using high peak current densitiesis that a thin, pulsating diffusion layer is produced adjacentto
the substrate.If this layer is small comparedto surface irregularities, then both the peaks and the
troughs of the irregularity are equally accessibleto diffusion. Sucha situation reducesthe tendency
of peaksto be magnified by excessivegrowth as would be the caseunder DC conditions where a
thicker diffusion layer inevitably forms. This will be discussedfurther in Chapter 5. As a consequence,by using very short, high peak current pulses, such a tertiary distribution is achievedand
the micro-distribution of the deposit is improved. Such an improvement in the microthrowing
power has beenshown by Andricacoset a143.using a citrate gold electrolyte. They depositedgold
onto a rotating disc electrodewith a small groove on it. They found that the microthrowing power
was significantly better using pulsed current of short duration than under DC conditions. The most
important criteria for such a current regime to be successfulis that the peak current density must
be such that deposition occurs under diffusion control. Another important condition for adequate
tertiary current distribution is that the mass transport rate should not vary across the electrode
surface. Such a condition is rarely achievedunder DC conditions but can easily be achievedwith
pulse plating.
One disadvantageof relying on tertiary current distribution to smooth deposits lies in their
susceptibility to hydrodynamic effects. If the pulsating difftision layer is disturbed by turbulent
flow conditions, the microthrowing power may be affected due to an uneven accessibility to
diffusion occurring.
As was mentioned previously, the use of very high peak current densities does require long
that the off-time can significantly influence the quality
off-times. It has been shown by PUippe42.
of the deposit. Working at average current densitieswell below the limiting current density, he
found that increasingthe off-time during pulsedgold depositionfrom a citrate bath led to an increase
in the grain size. He used a peak pulse current density of 100 mA Cm-2.With an off-time of 9
deposit
Increasing
ledtoanincreasein
the off time to 99 mswas
obtained.
smooth
a
IM,
surface texturing. He claimed that this was due to grain growth during the off-time.

14

CHAPTER 3

SELECTIVE PLATING TECHNIQUES

Selectiveelectrodepositionhasbeenpractisedsincethe early daysof electroplating in one form

or another. There are numerousways of depositingmetalsjust where they are required. The main
from
is
the
to
either
electrolyte
coming into contactwith areaswhere the plating
prevent
objective
is not required or to direct the electric field in sucha way that plating only occurs within the field.
Turner44-divided thesetechniquesinto 5 main categories.

1. Dielectric masking
2. Brush plating
3. Jet or gelled electrolyte plating
4. Anode placementand geometry
5. Electrolessplating

Each of these categorieswill be discussedin greater depth, with the emphasison currently
used methods. Jet plating will be covered in Chapter 6 and will not be discussedhere. Gelled
electrolyte plating consists of placing a gelled electrolyte onto the surface to be plated where
deposition is required. It is a rarely used techniqueand will not be discussedfurther.

3.1 DIELECTRIC MASKING

Dielectric masking encompassesa great range of different techniques. The principle is that
(a
dielectric)
is
in
intimate
material
contactwith the substrateleaving
placed
non-conducting
some
After
to
the
exposed
those
plating
electrolyte.
plating, the dielectric is removed
areas
requiring
only
leaving the component selectively plated. There are three main sub-categoriesof this method,
solvent based organic polymers, pre-formed masks and controlled depth immersion. This latter
fact
that the air abovethe level of the plating electrolyte makes a good
the
of
use
category makes
dielectric.

15

3.1.1 Solvent based lacquers

Prior to the developmentof solvent basedsystems,masking was generally carried out with
waxes, especially bees wax. This was melted and applied whilst molten by meansof dipping or
brushing. However, it wasnot really suitablefor high definition dueto its rapidly changingviscosity
as it cooled leadingto poor flow during brushing. With more demandingneeds,the industry turned
its attention to solvent basedsystems.
This categoryprobablyhasthemost widespreadusefor generalselectiveplating. Many different
systemshave beenuseddependingon the application. For generaluse on items of complex shape,
lacquers are widely used. Theseconsist of a resin type material, or a cellulose, either natural or
in
dissolved
that
a solvent, usually a ketone, that can be applied either by dipping,
are
synthesized
spraying or brushing. The type of resin or polymer usedis very dependenton the plating conditions
and very often, lacquersare tailored for highly alkaline or highly acidic plating electrolytes.
The geometry of the item dictatesthe method of application. Whilst dipping and spraying are
highly effective at covering large areas, delineating the area to be exposedcan be difficult. The
use of maskingtapesof various kinds which are removedafter coatingwith the lacquer often leaves
a weakenededgeand the electrolyte can often creepunder the lacquer allowing deposition or even
corrosion to occur there. Painting by hand is often the only way to ensure a good edge but this
doesrely on operator skill and the definition is often poor. Despite thesedifficulties, this method,
in combination with masking tape that remains on the item defining the edges, is still the most
commonmethodusedin the plating industry for complexgeometry items. Adhesion of the lacquers
may be enhancedby a low temperatureheat treatmentbut this is probably due to shrinkageof the
film as the remains of the solvent are removed. However, despite the use of plasticisers in the
formulations, these coatings tend to be brittle and can easily fracture or become detachedif any
stressesare introduced into the componenteg. thermal cycling, flexing when jigging etc.
Another type of solvent basedmaterial that has found increasingpopularity is that basedon a
soluble rubber or latex. This material, which uses toluene or xylene as the solvent has certain
advantagesover the former products. After the solvent hasdried, the coating retains a high degree
of flexibility. This gives it a greater resistanceto the thermal cycling that occurs during transfer
from hot solutions to cold rinses. Being flexible, thin section componentscan readily be handled
film.
This type of masking is frequently used for electrolessnickel as
the
the
of
application
after
high temperaturesare used in this process. The disadvantagewith this method is that the film is
in
it
dissolve
that
to
the
to
solvents
are
used
remove
after plating.
slow

16

3.1.2 Thick film inks

In the early days of printed circuit production, screenprinted inks were used to define the
tracks prior to etching. Originally, theseinks were similar to the lacquersmentionedpreviously,
being basedon cellulose. The methodof application, screenprinting, allowed thick films of a high
definition to be produced. As these films dried rapidly by solvent evaporation, the definition
obtained was fairly good. However, the flammability and toxic nature of the solvents led to the
developmentof resin basedinks that were able to be force dried and baked to give a very tough,
acid resistantfilm. They were removedusing chlorinatedsolventsor in somecases,aqueouscaustic
solutions. However, the early typeswere not suitablefor plating dueto leachingof organic material
into the plating electrolyte. Also, they were limited to acidic solutions. Modem formulations have
generally overcometheseproblems and are often used in the PCB industry.45.In particular, high
viscosity, UV cured inks based on acrylic or vinyl are commonplacefor many commercial
applications.
The screenprinting method of application is a stencil printing technique which usesa circuit
fabric
fabric.
The
defined
the
woven
mesh
of
a
screen
can be madefrom silk, polyester,
on
pattern
ink
is
forced
The
through open areasof the screenmesh not protected by
steel.
nylon or stainless
the stencil, onto the copper clad board by a squeegeewiped acrossthe surface of the screen. The
its
low
because
is
relatively
cost and reasonablygood definition. However, it
of
popular
process
has a lower limit of line spacingof about 0.3 mm.
Thick film inks may also be usedfor generalmaskingof items to be selectively plated although
they are expensivecomparedto air curing lacquers.

3.1.3 Photo-resists
Photoresistsare organic materials that can be applied to surfacesby a variety of methods to
form a chemically resistant,polymeric layer. They haveunique properties in that after application,
the chemical resistanceof the layers may be modified by ultra-violet light. By the use of light
blocking masks, the chemical activity of the areasexposedto the UN. radiation can be altered.
Photoresistsmay be classified into two main groups, namely positive and negative working. The
forms
hard
layer.
When this is exposed
when
applied,
a
chemically
resistant
resist,
working
positive
to UV light, the polymer becomessoluble in the chemicalsused for developing solutions. In the
UV
light,
forming
to
occurs
when
exposed
polymerisation
resists,
a more
of
negative
case
in
layer.
Photoresists
PCB
industries
the
are
and
used
mainly
microelectronics
resistant
chemically
boards
flat
the
and silicon wafers respectivelyare suited to the application
of
circuit
the
geometry
as
methods.

17

Photoresistsmay be further classified into two sub-divisionsbasedon the methodsof application. Liquid photoresists,as the namesuggests,are suppliedwith the photo-polymer dissolved
in an organic solvent. They are applied to the substratesby meansof spraying, dipping, roller
coating or spinning. After application, they are cured in an oven to remove the solvent and harden
the film. The dried film thicknesshas to be low (2.5 to 8.0 Jim) for adequatepenetration of the
UV light. Negative working liquid resistsare usually developedin chlorinated solvents. The main
disadvantagesof thesetypes of resist include their sensitivity to pin-holes in the mask that is used.
This can lead to spots of resist remaining on areasrequiring plating leading to broken tracks. In
addition, theseresiststend to plug the through holes in the board and are difficult to develop and
is
Controlling
the
thickness
resist
anotherproblem with the liquid resists.Positive working
remove.
liquid resists overcome the difficulties mentioned above with the exception of the control of the
film thickness.
The secondsub-division is the dry-film resist. Dry film resistsconsistof a thick (17 to 75 jim)
photo-polymer layer sandwichedbetweenMylar andpolyolefin films. Thesefilms allow the resists
to be wound into rolls in lengthsof up to 300 metreswithout the photo-polymer sticking to itself.
It is applied to the copper clad board by a hot roller process,the polyolefin film being removed
The
Mylar
film remainsin contactwith the resistup to the developing
to
rolling.
prior
automatically
from
damage.
developed
in
These
be
the
photo-polymer
resists
can
a number of
preventing
stage,
for
designed
Some
solvent stripping whilst others use aqueousor mixtures of aqueous
are
ways.
and solvent developers.The advantagesof the dry film resist include its relative easeof processing
liquid
from
"mushrooming"
being
they
than
the
the
thicker
resists,
prevent
subsequent
plating
and
over the resist layer.

3.1.3.1 Photoresist chemistry

The chemistry of photoresists is a vast subject with a great number of formulations and
is
beyond
It
detail
detailed
A
the
thesis
to
these
this
scope
systems.
of
operation.
of
mechanisms
description of photoresistchemistry is given in the work by Allen46.and the reader is referred to
this. However, sometypical photoresistchemistry will be describedto convey the generalchemical
principles at work.
3.1.3.1.1 Positive working resists
The photochemical reactions involved in the case of positive resists are such that the UV
radiation producesa cleavageof the polymer so that the molecular weight (MW) of the polymer
film is significantly reduced, in somecasesdown to the original monomer. Becauselow molecular
higher
MW
than
the
a
greater
solubility
polymer, exposedregions may
possess
substances
weight

18

be removedwith a suitable solvent or developer.Typical of the more modem liquid positive resist
systemsare basedon the photochemistry of diazonaphthoquinonesulphonateesters (NDS) in a
cresol-formaldehydecondensationpolymer binder (novolac). With exposureto near UV radiation
(360-440 rim), the NDS forms a keteneintermediatewhich reactswith residual water in the film
to form an indene carboxylic acid with the elimination of nitrogen. However, in the absenceof
water in the film, the ketenereactswith the phenolic -OH groups on the novolac to form pendant
ester linkages. As the resist is formulated with sufficient water in the film, the former reaction is
the most prevalent.
11

11
S_
Ht0
R

R'OH

i`

13

11

+N,

R=

solubd sing alkyl

R' = novolac

or

aryl

group

resin

Figure 2. The chemical reactionsinvolved in the exposureto UV radiation on the NDS/Novolac

photoresist system
Figure 2 shows the reaction mechanismsinvolved. In the initial applied state, the NDS acts as a
dissolution inhibitor for the novolac binder due to its hydrophobic nature. The indene carboxylic
is
hydrophillic
dissolution
by
formed
therefore
the
reaction
and
acts
as
a
photolysis
accelerator
acid
for the polymer film and thus allows the removal of exposedareas. After development, the resist
image is normally baked at a temperatureof 130 -C to "harden" it. At this temperature, the NDS
decomposesto the ketene.As the polymer dehydrates,the ketenereactsprimarily with the phenolic
it
inducing
the
of
polymer,
making
more chemically resistant to subsequent
crosslinking
groups
processing.

19

3.1.3.1.2 Negative working resists

Negativeworking resistsarebaseduponthe fact thatthe dissolutionratefor a polymer decreases
as the molecular weight increases.Ultimately, a fully cross linked polymer is insoluble in any
solvent. As a consequence,cross-linking high molecular weight linear polymers reducethe susceptibility to dissolution. Alternatively, suitablemonomersmay be polymerisedto createa cross
linked network. There are three basic methods used to create insoluble resist structures.
Photodimerization, photocrosslinking and photoinitiated polymerisation (free radical) are the
mechanismsusedto produceresistantpolymeric layers.
Photodimerizationis a processby which two linearpolymer chainsmaybe crosslinked together.
The simplest resist using this mechanismis polyvinyl cinnamate,made by the esterification of
polyvinyl alcoholwith cinnamoylchloride. Upon irradiation, the cinnamategroupsfrom two chains
can dimerize to form a truxillate as in Figure 3.

__b
_o

bi
C=O

CH

CH

/
CH
\CH/

CH\
CH

Q
Q

---------------------"
Polyv. nyl cinnaMate

Cross

chains

(inked

duner

Figure 3. The chemical reactionsinvolved in the photodimerisationof polyvinyl cinnamate.

A typical example of photocrosslinkingcan be seenin resistscomposedof cyclizised polyisoprene(CPI). Crosslinking is achievedby incorporating a bis(azide)photoactivecompoundin
the resist. Irradiation of an azidecreatesthe highly reactivenitrene which can react with the CPI.
As a bi-functional azide is used, two polymer chainscan be linked leading ultimately to a cross
linked network. Figure4 showsthe typesof reactionsthatcanoccur inthe crosslinkingmechanism.

20

\
R-N, -+
azide

N-H
I
-C-

R-N,
nitrene
Insertion

R-N,

R
jH

C=C/

-c-

Addition

Abstraction

R-R-H+

C=c

c-

/\
Figure 4. The chen-Lical
reactionsinvolved in the photo-crosslinkingof cyclisized polyisoprene
using a bis(azide)photoactivecompound.
Photoinitiatedpolymerisationworks by the inclusionof a photoactivecompoundin a monomer
base. Irradiation of the photoactive compound creates free radicals that can polymerise the
monomer. A typical exampleof this is the polymerisationof vinyl monomersusing alkyl ethers
of benzoin. The radiation cleavesthe C-C a bond of the benzoinether creating the free radicals
that lead to the polymerisationof the monomer.

3.1.3.2 Outline of Printed Circuit Board Production Methods

Detailed information on the production of PCB's is available in the literature but the most
in
found
by
be
Coombes.
However,
46.
the
treatise
edited
can
work
a brief outline
comprehensive
of the current production methodsis given here.
PCB production can be categorisedinto two processes,the subtractiveand the additive. The
subtractivemethod makesuse of a positive resist image to protect the underlying copper whilst
the unprotectedcopper is etchedaway. The resist imagecan be producedby either a positive or
former
The
makesuseof a positive mask (black circuit lines) whilst
system.
negativephotoresist
the latter requiresa negativephoto-mask(clear circuit lines). Whilst this is not a selectiveplating
process,it constitutesa large proportion of commercialquality circuit boardsproduced. it is also
the favoured choice for the production of prototype boards.

21

The additive processis further sub divided into three different classes,print, plate and etch,
panel plating and patternplating. Print, plate and etch consistsof defining the tracks etc by means
of a positive image mask and a negativephotoresist.The unexposedresist is removed in the
developmentleaving the copper exposedin the track regions. After suitablecleaning, the copper
is plated with a appropriatemetal etch resist such as tin, tin-lead, nickel or gold. After plating,
the resist is removedand the unwantedcopper is etchedaway leaving the tracks.
If double sided boards with plated through hole connectionsare required the panel plating
methodmay be usedin conjunctionwith print, plate and etch. Through-hole-platingis a technique
used where high componentdensitiesare required. This allows interconnectionsbetweeneither
side of the board, avoiding track cross-over. It consistsof drilling the appropriateholes in the
copper clad boardsprior to processing.In order to plate the non-conductingholes, it is necessary
to sensitisethe them by producing an adsorbedlayer of palladium on the hole walls. The board is
placedin an electrolesscoppersolutionandthe palladiumactsasa catalystto initiate the deposition
hole.
A
thicknessof between2 to 5 pin is appliedandthis is followed
the
the
of
walls
copper
onto
of
by electroplatedcopper to producea plating thicknessof 25tLmwithin the hole. This may require
a copperthicknessof up to 40jurn on the coppercladding. The print, plate and etchplating method
define
is
described
to
then
the features.However, this methodof panel followed by
used
above
as
has
significant disadvantages.Circuit featureslessthan0.4 mm cannot
plating
etch
print, plate and
be producedwith this technique.This is becauseof the total thicknessof unwantedcopper to be
etchedis very high andthis leadsto undercuttingof thetracksbeneaththe etchresist. This reduction
can be as much as 0.2 nun and slivers of etch resist metal can break away leading to subsequent
is
Where
tin
solder
used as the etch resist, this problem can be eliminated by
or
short circuits.
fusing with hot oil or infra-red heating.
The pattern plating process is the most widely used manufacturing process to produce
plated-through-holePCB's. It is suitable for fine feature geometriesas there is less undercut
involved. The manufacturingroute is the sameas that for panelplating up to the applicationof the
is
However,
the
the
after
electroless
copper,
photoresist
appliedand the image
copper.
electroless
produced as in the print, plate and etch method. Copper is then electroplatedonto the exposed
by
followed
After
holes,
into
the
the removal of the resist, the
the
etch
resist
metal.
and
areas
unwantedcopperis etchedaway.With this method,thereis muchlesscopperto etchandtherefore,
less undercutting occurs to the tracks. Dry film resistsare very applicableto this route as their
thicknessis of the sameorder as that of the plated copperand etch resist combined.
The masksused for the production of PCBs are critical to the final product. These can be
final
For
in
the
size may be drawn directly
prototyping,
a
mask
of
of
ways.
generated a number
onto a Mylar sheet but with obvious limitations to accuracyand tolerances. The artwork for
large
layouts
is
scale
produced
manually
using
with masterto final size
often
production purposes

22

ratios of up to 10:1. Theseare then reducedin sizeusing specialisedand expensivecameras.More

modem techniquesproduceartwork automaticallyto the final sizeusingprecisionx-y plotters from
computer generateddesigns.
The level of automationthat can be appliedto the large scaleproduction of PCB's meansthat
large numbersof boardscanbe producedat a relatively low cost. However, the costsof producing
high precision, fine geometry(< 0.3mm) one-off boards can be very high consideringthe generation of the artwork constitutesa large proportion of the overall cost. In the caseof greater
geometrylines. theuseof laserprinters or plottersto directly generatethe artwork hasnow become
the main route for the production of suchprototype circuitry.

3.1.4 Pre-formed masks

Pre-formed masksare usedmainly in the field of the continuousselectiveplating of strip or
pressedstrip. Most electrical connectorsare producedfrom phosphorbronze or beryllium copper
form
been
has
to
the shapeof the connector. These then require a nickel
punched
strip which
deposit followed by hard gold plating on the mating facesto provide necessarywear and contact
lead
frame,
is
Another
type
the
of
continuous
strip,
produced this way.
resistanceproperties.
These are manufacturedfrom either Kovar or stainlesssteel. Lead frames are used to connect
integratedcircuits (IC's) from the inside of their hermetically sealeddual-in-line package(DIL)
to the outsideworld, ie the circuit board. This requiressoft gold to be plated at the internal ends
between
bonding
frame
facilitate
lead
the
thermo-compression
to
wires
of
gold
and the IC.
the
of
In both cases,the gold is only requiredin discreteareasof the strip. By the useof selectiveplating,
One
have
been
saved.
of the earliestgold reductionswas brought about by
tons47.
of
gold
many
the use of controlled depth immersion. This will be discussedin the next section.
The use of selectiveplating of continuousstrip becamepopular in the early '70s. In 1975,
Heiestad4s.described a variety of selective strip plating equipment that he was involved in
developing. These included anode geometry control (shielding), stationary mask striping, tip
The
plating
and
mask
anodegeometrymethodis described
stripe
spot
plating.
mask
moving
plating,
in section 3.3. Stripe plating is a processin which a stripe of metal or metals is plated onto a
continuous strip of metal ribbon. The stationary mask method made use of a rubber lipped
longitudinal slot placedwithin the plating cell. The moving strip waspassedover this slot and was
tensionedagainstit to obtain a solution seal.The electrolytewas pumpedat high velocity through
the slot and onto the strip. In this way, stripesof 2mm width with a toleranceof 0.13 nun could
-+
be achieved.Current densitiesof up to 600 mA cnr2were usedfor the gold plating. The moving
it
by
the
the
mask
synchronising
and
strip
of
as
wasmoved
means
was
achieved
maskstripe plating
throughthe plating bath. A split ring andrubberbelt combinationwasusedfor the mask. However,

23

its plating speedwaslimited by poor anodepositioning andtheuseof relatively low current densities
of between 50 and 100 rnA cnr2 were used. The processdid have the advantageof allowing the
plating of pre-punchedstrip lead frames. Mask spot plating was achievedby using a wheel mask
constructed from G10 fibreglass with appropriate holes for delineating the deposit. This had
problems with speedand registrationbut showedthe principle of operationvery well. Strip speeds
for the various processeswere describedand speedsrange from 2m min-I for intermittent wheel
spot platers up to 12m,min-'. for continuouslead frames, both receiving 50 u in. of gold.
At the sametime, Texas InstrumentS49.
reported the use of a spot plater for plating nickel and
gold onto continuouscontactstrip. A Teflon mask incorporating a platinised tantalum meshanode
was used. No mention was made on whether the mask was stationary or moving or of the strip
speedused.
Menziesm.describedreel-to-reelplating in 1978.The two techniquesmentionedwere controlled
depth immersion and stripe plating, similar to that describedpreviously. At the sametime, Rehrig5l.
described a step and repeat spot plating unit for the plating of lead frame bond pads in which the
in
The
that
closed
a
clarnshell
a
mask
opened
and
manner.
mask
out
using
carried
was
spot plating
was constructedfrom silicone rubber.

Theseincludedcontrolleddepthimmersion,
Hainet02- reviewedselectiveplatingtechniques.
fixed masksandmovingmasksaswell whatwastermedasfluid flow masking.This wasa method
limitations
They
HSSJE.
the
commented
on
various
advantages
and
to
of themethods,
equivalent
distortion
due
fixed
to
can
create
of
and
slow
problems
strip
speeds
that
systems
mask
noting
friction betweenthe maskandthe strip.
In 1982, Turner53-describedthe latesttechniquesfor the selectiveplating of connectorswith gold.
He describedhow high agitation rates and high metal ion concentrationsenabledhigh processing
in
densities
in
bath
250
He
Current
be
the
the
to
region
of
gold
were
mA
Crrr2.
achieved.
speeds
dielectric
flow
Oetting
fluid
in
that
of
masking
masking
and
air) was the
combination
a
claimed
for
high
Details
how
this was obtained
technique
speed
continuous
strip
plating.
of
successful
most
in
this reference.
given
were not
A more recent review of the selectiveplating of precious metals for connectorshas been given
by Wingenfeld. 54.He statedthat the moving masksystemin conjunctionwithjetting of the electrolyte
is the most widely used selectiveplating system. A wide range of configurations are describedfor
many connector configurations.

24

3.1.5 Controlled depth immersion

Controlled depth immersion is a relatively simple selectiveplating technique. The continuous
strip is fed into a plating electrolyte vertically and at a controlled depth. The immersed region
therefore gets plated whilst the remainderdoesnot. The solution level is maintainedby meansof
is
The
into
from
tank.
the
tank
the
electrolyte
pumped
plating
a reservoir to
end
of
at
each
a weir
described
provide a rapid flow pastthe work allowing high current densities to be used. Hain et a152.
the advantagesof the systemas being simple and versatile but listed the disadvantagesof surface
turbulence and capillary action reducing the selectivity. As a consequence,the feed-through rates
have to be low. Also, as many componentssuch as connectorsrequire plating on one face only,
is
is
immersed
there
the
the
component
plated,
a considerablewastageof gold.
of
as
whole

3.2 BRUSH PLATING

Brush plating is a generic term that covers a range of techniquesused for selectivedeposition
by meansan anode, covered by an absorbentmaterial soakedin a plating electrolyte and rubbed
being
Its
date
back
days
to
the
plated.
origins
probably
the
early
of
surface
cathodic
across
it
in
decorative
For
the
was
common
practice,
particularly
years,
plating
many
electroplating.
industry, to usethis methodfor touching up defective electroplate.In those days, a piece of anode
This
in
"tampon"
in
the
the
used.
was
soaked
plating
electrolyte
was
and
a
rag
material wrapped
defective
The
history
development
the
and
rubbed
to
area.
across
supply
and
a
power
was connected
by
Rubinstein.
55-56.57.
The
been
has
brush
reviewed
extensively
problem with using
plating
of
is
deposition
deposit
that
materials
rates
and
anode
and
quality are very
conventional electrolytes
developed
high
The
Modem
specially
concentration
metal
electrolytes.
use
metals
systems
poor.
high
ion
form
this
in
complex
as
allows
organo-metallic
the
metal
an
concentrations
of
are usually
is
high
A
conductivity
also a requirementof the system.
to remain soluble.
Special insoluble anodesare used. Theseare usually made from high purity graphite although
from
Soluble
a
platinum/iridiurn
alloy.
anodesare unacceptableas at the
made
are
small anodes
high current densitiesemployed,polarisation rapidly occurs leading to a significant drop in current
density. The anodescan be specially shapedto conform to the job in hand. The process usually
is
in
heat
design.
It
the
modular
of
so
anode
consists of a metal
quantity
generatesa significant
fins.
The
is
fitted
handle
aluminiurn
graphite
cooling
or
with
platinum
alloy
anode
cored, plastic
fitted to the metal insert at the cooling fin end and electrical connection is made at the other end.
The work-piece is connectedto the negativeterminal of a high voltage, high current power supply.
The usual rating for sucha supply is 30V/30A althoughhigher power/voltage models are used for

25

certain applications. The anodeis wrappedwith cotton batting of a long fibre variety. To reduce'
wear on the batting, it is sleevedwith surgical tubing made from Dacron. Polypropylene wool is
sometimesused as an alternative.
The tampon or stylus as it is generally called, is dipped into the plating electrolyte and rubbed
in
frequent
be
to
the
a
circular
motion,
with
replenishmentsof electrolyte.
plated
surface
across
For cylindrical shapeditems, thesemay be attachedto a slowly rotating lathe or turning head and
the stylus held in steadycontactwith the work-piece. In theseapplications, the electrolyte may be
fed directly to the stylus by means of a small pump. In this way, the process can be made
semi-automatic.
Control of the thicknessis basedon precise amp-minute meters. Due to the varying current,
distance
in
from
the
the
depends
the
the cathode
of
anode
the
stylus,
of
electrolyte
volume
on
which
is
It
is
usual to apply a voltage within a range specific
recommended.
not
the
ammeters
use of
etc,
to the electrolyte and monitor the current/time integral.
There are many advantagesclaimed for the brush plating technique. Refractory metals and
difficult to plate metals such as aluminium,are easily plated with this method. It is claiMed56.that
the adhesion is superior to conventional methods although the mechanismby which this occurs
has not been made apparent. It is also claimed that the hydrogen embrittlement of high tensile
deposition
brush
In
high
by
the
is
the
plating.
of
of
particular,
cadmium
use
onto
eliminated
steels
de-embrittlement
heat
is
This
does
treatment.
a
subsequent
require
confirmed
not
strength steels
by the fact that U. S. Air Forcehasapprovedtheprocesswithoutthe de-embrittlementheattreatment.
lists a very wide range of applications for the brush plating process. These
Rubenstein56.58.
flexible
deposit
through
to
from
that can
waveguides,
components
with
any
engine
aircraft
range
be conventionally deposited.Someof the more commonusesare in the repair of damagedor wom
by
brush
built
be
These
with
up
an
electrodeposit
means
of
plating and then
can
components.
be
Plating
instances,
high.
For
this
In
may
not
even
necessary.
rates
are
very
many
re-ground.
1.7
be
deposited
2.5
deposits
to
to
sec-1.
can
up
whilst
silver
at
Am
at
up
gold
Am sec-1.
example,
Deposit quality is very good becausethe high current densitiesemployed produce deposits with
a very fine grain size.

Selectivityis achievedbecause
only thoseareasthatcomeinto contactwith the electrolyteare
large
Components
fit
into
too
that
to
has
This
are
advantages.
conventionalplating
many
plated.
in
functional
For
the
be
areas.
enginecomponents,the entireengine
tankscan selectivelyplated
down
If
that
the
be
to
wom
region
needs
expose
re-plating.
an area
to
stripped
may not need

26

be
Because
is
there
masking
conventional
methods
can
cut
off,
applied.
a
sharp
no
requires
immersion in the electrolyte, theseconventionalmaskingsystemsremain in placemuch better than
if immersed.
Wingenfeld54.recently reported the use of the brush technique for the selective plating of
He
described
kinds
brush,
brush
two
the
of
moving
and the
connectors.
electrical
reel
continuous
in
brush58The
brush.
wrapped
consists
of
a
cylinder,
an absorbentmaterial,
moving
stationary
is
from
is
The
into
dipped
titanium,
the
cylinder,
which
made
platinised
used
electrolyte.
partially
as the anode. This slowly rotatesand the connector strip passesalong the cylinder with only the
is
it.
In
Plating
in
this
selective
plating
achieved.
with
rates of
way,
contact
area requiring plating
is
becoming
less
This
be
technique
this
6
with
method.
popular
achieved
can
up to gm/min. of gold
degree
become
the
the
contact
reduces,
required
and
area
of
of selectivity
smaller
as connectorsizes
brush.
brush
been
by
The
is
has
It
59.
be
the
longer
stationary
replaced
aV shaped
achieved.
can no
hollow platinised titanium block covered with an absorbentmaterial. The angle of the V is such
is
0.8mm.
The
into
low
has
electrolyte
of
about
pumped
at
area
pressure
the
a
contact
that
point
by
become
holes
the electrolyte by capillary
the
to
A
block.
wetted
material
allows
the
series of
block
V
the
the
they
touch,
then
The
of
and
where
along
passed
electrolyte
are
components
action.
is
block
but
The
constant
mounted onto an adjustmentplatform
rate.
slow
gently oozes out at a
block
be
By
block,
larger
tilting
tilt
to
the
the
the
of
set.
areas
angle
of
the
and
that allows
position
between
5-6
this
Plating
be
are
obtained
with
method.
of
rates
lim/min.
plated.
may
In general, the brushplating methodhasmany advantagescomparedwith conventionalmasking
deposition
be
in
deposition
High
can
are
obtainable,
carried
out
situ and many
rates
methods.
difficult to plate metals present few problems with adhesion. However, there are a few disadis
in
the
The
the
very
good
especially
process
not
absenceof additional
of
selectivity
vantages.
is
dependent
the
The
the
of
operator, exceptwhere automation
on
skill
operation
methods.
masking
is used.

3.3 ANODE PLACEMENT AND GEOMETRY

Selectiveplating canbe achievedby thejudicioususeof anodedesignand geometryof the

it
is
how
be
how
this
to
In
achieved,
to
can
necessary
understand
understand
order
plating cell.
In
distribution
the
absenceof any surfaceoverpotential
distribution
are
related.
current
and
metal
distribution
During
applies.
current
primary
electrodeposition
(eitheractivationor concentration)
be
polarisation
can
concentration
effectivelyeliminated.
although
this situationcan neveroccur
in
but
the caseof certainsystemsthat exhibit
be
There will always someactivationpolarisation
is
However,
if
ie
this
the
minimal.
sulphate
fast
copper
electrolyte
reactions
electrode
very
distribution
higher
the
is
than
resistance,
primary
current
activation
will occur.
resistance much

27

In this case, the current distribution on a cathodewill dependlargely on the distancebetween it

and the anodeas well as the electrolyte resistance.The closer the electrodes,the more even will
be the deposit.
Secondarycurrent distribution occurs if the cathode experiencessignificant overpotentials.
Concentration polarisation usually gives rise to secondaryelectrode reactions such as hydrogen
evolution. Therefore, in regionswhere the concentrationpolarisation is highest, local high current
density areas, the deposition rate is reduced. This causesthe metal distribution to deviate from
that expectedunder primary current distribution.
Becauseof thesefactors, it can be seenthat by reducing the distancebetweenthe anodeand
fast
that
allows
electrodereactions,reducingthe electrolyte resistance
electrolyte
cathode,using an
and eliminating concentrationpolarisation, electrodepositscan be produced selectively by means
for
Landau'O.
the electrodepositionof precious
patented
such
a
system
anodes.
shaped
of small,
The
plating cell made use of an anodethat conformed to the shape
connectors.
plug
onto
metals
The
be
the
to
comb.
anodewas placed adjacentto the comb, with
connector
the
on
plated
area
of
flux
In
between
the
this
them.
way,
current
was concentratedon the part of the comb
gap
a narrow
To
eliminate concentrationpolarisation, the electrolyte was pumped
required.
was
where plating
hundred
Current
densities
in
200
the
cm
of
several
sec-1.
a
rate
the
at
region
of
mA
electrodes
past
found
distribution
It
that
the
closely matched the primary current
metal
was
Crn-2were used.
distribution.
An improvement on this design was made by Bacon et al6l. who made use of a focusedanode
but
distance
from
it.
to
the
In
the
was
not
placed
close
cathode
anode
at
this
some
method,
cell.
The current flux was focusedon the required area by meansof a dielectric slot, which was part
of the cell. In this way, a virtual conforming anode existed at the same point as would a real
had
design
longer
This
the
the
that
anode
advantage
no
presentedan obstacle
conforming anode.
to the electrolyte now, thus reducingthe pressuredrop and the uniformity of the deposit no longer
dependedon the exact spacingbetween the comb and the conforming anode, which was critical
in the former design.
62.63.64.
plating.
has
in
been
The useof closeproximity anodes
studied conjunctionwith pulse
currentdensitiesproducedby pulseplatingfavourprimary current
Becausethehigh instantaneous
in selectivitywereobtained.
distribution,improvements

28

3.4 AUTOCATALYTIC

(ELECTROLESS) DEPOSITION

Autocatalytic or electrolessplating can be made selective on non-conductingsubstratessuch

as PCB's or MICS if the catalyst that initiates the deposition is put onto the surface selectively.
There have been a number of recent developmentsin the printed circuit industry that use this
method. Cook65-reported a novel approachto selectivemetallisation of through hole PCB's. The
drilled board is conditioned in an atmosphereof sulphur trioxide, produced from oleum. The
functional
leaves
chemical sites of S03H on the board. Subsequentto this, a
conditioning process
in
is
layer
through
the usual way. The board is then
applied
and
exposed
a
mask
photoresist
processedthrough a palladium activator and the regions exposedthrough the resist reduce the
highly
boards
The
through
then
a
stableelectrolessnickel bath to metallise
are
processed
palladium.
the exposedregions and the board is finished in the usual way.

29

CHAPTER 4

HIGH SPEED ELECTRODEPOSITION PROCESSES

The previous chapterdescribedthe various methodsused to obtain selectivedeposition. Many

high
techniques
made
use
of
the
also
speedplating techniques.This chapterdescribes
mentioned
of
the theory and methodologyof high speeddepositionfor both selectiveand non-selectiveplating.
4.1 THEORETICAL ASPECTS
For many processesthat require large volumesof componentsor bare metalsto be plated, there
is an obvious commercial advantageto produce theseas quickly as possible. In order to do this,
high current densitiesneedto be applied. However, the current density cannot be raised above a
know
To
limit.
to
themechanismsthat control the rate of deposition
we
why,
need
understand
certain
be
how
manipulatedto the advantageof the plater.
these
can
mechanisms
and

4.1.1 Transport mechanisms and the diffusion layer.

For a metalto be depositedfrom an electrolyte,metalionsneedto be presentat the cathode

into
incorporated
become
During
deposition,
the
growing
and
surface.
to
electrons
accept
surface
interface.
These
by
ions
ions
the
are
replaced
at
metal
arriving at the surface
areconsumed
metal
by meansof diffusion, migrationandconvection.Convectionresultsfrom the movementof the
bulk electrolyteby stiffing etc. Migrationoccursasthe resultof the electricfield on the charged
ions. For example,CU2+ions havinga positivechargewill migrateunderthe influenceof the
However,
Au(CN)2-,
the
field
a
complexed
anion
such
the
as
cyanoaurate
to
cathode.
anion,
electric
influence
be
The
by
the quantityof other
can
the
of
migration
to
affected
anode.
will migrate
do
in
in
that
take
the electrodereaction,aseachcharged
the
not
part
electrolyte
chargedspecies
for
In
is
large
the
the
a
portion
carrying
of
current.
presence
of
a
responsible
excessof
species
interest,
influence
the
the
than
species
electroactive
of
of migrationon each
chargecarriersother
individualelectroactiveion is minimised.Diffusionis a processthatoccursby meansof a random
is
in
bulk
ions
but
Diffusion
the
distance
a
continuous
the
process
electrolyte
of
net
walk process.
interface
deposition,
during
However,
is
the
66.
at
metal ions are being removed
travelled zero.
leaving a lower concentrationcloseto the interfacecomparedto the bulk solution. Theseare
has
been
Ions
because
diffusion
by
concentration
gradient
set
a
up.
outsidethe interface
replaced
interface
lower
influence
diffuse
the
the
to
region
at
concentration
the
under
tend
to
of
regionwill
the concentrationgradient.

30

The region over which this directional diffusion occurs is known as the diffusion layer. The
thicknessof the diffusion layer is very dependenton the prevailing hydrodynamicconditions within
the bulk of the electrolyte, the convection.In unstirred solutions,the diffusion layer thicknesscan
flow,
it
high
0.05
conditions
of
electrolyte
can be as low as 0.002 cm.
under
cm whereas
reach
The diffusion flux J,) is relatedto the current density. It can be found using Ficks law of diffusion
is
ignored
if
migration
and

dc

dx)

nfJDs-D

(4)
: 'o

This can be put in terms of the concentrationat the interface by

(Cs-co)
i
JD_-D
6
nF6

(5)

On solving for i we obtain

-i-

nFL(cb - co)
5

(6)

If the current density is raisedsufficiently, diffusion will not be able to re-supply the ions and
This
drop
limit
interface
density
to
the
represents
the
will
zero.
of
current
at
the concentration
hydrodynamic
be
conditions.
of
set
any
under
that can applied

nFDcn
t =b

dependent
is
be
from
temperature
diffusion
as
can
seen
Also, the
coefficient

31

(7)

D'_
T

constant

(8)

It can be seenfrom equation(7) that the magnitudeof the limiting current density is controlled
by the thicknessof the diffusion layer, the concentrationof metal ions and becausethe diffusion
by
(8),
The
difftision
is
the
temperature.
thinner
temperature
the
to
equation
related
coefficient
layer and the greaterthe metal ion concentration,the higher the value of 'L. There is a certain limit
to the metal ion concentrationthat can be used. This is dictated by the solubility of that particular
ion. However, the thicknessof the diffusion layer is dependenton the degreeof agitation of the
bulk electrolyte.
It follows that for high speedelectrodeposition,high metal ion concentrationsin conjunction
be
high
temperatures
high
used.
should
and
of
agitation
rates
with

4.1.2 Realistic limiting current densities

Despite the fact that the limiting current density is the absolutelimit on the deposition rate for
it
has
found
by
been
deposit
that
the
a
number
of
workerS4.5.6.7.8.
conditions,
a particular set of
deterioration
is
below
'L.
This
by
formation
deteriorate
the
begins
apparent
to
at
some
value
quality
is,
important
deposits.
It
therefore,
dendritic
to ascertainthe
nodular
powdery
or
growth
of either
fraction of the limiting current density at which depositsbegin to deterioraterather than the limiting

is
deterioration
high
This
itself.
to
the
density
value,
certainly
related
with
exchange
current
"'L*
degradation
lower
It
logical
density
that
at
a
ratio
of
would
exhibiting
seem
systems
current
if the diffusion layer thickness could be reduced without affecting the critical ratio of '/'L then
higher deposition rates could be obtained from any particular electrolyte.

4.2 MEASUREMENT OF THE LIMITING

CURRENT DENSITY

of any systemcan only be obtainedif the

Information on the masstransfercharacteristics
'LP
is
This
be
density,
known.
by
direct
limiting
can
made
current
the
measurement
magnitudeof
density
by
between
the
the
current
and
or
overpotential
measurement
of the
of the relationship
is
difficult
latter
This
layer.
have
diffusion
to
technique
achieve
there
the
although
thicknessof
67.
beensomesuccessfulattempts.

32

4.2.1 Limiting current density measurement methods.

Measurement
of 'L for any electrodereactionrequiresthat the surfaceconcentrationof the
reactingspeciesattheelectrodeis reducedto ascloseto zeroaspossible.By plottingtherelationship
betweenthe overpotential,tj andthe log of currentdensity,log 'LOthe limiting currentcondition
can be seenas a plateauwherethe currentdensityremainsalmostconstantwith increasing71.
Theseplotsmaybeobtainedbyapplyingincrements
of eithercurrentor overpotentialandmeasuring
the resultantchangein theuncontrolledvariable.Figure5 showsan idealpolarisationcurve.The
limiting currentdensityis clearlyvisible. The increasein currentat the endof the plateauis due
reductionprocesssuchashydrogenevolution.However,suchan
to a consecutive
electrochemical
68.Firstly, the surfacearea
idealplateauis difficult to obtainin practicefor a numberof reasons.
formation
deposition
deposits
in
during
due
increases
to
the
the region
of
rough
the
electrode
of
Secondly,
if
density.
'L*
This
the
true
current
competingelectrochemical
changes
effectively
Of
deposition,
hydrogen
as
evolution,thenthepartialmetal
with
such
simultaneously
occur
reactions
depositioncurrentis maskedby the currentdueto the secondaryreaction.Thirdly, at very high
is
found
high
transfer,
under
of
electrolyteagitation,the sizeof
as
conditions
such
ratesof mass
A similar effectis seenwith high metalion
the limiting currentplateauis reducedor disappears.
Both
due
in
these
to the onsetof the consecutive
the
are
phenomenon
electrolyte.
concentrations
'L
'L
in
these
the
circumstances,
of
occursat a much
as
under
region
overpotentials
at
reaction
higher valueof Tj. Finally, the rateof changein the perturbationappliedhasa stronginfluence
Too
fast
increment
lead
to non-steady
the
an
can
stateeffectsoccurring
plateau.
of
ontheappearance
diffusion
layer
be
do
to
state
established.
a
steady
allow
not
which

Log Current

Density

Figure 5. A typical polarisation, curve showing the limiting current density.

33

In addition, it is important when measuring'L that the effects of migration are reduced. The
contribution to the value of 'L of migration can be seenas the (I - t) term in equation (1). This
influence can be significantly reducedif an excessof a supportingelectrolyte is added, which will
then carry the major portion of the current. Such an electrolytic material should not influence or
be involved in the cathodic reaction of interest. Despite thesedifficulties, there are a number of
basic techniquesthat canusedto obtain the necessarydatato constructsucha polarisation curve.68.

4.2.1.1 Galvanodynamic methods.

The simplestapproachto obtaining'L is by applyinga controlled,incrementingcurrentand

impedence
high
the
voltagemeasuring
with
a
reference
electrode
and
measuring overpotential
in stepsor continuously.The successof this methodis
device.The currentmay be incremented
being
the
dependent
species
examined.For thesystem
as
well
as
the
of
measurement
on conditions
CO,afinite timeis required.Hickman69.
to attainasteadystatein termsof zerosurfaceconcentration,
in
8
free
time
or
was
order
of
minutes
more
needed
conditions,
a
that
convection
under
reported
'L*
disc
found
Selman
the
that
using
rotating
electrode
of
a168.
et
values
to obtainreproducible
(RDE), steadystatecurrentsrequireda minimumtime of
iL
t" di/dt

60Sc"'w-'

(9)

This was found to be three times as high as for the equivalenttime using the potentiodynamic
it
despite
is
However,
to
the
below).
this,
(see
use
galvanodynamicmethod
often
preferable
method
for metal deposition reactionsas there is less rougheningof the deposit close to 'L than with other
methods.18.

4.2.1.2 Potentiodynamic methods.

method,the potentialof the working electrodeis altered

In the caseof the potentiodynamic
The
difference
to
electrode.
a
reference
with
respect
potential
continuously
or
either step-wise
betweentheworkingelectrodeandthereferenceelectrodeis maintainedby meansof apotentiostat.
The currentflowing throughthe cell is recordedandplottedasbefore.Onceagain,it is essential
for
is
before
diffusion
the
each
value
of
applied
attained
potential
condition
that a steadystate
found
it
been
has
the
times
However,
that
to
minimum
reach
is
steady
state
are
recorded.
current
However,
density
initially
68.
the
as
current
method.
1/3
the
equivalentgalvanodynamic
of
about

34

rises more rapidly during a potential ramp comparedto a current ramp, this can lead to excess
surface roughening of the electrodewith the potentiodynamicmethod. As a result, excessively
high limiting current densitiescan be measured.
Relatedto the potentiodynamicmethodis the potential steptechnique.70-This method involves
separatelyestablishingthe approximatepotential, EL, at which OS found, by a potentiodynamic
by
is
followed
This
plotting the current-time relationshipat potentialsbelow, at and above
sweep.
this arbitrary value of EL. The value of EL used for the potential step analysis is that at which the
smallest variation in current magnitude is observed. Then, a potential step of magnitude EL is
applied to the electrodeand the current measuredover a period of time. The steady state current
'L.
is
is
This
by
the
this
value
of
claimed to have the advantageof being
method
method
measured
less sensitive to surfaceroughnessof the working electrode.

4.2.1.3 Convective control methods.

This method canbe usedif forced convectionis involved. A constantcurrent density is applied
The
is
in
high
then
conditions.
velocity
reduced
velocity
controlled manner until
convective
under
indicates
limiting
is
This
density
has
been
in
that
the
rise
current
observed.
potential
a steep rise
is
This
for
particularly suited to electrolytes
the
convective
velocity.
method
associated
reached
drop
is
the
the
low
ohmic
under
conditions
of
as
measurement
constant.
conductivities
with
There are severalother methodswhich include minor variations on the aforementionedthemes
but their use is limited to specific situations. Once the limiting current density for any particular
has
been
it
is
situation
established,
relatively easyto characterise
geometry/hydrodynamic
electrode
the masstransfer properties of that systemin terms of the Sherwoodnumber by equations(2) and
(3)

When measuringlimiting current densities,the problem of deposit growth can be serious. This
is especially so in convectivesystemsthat allow the rapid depositionof metals. In order to establish
in
hydrodynamic
flow, use is often
terms
the
of
such
a
system
of
transfer
characteristics
the mass
is
frequently
A
ferricyanide/ferrocyanide
the
used
redox
couple
alkaline
couple.
redox
made of a
ferrocyanide,
is
the
to
Ferricyanide
with
advantageof the system exhibiting
reduced
electrolyte.
have
been
Such
in
limiting
large
systems
used
extensively
plateau.
current
establishing the
a
in jet electrolysis.
flow
fluid
between
transfer
and
mass
relationships

35

4.3 PRODUCTION PROCESSES

Whilst there hasbeena large quantity of work producedthrough high speeddeposition plants,
relatively little has been published on the plating conditions and deposit morphology. This is
presumably becauseof the commercial confidentiality of such processes.In 1982, Safranek7l.
reviewed the latestdevelopmentsin the high speedplating of chromium, copper, nickel, zinc, gold
and silver. He reportedthat the first commercialusesof the techniqueoccurred in the early 1940's
when thin layers of tin were depositedonto continuoussteel strip at current densitiesof up to 0.5
A Crrr2.This was achieved by passing the steel strip at high speed (1.2 m sec-1)through the
has
been
Since
then
the
process
used for the high speedzinc plating of steel strip and
electrolyte.
wire. However, the application was limited until the 1970's, when suitable pumps capable of
continuous high speedmovementof electrolytes were developed. He concluded that generally,
high temperatures,high turbulent flow rates (in excessof 1.2 rn sec-1)and high metal ion conhigh
deposition
to
achieve
needed
were
rates. He reported rates of deposition as high
centrations
as 120 itni min-1for thin coatingsof gold and 180 14mmin-' for silver. For tin and zinc, rates as
high as 140.jim min-' and 80 tLmmin-1respectivelywere achieved.

Apart from the platingof steelstrip andwire, the most importantapplicationof high speed
depositionhasbeenwithin theelectronicsindustry.As mentionedin theprevioussection,gold is
industry.
The
this
mostcommonapplicationsof gold are for the plating
within
extensively
used
frames,
lead
PCB
edgeconnectorsandtransistorheaders.Other appliconnectors,
of electrical
for
bonding
deposition
bumps
include
the
the
of
gold
spots
or
of gold connectorwires to
cations
integratedcircuits. Sewell72.
reportedthe reel-to-reelselectivepuregold platingof leadframesat
high electrolytevelocityusinga mechanicalmaskandelectrolytejetting. Currentdensitiesof up
to 0.6 ACr1r2wereusedwith electrolytevelocitiesof up to Im see-'.Thecurrentefficiencieswere
found
It
for
differing
that althoughhigh depositionrates
concentrations
of
gold.
was
measured
%,
100
deposit
deteriorated
to
be
the
rising
efficiencies
quality
with
astheefficiency
achieved
could
This
the
maximumoccurredat currentdensitiesof around0.12 ACM-2
maximum.
approached
Above
ion
deposit
1-1
24
this
the
concentration.
value,
metal
appearance
g
changedfrom a
with a
brown
later
The
depositsshowedpoor eutecticdie
fine
to
a
rougher,
colour.
crystalline
yellow,
Plating
for
24
1-1
properties.
rates
a
g
gold citrateelectrolytewerereported
welding
attachandwire
factors
in
high
deposition
The
6
the
be
significant
most
speed
of gold werefoundto
to
inim'.
Itin.
be the flow rate, compositionandtemperature.
In contrast to the previous author, Dorey et 03. who examinedgold deposits produced in a
Chapter
flow
(see
5),
fluid
for
but
that
masking
concluded
thermocompression
using
similar way,
bonding, a gold with a distinctly "foxy brown" colour was optimum. Both a citrate basedelectrolyte
126
1-1
Au
1-1
Au
The
hardness
22
with
g
electrolyte
were
a
proprietary
used.
and
g
of the
with
200
Knoop.
Flow
137
between
39
deposit
to
to
rates
of
up
cm sec-1were usedalthough
was
optimum

36

the optimum was found to be 13 cm/secusing a current density of between0.58 to 0.86 A crn-2.
ScanningElectron Micrography (SEM) revealedthat the "foxy brown" appearancewas due to a
high degree of nodulation. This was not surprising considering the relatively low flow rates
employed.
The aforementionedwork was an extensionof the resultsof Rehrig.51-He describedthe deposit
both
DC
using
morphology
and an asymmetric waveform using high rates of
and
characteristics
electrolyte flow in a spot plating unit. Unfortunately, the electrolyte velocity was not mentioned.
Gold concentrationsof between30 and 40 g 1-1were used. The influence of the nickel undercoat
in
He
DC
for
included
bondability
the
that
claimed
assessment.
current
was
unsuitable
good
also
was
300
in
deposition
A
densities
mA
CM72.
of
wide
range
of
excess
conditions were examined
at current
using an asymmetric AC waveform, with a peak cathodic current density of between 1.0 A Cm-2
and 3.0 A CM-2.The AC frequency was tested between 60 and 50OHz. Anodic peak current
densities were examinedbetween0 and 0.4 A Crn-2.It was found that it was essentialto use an
Using
bondability.
for
an anodic current density componentof 0.25 A CM-2,
good
anodic current
The
deposit
bonds
morphology
such
of
a
showed a significant grain surface
satisfactory.
were
all
deposits
He
found
that a certain
cycle,
anodic
smooth
no
were
produced.
with
whereas
projection,
degreeof surfacemicro-Toughnesswas necessaryfor good bondability. The peak cathodic current
density also influenced the grain structure and bondability. At current densities of 3.0 A Cm-2the
deposit
but
lacked
high
the
was
powdery
and
adhesion.He concluded that
was
surface roughness
in
bondability
factor
important
obtaining
good
was the presenceand magnitude anodic
the most
for
If
low
the
the
the
this
too
nickel
of
plating
solution
used
undercoat.
pH
and
was
offset
current
then poor adhesion of the gold occurred. The frequency of the AC waveforin did not have a
bondability.
influence
the
on
significant

EndicottandCaseyXexaminedthehigh speedplatingof goldusingdilute electrolytesfor the

frames.
A
1-1
10
lead
The
gold
concentration
of
g
was
used.
of
plating cell
plating
reel-to-reel
for
The
18.3
Electrolyte
selectivity.
strip
was
optimised
speed
at
mask
m
moving
mirr'.
a
employed
but
details
the
to
the
through
mask
no
of
strip
relative
electrolytevelocitywasgiven.
pumped
was
it was foundthat aI Itm depositcouldbe achievedat this strip speedusinga currentdensityof
0.8 ACm-2.Thedepositsproducedwererelativelysmoothandnodulefreeandwereableto sustain
for
die
bonding.
high
thermocompression
wire
and
performance
a consistently
It is interestingto notethedifferentperformances
of thesystemsusedby thepreviousauthors.
Whilst a micro-roughsurfacewasfoundto beoptimumfor some,theoppositewastrue for others.
Rehrig5l.notedthat for gooddie attachperformance,a soft gold (lessthan 152 kg mm-2)Was
his
(<
124
found
Knoop).
In
both
Dorey73that
was
also
soft
optimum
gold
also
cases,
required.
Dorey's
being
brown
with
and Rehrig'sbeing matt
micro-roughened
considerably
the gold was
it
but
be
did
Endicott
measurements
out
micro-hardness
must
carry
assumedthat the
not
gold.

37

depositwas soft enoughto form a thermo-compressionbond. The real difference in the performance
defined.
in
flow
is
likely
different
to
the
clearly
which
was
not
rate
electrolyte
the
reside
methods
of
As flow rate affects the thicknessof the diffusion layer and thus the ratio of '/'LOthen this could
be the reasonfor the differences.
It is quite evident that high speeddepositionprocessesare required for rapid through-put of
for
I
deposition
(about
high
sec7l
Processes
that
of
rates
Jim
give
quite
are available
materials.
for
flow
further
by
increase
it
is
this
rates
and
but
to
electrolytes
optimising
still possible
gold)
particular applications.

38

CHAPTER 5

ELECTROCRYSTALLISATION

AND MORPHOLOGY

It was mentioned in section 4.1.2. that deposit quality deterioratesat some value of current
density below the limiting current density. This degradationtakes the form of rough, nodular,
dendritic or powdery deposits. It is obvious that the mechanismof growth goes through changes
as the current density is increasedand these changesare related to the rate of masstransport of
is
limitation
However,
ions
transport
the
to
the
not necessarilythe
mass
surface.
growing
metal
known
by
influencing
factor.
Electrodeposits
as electrocrysa
mechanism
are
produced
only
tallisation. An understandingof the mechanismsof electrocrystallisation is needed in order to
densities
high
how
are produced.
the
current
at
structures
observed
establish
various morphological

Crystallographic
planes

Surface
w

(2lmmmgEmm
Bulk

metal

Figure 6. A schematicrepresentation
of the surfaceof a metalshowingthe randomexposureof
crystalplanesat the surface.

5.1 SOME FUNDAMENTAL ASPECTSOF ELECTROCRYSTALLISATION

Electrodeposits
are crystallinein natureasarethe metalsonto which they are deposited.The
in
influence
the
on
way
which electrocrystallisation
the
substratecanexerta significant
natureof
flat,
Most
how
All
uneven.
apparently
are
metalsconsistof
surfaces,
no
matter
metal
proceeds.
boundaries
If
them.
separating
any crystalplaneother
grain
crystallites;
with
orientated
randomly
it
faces
the
will presenta seriesof steppedcrystalplanesor
solution,
plane
than a close-packed
kink
in
be
dislocations
There
and
vacancies
which
are
sites,
present
mostmetals.
will
also
edges.

39

A schematicrepresentationof the surface can be seen in figure 6. This is true even for single
crystals. This provides a depositingmetal ion with many different locations in which to join the
lattice. How it does so is dependenton the conditions at the interface at the time of deposition.
Having establishedgrowth sites,the depositwill then grow in a fashionthat is highly dependent
on the prevailing conditionssuch as current density, ionic form, temperature,nature of the metal
deposit etc. It is well known that electrodepositscan follow many different growth habits ranging
from compactepitaxial to single crystal needletypes. The first comprehensiveattempt to classify
His classificationwas basedon observationsmadewith
thesestructureswas madeby Fischer.75.76.
the optical n-dcroscope.He concludedthat there were six main forms of growth, with a number
of subdivisions of thesetypes.

1. Field oriented isolation type (FI)

2. Basis-orientedreproduction type (BR)
3. Twinned transition type (T)
4. Field oriented texture type (FT)
5. Non-oriented dispersiontype (NT)
6. Rhythmic lamellar type (RL)

Fischer concludedthat all thesedifferent growth forms were the result of differing degreesof
inhibition of the growth surfaceby foreign substances.Thesesubstancescould be organic molecules
deliberately addedto modify structures or impurities. In addition, anions could act as inhibitors
is
The
list
increasing
degree
the
the
reduction
of
above
ordered
with
process.
products
could
as
of inhibition.

Field orientedisolationtypes are generallyreferredto as dendrites,whiskersor needles.

Accordingto Fischer,theseform asa resultof low or no inhibitionat the surfacein conjunction
with low metalion contentandhigh currentdensities.
Basis orientedreproductiontypes refer to epitaxialor pseudomorPhic
growths. Theseare
density
in
inhibitors.
low
This typeof deposit
the
or
current
absence
of
at
overpotentials
produced
is produced mainly from simplesalt electrolytes.
The twinnedtransitiontype occursin the presenceof moderatelevelsof inhibitor. It is charformation
is
degree
high
by
twin
termedre-entrant
crystal
centred
around
of
what
acterised a
grooves.

40

Field orientedtexturetypesoccur whena considerableareaof the surfaceis coveredby inhibitor

molecules. This leadsto two dimensionalnucleationwith a subsequentoutgrowth forming layers.
Lateral blocking by the inhibitor moleculespreventsmerging with adjacentcrystallites. This leads
to a structure consisting of numerous fine fibres oriented in the direction of the field and are
associatedwith a strong preferred crystallographic orientation.

Non orienteddispersiontypesare associated

with considerableinhibition and consequently
depositionproceedsunderconditionsof high overpotential.The depositsconsistof fine grained,
A
100
500
to
anddo not showanypreferredorientation.
equiaxedcrystallites,typically
The rhythmic lamellar type is associatedwith relatively high levels of inhibition and manifests
itself as a lamellar or layeredstructureparallel to the surface. This structure is thought to form as
a result of periodic fluctuations in the degreeof inhibition as the deposit grows. It is believed that
the effects of the reduction reactionsoccurring at the interfacecausea fluctuation in the adsorbtion
inhibitor
is
inhibitor
that
the
the
generatedas a consequenceof the reduction process. In the
or
of
latter case, a new layer forms only after a minimum concentrationof inhibitor has been formed.
During the production of suchstructures,periodic variations of the overpotentialmay be observed.

Theseclassifications
providea goodguide-lineto depositstructuresalthoughthereare some
deposits
included
the
as
rounded
such
mound
and
nodular
structures
observed
with
not
structures
densities.
high
in
deposits
formed
Such
current
structures
often
observed
are
producedat relatively
In
have
been
diffusion
they
conditions.
controlled
addition,
also
observedwith
strongly
under
is
It
has
been
Fischer
hardened
that
the
although
now
accepted
model
electrodeposits.
gold
cobalt
it
individual
does
theory,
the
general
anomaliesthat may
as
a
not
explain
many
satisfactory
quite
be observedwhen studyingindividualsystems.An exampleof this is in the caseof hard gold
deposits.
Nakahara'n.studied the "rounded mound" structure of cobalt hardened gold. He found that
diameters
have
low
distributed
thicknesses
were
mounds
visible
and
even
at
of the same
uniformly
deposit.
found
increase
in
These
the
to
thickness
the
of
size as the deposit
mounds
were
as
order
thickened and ultimately impinged on one another. Transmission Electron Microscopy (TEM)
A
in
fine,
200-300
diameter.
deposits
In
that
the
consisted
of
uniform
grains
addition,
revealed
the grains had a preferred orientation of I 11 normal to the surface. According to the Fischer
Nakahara
should
not
possess
any
preferred
orientation.
grains
went on to
such
classification,
had
l5o
by
that
to
that
the
texture
the profile
that
a
spread
of
about
corresponded
extended
observe
from
inferred
bounded
He
by
III close
this
that
the
the
the
surface
of
mound
was
mound.
of
further
Transmission
Electron
Microscopy
growth
occurred.
which
also showed
onto
packedplanes
density
inclusions.
incorporation
high
He
the
of
of
a
non-metallic
concludedthat
of
clear evidence
these inclusions, presumably the potassiumcobalticyanide mentioned in Section 2.2.2, inhibited

41

lateraldiffusionduringdepositionand hencethereis anamplificationof randomsmall protuberances

formed in the initial layers. He went on to suggestthat adsorbtionof inhibiting molecules on the
top surface causedcontinuousnucleationand is responsiblefor the small crystallite size.
Such rounded mounds are observedunder certain conditions of Physical Vapour Deposition
(PVD). Sheppardand Nakahara78.observedthat under conditions of low surface temperature,
PVD deposits show a similar structure. Under low surface temperatureconditions, the rate of
surface diffusion is very low. This is analogousto the electrodepositionsituation where adsorbed
molecules inhibit surface diffusion. Under the Fischer classification, such a deposit should be a
Field Oriented Texture (FT) type. However, the depositdoes not possessall the criteria used for
the description of FT types, particularly the small grain size, and therefore the classification shows
its limitations.
Another of the limitations of the Fischer schemeis its reliance on the inhibition processalone
interaction
to
the
of the growing interface with either the diffusion layer or the
no
reference
with
hydrodynamic boundary layer that exists in convected electrolytes. As a consequence,more
elaboratetheories have beendevelopedto accountfor such interactions.

5.1.1 Electrocrystallisation at low current densities.

Bockris and Razumney79-have been influential in establishingsome of the theories of electrocrystallisation. They proposedthat at low current densitiesor more particularly, low overpotentials, the following mechanismprevailed. The hydratedmetal ion in the Outer Helmholtz Plane
under the influence of the electric field approachesthe metal surface where it lands on a crystal
hydration
is
but
is
distorted
due
However,
the
to the presenceof the
sheath
still
attached
plane.
incorporated
into
it
it
be
lattice,
has
lose
its
hydration sheathand
Before
the
to
crystal
can
plane.
be electronated.It is likely that partial electronationoccurs at this stageas in this form, an adion,
it has less than the full ionic charge of an ion in solution. In order to lose its remaining water
molecules, the adion diffuses to a stepwhere somewater moleculesare replacedby co-ordinating
The
diffuses
kink
then
the
to
the
adion
step.
along
step
a
site where further
at
atoms
metal
co-ordinating metal atoms replacethe water moleculesuntil the adion becomesfully co-ordinated
lattice.
In
ions,
in
incorporated
the
the
case
of
complexed
a similar growth mechanismoccurs
and
lost
instead
hydration
Further
ligands
the
the
the
complex
that
of
are
of
sheath.
adions are
except
incorporated and growth continues. Dislocations are particularly important to this mechanismof
is
in
the
the work of Bockris and Razumney
of
growth
adequately
covered
and
perpetuation
growth
here.
The
determining
be
detailed
is
step
of
such
rate
growth
mechanisms
often the
not
will
and
OmV.
I
Such
is
diffusion
to
the
up
overpotentials
of
adions,
a
growth
of
mechanism
often
surface
termed epitaxial or pseudomorphicas it closely continuesthe underlying structure of the substrate.

42

5.1.2 ElectrocrystaUisation at high current densities.

With increasing overpotentialand therefore increasingcurrent density, growth proceedsby 2
dimensionalnucleation, with groups of adionsincorporatingtogetherat step sites. Charge transfer
(activation control) now becomesthe rate determiningstepand this tendsto control the manner in
which the deposit grows.80.The stepssweepacrossthe surface and form well-faceted crystallographic structures.With increasingoverpotential, diffusion of metal ions from the solution begins
to influence the mode of growth. When the concentration overpotential is comparable to the
activation overpotential, deposition is under n-dxedactivation and masstransfer control. Because
of the high surface concentrationand high overpotentials,adionshave sufficient kinetic energy to
form nuclei on the crystal planes, forming a fine grained structure which is no longer epitaxial.
This mode of growth continues with increasing overpotential and current density until at some
overpotential determinedby the ratio of "'L, activation control is lost and masstransfer becomes
has defined
the rate controlling step. Deposit growth then becomes increasingly nodular. West8O.
the critical current density ratio in terms of the exchangecurrent density, i,,

RT (
-F In I-(

RT
(I-P)nF)

In

('io)crit

(to)

thus giving
)cru-

(!

0Nil

i_
`ii

'bb

(11)

t/

where x in this case is an empirical constant. These equationsindicate that (i /i),,,,

is small for

large values of i.. This is supportedby experimentalevidencethat nodular growth occurs for "'L
values of 0.9 for iron and nickel ( =2x 10,9)but for copper, '/'L is about 0.4 ( =4x 10-5)81.
Growth now proceedsthrough 3 dimensionalnucleation, in which nuclei form and grow not only
in the radial direction but also in the axial direction, ie perpendicularto the surface. This mode of
is exceeded. With
growth is responsible for the increasing nodulation of deposits as
increasing overpotential, a number of unique growths may be observed,such as dendrites, needles
and tip splitting branches(also known as densebranchedmorphology, DBM).

High speeddepositionis concernedwith obtainingcompact.high qualitydepositsat ashigh a

in
is
It
density
to
therefore
examine
greaterdetailthe way in which
as
possible.
necessary
current

43

is
(iiiL),,.,,
occur
as
approached.In this way, it maybe possibleto understand
morphological changes
the way in which deposit deterioration occurs and may lead to a meansof increasing the rate of
deposition whilst maintaining the quality of the deposit.

5.1.3 Mechanisms of surface irregularity amplification.

Electrodeposits
formedat "conventional"currentdensitiesaregenerallysmoothandcompact.
However,as the currentdensityis increased,surfacerougheningis observedto increase.There
havebeenmanystudiesonthemechanism
examined
of surfaceroughening.GabeandRobinson82.
the formationof powderanddendritesin copperdepositionusinga rotatingcylinder electrode.
Theyfoundthattheincidenceof dendriticorpowderdepositionwas
relatedto thetransitionbetween
chargetransferto masstransfercontrol.Theyestimatedthatthecritical ratio, "'L9 for copperwas
0.4. Ibl83-reviewedthe subjectof powderformationby electrodeposition
andits relationto mass
transfer.He concludedthat powderformation(anextremeform of nodulation)occurswhen'L is
development
reached.He alsoconcludedthatroughness
wasattributableto instabilityof thedeposit
surfaceunderdiffusionlimiting conditions.Instabilityheremeansthe selectivegrowthof surface
perturbations,leadingto roughening.As explainedabove,underconditionsof diffusioncontrol,
3 dimensionalnucleationoccurswhichcanleadto noduleformation.It hasbeenshownby Kindler
that for copper,at currentdensitiessubstantiallybelow 'L, a largenumberof nodulescan
et a184.
form. Thesenodulesappeared
to be largefacetedcrystals,overgrownwith a fine microcrystalline
structure.They claim that the fine structuredepositspreferentiallyon the largecrystals,leading
to noduleformation.The numberof largecrystalsalsoincreases
with increasingcurrentdensity.
Therefore,surfaceperturbations
arecommonbelow'L.DegrezandWinandalstudiedthedeposition
of copperat high ratesusing a high speedflow channel.Under thesecontrolledmasstransfer
conditions,theyconcludedthatrougheningof depositswastheresultof 3 dimensionalnucleation,
the onsetof which was proportionalto the combinedkinetic and concentrationoverpotentials.
havealsoidentifiedthe factorsthat enhancepowderformation.Theseare a
DespicandPopov86decreased
of depositingions,anoverallincreasein theconcentration
concentration
of theelectrolyte
in thetemperature
(supportingelectrolyte),an increasein theviscosity,a decrease
anda reduction
in the electrolytevelocity. All thesefactorsresultin a loweringof the limiting currentdensity.
havepresented
Bockriseta166.
a simplifiedexplanationfor instabilityoccurringunderdiffusion
control in the presenceof surfaceperturbations.Figure 7 showsa schematicdiagram of the
interfacial regionwith a singlesurfaceperturbation,theheightof which is considerablylessthan
the diffusionlayer thickness.If depositionproceedsunderdiffusioncontrolanda linear diffusion
gradientis assumed(not strictly true), thenthe diffusioncurrentwill be givenby

44

iaDnFCa-Co

(12)

As the thicknessof 6Pk is less than that of 6.,, ip,,. will be greater than i.. due to both field and
f, k
f
diffusion distanceeffects. Therefore, the peakwill increasein height. In addition, the electric field
becomesconcentratedat a perturbation further increasingits rate of growth. This implies that any
slight surface perturbation will always lead to a rough deposit. It is obvious from practical
observationsthat this is not always the caseand there are other factors at work that can lead to
stabilisation of the surface. Therefore there have been many attemptsto analyse all the factors
responsiblefor surface rougheningand put these into a stability theory.

Bulk

D.Ffus. on
layer

electrolyte

S'..

s.,..

y
Figure 7. A diagram showing how the thickness of the diffusion layer is lower above a surface
perturbation provided the perturbation is small.

5.1.4 Stability theories for roughness development.

Most of the stabilitytheoriesfor electro-growthhavebeendevelopedbasedon the analogous

The
during
from
the
melt.
analogyof electro-growthwith
solidification
crystal
growth
of
situation
driving
forces
is
During
the
controllingcrystalgrowth
one.
solidification,
a
reasonable
solidification
diffusion
from
(
ions
heat
diffusion
to
the
to the
equivalent
away
crystal
of
growing
metal
are
Mullins
degree
(
to
overpotential).
the
the
of
undercooling
equivalent
andSekerka87and
surface)
during
for
the solidificationof a binary alloy by
theory
a
surface
planar
a
stability
postulated
dependence
time
the
of the amplitudeof a sinusoidalperturbationof small amplitude
calculating

45

introduced to the plane. They also addressedthe morphological stability of a particle growing by
diffusion or heatflow. 88.Their conclusionwasthat althougha surfaceperturbationwill be amplified
and thus be unstable, stability could be achieved by the effects of the surface tension of the
crystallites, termed capillarity, providing the curvature of the perturbation was sufficiently small.
Aogaki89-extendedthis theory to the formation of electrodepositedmetal powders. Landau and
Shyu9Oapplied the theory to the developmentof surfaceroughness.This was further extendedby
The previous theorieswere claimed to be deficient as they did not take account
Barkey et al. 91-92.
of the ohmic overpotential. They concludedthat the morphological stability of the electrodesurface
is controlled by the electric field, the fraction of the limiting current and the surface energy.
However, the model developedby Barkey etal did not correctly predict the magnitudeof protrusion
spacing and were half that found by experiment.
Chen and Jorne93-included a damping factor to account for the degree of influence a perturbation
has on the diffusion layer thickness. They claimed that if the perturbation is very small compared
to the thickness of 6, then the diffusion layer boundary would be unaffected and could be taken as
being flat. This was not taken into account in the previous treatments. They went on to develop a
mathematical treatment and formulated a stability theory which agreed with experimental evidence.
They showed that the surface tension was the only stabilising factor in the system. Without the
influence of the surface tension, the perturbations would always grow with time. They pointed out
that the surface concentration of adions influences the stability by affecting the surface tension. In
the case of a zero surface concentration, the surface tension loses its stabilising effect and all the
surface perturbations will tend to grow. Instability is also encouraged by the magnitude of the
concentration gradient at the surface with large concentration gradients encouraging the growth of
increasingly smaller perturbations. In addition, increasing the metal ion concentration and reducing
the thickness of the diffusion layer both encouraged instability. This, in effect, is the same as
increasing the concentration gradient

5.1.5 Theories of needle, dendritic, densebranching morphology (DBM) and fractal growth.
Deposits produced above the critical ratio of "'L not only produce rough nodular deposits.
Under certain conditions of electro-growth, needles, dendrites, tip splitting dense branching
morphologies and fractal structureshave been observed. Figure 8 shows schematicdiagrams of
these morphological structuresproduced by electrodepositionin a2 dimensional Hele-Shaw cell
(Seelater). Whilst thesestructureshavebeenproducedin a two dimensionalcell, they sharemany
characteristics with those produced in the more conventional three dimensional systems. In the
caseof a needlegrowth, this is characterisedby a numberof thin needle-likecrystals with parabolic
tips exhibiting little or no lateral growth habit. This shouldnot be confusedwith whisker formation,
which are causedby the interaction of foreign molecules with a growing surface.75.A dendrite is

46

essentially a needlegrowth with lateral side arms growing at specific angles to the main growth
direction. Further lateral growths are often observedon theseside arms. The DBM structure is
characterisedby its lack of crystalline regularity althoughthe DBM also differs from a dendritic
structure in terms of its tip splitting habit. They also exhibit a regular growth front, with all the
leadingtips in the samespatialposition relativeto the electric field. Fractal growths arecharacterised
by their irregular growth fronts. Each of thesestructuresmay be produced electrochemicallybut
they are also observedin solidification from melts, precipitation from supersaturatedsolutions and
amorphousannealing.This would indicatethat thereare commoncausalprinciples to thesegrowths
irrespective of the nature of the growth medium.
The earliest theories of dendritic and needle growth are attributed to Barton and Bockris94.
.
They proposed that dendritic growth proceededfrom a surface perturbation by means of mass
transfer control. They startedwith the growth of a macrospiral (the growth of a spiral dislocation)
that has a very small tip radius (r -10-6cm). Under theseconditions, diffusion to the tip is controlled
by spherical diffusion as opposedto planar diffusion. The current density at the tip is given by
DnFc b/r insteadof DnFcb /6. Since r<<6, the limiting current density is much higher on the tip.
They also argued that becauseof the high step and kink density, the tip has a higher exchange
current density and the activation overpotentialwould be much lessthan on the surrounding planar
surface. This leadsto an acceleratedgrowth of the tip which subsequentlydevelopsinto a needle.
The important factors relating to the initiation of needleand dendritic growth have been identified
as being two critical overpotentials, the first being required to initiate the growth of the screw
dislocationsand the secondto producediffusion controlled conditionsat a rate necessaryto produce
the tip radius suitable for sphericaldiffusion. 95.An initiation period was identified in which these
identified
Critical
formation
for
both
dendrite
overpotentials
were
occurred.
and
powder
changes
for copper and cadmiumby Popov et al. 96-97-98,
using the Barton-Bockris theory. Whilst the theory
is able to explain the growth of needles,there still remained the question of the instability of the
individual
It
branching.
dendrites
treated
the
to
with no reference to the
also
as
needle growth
influence that other protrusions had on their neighbours.
Despic and Popovm.commentedin their review of transport controlled mechanismsthat as
twinning is frequently observed in dendrites, the regular angled sidearmsmay be due to growth
from twin sites. Twin sites represent low energy sites for lateral growth and as such enjoy an
enhancedgrowth rate. This would accountfor unique anglesobservedany particular metal as the
However,
by
is
the
twin.
they were unable to offer a
the
properties
of
crystal
controlled
angle
dendrite.
for
the
the
the
of
spacing
sidearms
on
regular
reason

47

--d-

in a Hele-Shawcell. (a)
Figure8. Typicalmorphologicalstructuresproducedby electrodeposition
(DLA)
A densebranchingmorphologystructure(DBM), (b) a fractalor diffusionlimitedaggregate
structure,(c) a dendriticstructure,(d) a needlestructure.

48'

One important distinguishing feature of a dendrite is the long range crystalline order present.
It has been suggested'03.
that a stacked plane structure provides the necessaryanisotropy that
stabilises the growth of a dendrite and prevents it forming similar but disordered fractal or tip
splitting structure.
Dense Branching Morphology structures occur if the influence of anisotropy is reduced by
other external factors. This type of morphology is characterisedby the formation of irregular
branching structuresthat undergo random tip splitting. However, there is generally a long range
has examinedthe differences between
order in that they follow a regular growth front. Barkey-11.
this type of morphology and dendritic structuresby examining Schlieren photographsduring the
growth of both dendritesand DBM structures.Thesephotographshighlight density differences in
liquids allowing the shapeof the masstransfer boundary layers to be seen.He concludedthat it is
the shapeof the masstransfer boundary layer that selectsthe developmentof either a dendrite or
a DBM structure. In the caseof a dendrite, the boundary layer resemblesa shock wave with the
tip of the dendrite being close to the boundary layer. In the caseof the DBM, the boundary layer
distance
some
advancing
aheadof the tip splitting branches.He went on to conjecture
observed
was
that in the caseof the DBM, a hydrodynamic instability is set up due to the fast growth of the tip
less
interaction
the
the
of
viscousboundary layer and the bulk. This createsa gradient stress
and
across the liquid interfaces that setsup a dynamic surface tension. It is this surface tension that
front
the
and prevents random variations in the growth velocity of different
growth
stabilises
branches.Thus, a continuous,regular growth front is preserved.The tip splitting results from the
growth of a surface perturbation via a Mullins-Serkerka type instability betweenthe fluid layers.
In the event of a significant protrusion, growth occurs of that protrusion resulting in tip splitting.
This type of morphology is rarely seenunder conventionalconditions of electrodepositionbut may
be realised under conditions of high overpotential and low metal ion concentration.
Fractal structureshavebeenlikened to Diffusion Limited Aggregates(DLA) observedin other
by
These
particle
aggregation.
characterised
a non-uniform growth
as
smoke
are
such
systems
front and a lack of symmetry. In addition, they havebeenshownto possessno long range ordering.
Such structures occur if the surface tension effects seenin DBM are reduced. As a consequence,
the Mullins-Serkcrka instability predominatesallowing surfaceperturbations to grow unchecked
in
This
a random structure that hasbeenfound to possessa fractal Hausdorf
results
and at random.

49

dimensioft*. One other important property of fractal objectsis what is known as scaleinvariance.
These objects are invariant under a transformation which replacesa small part by a bigger part,
that is, under a changein scaleof the object.
Recent work has been carried out on the morphology selection mechanisms of dendritic and
allied growth by means of two dimensional electrodeposition cells known as Hele-Shaw cells. 99.
The cell consists of 2 sheets of plexi-glass separated by a narrow gap of about
100.101.102,103.
0.001-0.01 cm which contains the electrolyte. A ring anode is set around the edge of the plates
and a small hole is supplied in the top plate for the insertion of the cathode. The cathodes used
vary but are usually copper wire. By applying a suitable potential across the cell, a variety of two
dimensional dendritic and fractal structures may be grown. The type of structure is highly dependent
on the nature of the electrolyte and the growth conditions. It has been found that for true dendritic
growth, crystalline anisitropy must be influential. If the influence of anisotropy is reduced, then
DBM and fractal growths predominate. The conditions controlling the type of structure produced
can be summarised by figures 9a and b. 101-100.

The differences in the morphological diagramspresentedabove are presumably due, in part,

to differences in interpretation of the types of structure observedand partly on slight differences
in experimentalset-ups.Additionally, it hasbeennotedthat there is a considerableregion of overlap
betweenmorphology transitions.

The work by Ben-Jacob

andothers(seereferencesabove)hasbeenprimarily to correlatethe
formationof similar patternsover a wide rangeof physicalandorganicsystemsthat havemuch
in common.Suchdiversepatternsas that of a snowflaketo the structureof a coral reef or the
both fractalanddendritic,to the formationof aggregations
formationof electrodeposits,
of soot
particlesare believedto be subjectto unifying underlyingprinciples.It is now recognizedthat
interplay
interfacial
between
dynamics,suchas
the
the
result
of
are
microscopic
structures
such
diffusion, andmacroscopicformsunderhighly non-equilibriumconditions.

Me Hausdorf dimension, also termed the fractal dimension D can be derived as follows. Mic density correlation function c(r) of a
fractal may be defined as die averagedensity of an object at distancer from a point on the object and is an measureof the average
environment of an individual particle making up the object. Ile term c(r) reflects the scale invariance and it may be shown that the
only way in which c may vary is as a power law in r. Any other function would have an intrinsic scale. 71e term c may be written
in the following form:
e(r)-

kr'(d-

0)

Here, k is a constant and the exponent is written in terms of the dimension of space.d and D is the fractal or Hausdorf dimension.
Now, c(r) is a decreasingfunction of r as the averagedensity decreasesas the object becomeslarger. Consider how the mass of an
object, M, scaleswith the mean radius, R. We can estimatethis by multiplying a typical density from the above equation, by the
volume:
A,f(R)-

KRO'dRd- KR1

The termK is anotherconstant.It maynow be apparentwhy D is calleda dimension.For simpleobjects,D coincideswith the
a non-integer
usualnotionof dimension.But for fractals,D is not an integer.lberefore, if an objectcanbe shownto possess
Hausdorfdimension,it cantruly be calleda fractal.

50

For a quantitative description of this interaction between the microscopic and macroscopic
forces that dictate morphology selection,the readeris referred to reference 103. However, a brief
Under
be
here.
description
conditions of non-equilibrium growth, such as
given
will
qualitative
the formation of a snowflakeor the growth of a dendrite,the initial stablesolid phasewill propagate
into an unstableor metastablephase.In the caseof the snowflake, a collection of solid stablenuclei
it
In
dendrite,
into
the
the
the
case
of
supersaturated
water
vapour
phase.
unstable
propagates
ie
into
is
in
highly
into
tip
that
a
state
a
moving
a
non-equilibrium
an
electrolyte
propagates
continuously changing diffusion and hydrodynamic layer. The rate of growth of the stable phase
is limited in both casesby a diffusion process. As a result, the kinetics of the diffusion process
determine the macroscopicapproachof the solid phaseto equilibrium. In doing so, the system is
driven towards the formation of irregular or dendritic shapes.The exactform of the resultantshape
kinetics
depend
tension,
things
and anisotropy. and these are
as
surface
surface
such
on
will
determined by the exact conditions of growth and the nature of the growing material. Together
with diffusion kinetics, these microscopic forces determine the macroscopic approach towards
equilibrium and influence the structureson many length scales.
The reasonfor investigatingsuchnon-equilibrium crystallisationmodesis that under conditions
interface
high
is
due
far
from
to
the
the
overpotentialsapplied.
equilibrium
ofjet electrodeposition,
As such, it is to be expectedthat such structuresare likely to occur close to the upper deposition
limit during jet deposition. This is indeed observedand will be discussedlater.

51

lOM

CT
N

0.10M

O,O1M

1.0

5.0
APPLIEDVOLTAGE

10.0

(a)

LOM
OPEN

STRINGY

0,10M
N

DENDRITIC

HIM

1.0

HOMOGENEOUS
A
,
5.0
10.0
APPLIEDVOLTAGE

(b)

Figure9 (a) Morphologicaldiagramof zinc depositsfrom theHele-Shawcell (After Grier et al,01.

(b) Morphologicaldiagramof zinc depositsfrom the Hele-Shawcell (After Sawadaet al'OO.
)

52

CHAPTER 6

HIGH SPEED JET ELECTRODEPOSITION

There have been relatively few papers published on the subject of high speed jet deposition.
Of these, deposit morphology has not been given serious consideration. The emphasis in these
for
jet
been
has
the
transfer
mass
characteristics
of
models
mathematical
establishing
on
papers
Although under
deposition. Of these, a high proportion deal with a submerged jet, '. 104-105.106.107jet.
2.108.There
to
transfer
the
these
results
are
applicable
un-submerged
mass
certain conditions,
have been a number of papers published concerning the use of jets in electrochemical machining
but these are of little consequence to this study and will not be referred to. The earliest published
by
Zarb.
He
described
109jet
was
a system that made use of multiple
electrodeposition
work on
jets in order to produce selective gold deposits on lead frames. No masking was used. He claimed
in
15 seconds could be achieved using a pure gold electrolyte.
2
deposition
of
that
rates
tLm

In 1974, Fletcher,"O. describingan invention of G.D. Oliver, filed a Patenton behalf of NASA
describing a selectiveplating methodusing a pressurisedjetof electrolyte. Thejet could be moved
digitising
information
be
By
of
means
a
video
system,
on
a
pattern
could
under computer control.
introduced into the control system. The jet was scanned,raster fashion, acrossthe substrateand
In
in
the
this way,
times
the
with
control
pattern.
accordance
appropriate
at
the current was applied
in
dot-matrix
be
the
much
a
printer producesa picture.
same
way
as
written,
could
a plated pattern
No other publication by Oliver has been found and therefore few details of the process and the
deposits
the
produced are available.
of
morphology
Before examining the mathematical models for the mass transfer within jets, it is essential
hydrodynamics
the
the
of such a system.
of
nature
understand

6.1 CliARACTERISTICS

OF FLUID FLOW WITIHN JETS

Many studieshavebeencarried out on the flow characteristicsof submergedand un-submerged

jets. The flow patterns created within both systems are very complicated. The Navier-Stokes
for
Therefore,
flow
difficult
describe
the
the
to
whole
solve
system.
many
that
are
could
equations*

theequationsof motionfor a Newtonianfluid of a constantdensityandviscosity.It relates

*Ile Navier-Stokes
equationsrepresent
lbe
derivation
is
beyondthe
in
fluid
the
terms
the
co-ordinates.
of
in
z
cartesian
equation
x,
y
&M
of
of
volume
the motion a unit
in
is
here
it
However,
vectorterms
given
this
work.
scopeof
I
av
VP+VV'V +g
; -,+v -VV123and124,togetherwith theequationwrittenin rectangularco-ordinates.
A fuller descriptionmaybe foundin References

53

workers have divided the flow into four distinct regions as can be seenin figure 1. Theseregions
are termed 1) The free jet region, 2) The impingement region, 3) The wall jet region, 4) The
hydraulicjump. The hydraulicjump is uniqueto non-submergedjets. Whilst there are considerable
differences between the flow mechanisms,it has been shown that when the nozzle is within a
specific distancefrom the surface, then conditions of flow are similar for both the submergedand
un-submergedjets within the impingementregion. The wall jet characteristics,however are significantly different due to interaction betweenthe surrounding medium.

6.1.1 Flow within the free jet region

Thefreejet is theregionbetweenthenozzleandtheimpingement
zoneprior to anyinteraction
Schlichting"L
jet systemusing
target
the
studiedthe freejet within the submerged
surface.
with
boundarylayerequations.He foundthatajet will becomecompletelyturbulentat a shortdistance
from the dischargepoint asthe emergingjet becomespartly mixedwith the surroundingfluid at
flow
decreases
in
direction
jet
flow
Consequently,
the
the
the
mass
of
and
spreadsout with
rest.
However,
in
thetotalmomentumremainsthesame.Studiesof non-submerged
velocity.
a reduction
jets'12-haveshownthatthevelocityremainsnearlyconstantcloseto thenozzleexit. However,as
jet, at somedistancefrom the nozzle,turbulenceoccursdue to a
in the caseof the submerged
j
The
bell shapedwith themaximum
the
within
et.
velocityprofilebecomes
profile
varyingvelocity
jet
line.
This is a resultof entrainmentof thesurroundingair and
the
centre
on
velocityoccurring
discussed
thetheoreticalsolutionto the Navier-Stokes
equationfor
the flow breaksup. Squire'13laminarflow in a freejet.

6.1.2 flow within the impingement region

the surface,theaxial centre line velocitydecreases

As the freejet approaches
rapidly to zero
Within
flow
is
is
the
the
this
transformedto
termed
point.
zone,
axial
velocity
stagnation
what
at
found
The
Navier-Stokes
by
Schlichting.II'.
to
the
solution
exact
equation
was
velocity.
a radial
The stagnationzoneis, in effect,a regionin whicha staticboundarylayerdevelops,the thickness
flow
The
between
is
dependent
the
transition
thestagnation
prevailing
on
conditions.
point
of which
been
be
jet
has
by
Dawson'
However,
be
14.
to
the
calculated
wall
r/d4.
as
will
seen
and
region
below, this valuedependson the valueof H/d.

54

6.1.3 Flow within the waUjet.

The walliet region hasbeenextensivelystudied3.115.116.
as it is observedin other flow situations.
The equivalent of wall jets can be found in laminar flow in pipes, channelflow and flow acrossa
flow
in
At
the
the radial direction in the
the
stagnation
region,
accelerates
rapidly
edge
of
plate.
form of a thin layer. As the fluid spreads,a boundary layer developsadjacentto the surface. The
flow adoptsa Blasiustype flat plate profile*. The boundarylayer increasesin thicknesswith radial
layer,
flow
is
by
boundary
Outside
this
and
unaffected
viscous stresses.
uniform
position.
In an un-submergedjet, there comesa point, dependenton the original axial velocity, at which
the thickness of the boundary layer approachesthe total thicknessof the wall jet. This is known
flow
is
forces
The
to
viscous
transition
whole
subsequently
subject
and candescribed
the
region.
as
Due
from
to
the
the plate, the bulk velocity gradually
viscous
effects
solution2.
using a similarity
becomesretarded.Whenthe thrust of the pressureof the flow is equalto the rateat which momentum
is destroyed, a hydraulic jump occurs in order to conservemomentum. In effect, a standingwave
is created. Flow beyond the jump region then continuesundisturbed.

6.2 MASS TRANSFER CHARACTERISTICS OF IMPINGING JETS

havebeendevelopedby bothmathematical
Masstransfercharacteristics
modellingandtested
by experiment.Both submerged
andun-submerged
systemshavebeenevaluated.Much work has
beencarried out using the analogoussystemof heattransfer.Whilst the generalbehaviourof
from
different
jets
that of non-submerged
systems,undercertainconditions,
very
are
submerged
behaviourwithin the impingementregionis very similar. Therefore,some of the characteristics
be
will
revued.
system
the
submerged
of
6.2.1 Mass transfer in submerged jets.
Mass transfer and heat transfer are analogousin their behaviour. As such, work carried out
Work
by
to
heat
transfer.
experiments
transfer
and
are
applicable
mass
models
undertaken
using
Gardon and Akfirat' 16.
measuringheattransfer with airjets hasshownthat at large nozzle to surface
distances,the heat transfer decreasedin a monotonic mannerfrom the stagnationpoint. However,
in
heat
d'/d
0.5.
local
H/d,
transfer
at
was
observed
maximum
=
a
at small

Me Blasiusflat plateboundarylayerproffleis foundin a numberof hydrodynamicsituations.In particular,whenflow accelerates

increases
develops,
distance
layer
the
boundary
the
of
flat
plate
and
start
commencing
at
with
alongtheplate.The
a
plate,
a
along
friction
inducedby the wall. Nakoryakov3
flow
function
is
has
layer
the
the
the
and
viscosity
the
rate,
a
of
that
attains
thickness
describeddie analysisof masstransfer in this region.

55

Mass transfer in a submergedjet systemwas also shown to be highly dependenton the distance
betweenthe nozzle and the impingementsurface. Giralt'17- and Scholtz"s. have explained that
with large nozzle to surfacedistancesie H/d 2:8.0, the flow in the free jet has a fully developed
bell-shapedprofile. As a consequenceof this, the accelerationof the wall jet commencesat the
stagnationpoint and masstransfer is greatestat the stagnationpoint. At smaller values of H/d, the
jet still retains much of the flow characteristicsof the nozzle. Providing the flow within the nozzle
is uniform to begin with, then this profile is retained.Consequently,the accelerationof radial flow
is
d'/d
0.5.
This
the position at which the boundary
corresponding
with
at
a
position
commences
=
layer is thinnest and the masstransfer highest. In betweenthesevalues of H/d, the masstransfer
is relatively constant. Other experiments and theoretical calculations using controlled flow
conditions'19.have shown that with uniform flow distribution, the position correspondingto d'/d
= 0.5 exhibits the greatestmasstransfer. With a parabolic flo profile, this position corresponds
*w
to d'/d = 0.1.1M Mass transfer within the impingement region has been studied by Chin and
Using disc electrodesof various radii, they measuredthe masstransfer using the limiting
Tsang.105.
found
limiting
They
density
that
the
average
current
remained constantup to
method.
current
dI/d = 0.5 for laminar jet flow. However, under conditionsof turbulent flow, this value increased
to 1.0. These phenomenonmay be explained in terms of fluid acceleration.The fluid velocity of
the wall jet along the substratemay be derived from inviscid theoryl. as

U., - 1.161
r
U., -0.451611
r

f or
for

H/d -

0.25

H/d-

1.0

f or

non-unif

for

uniform

orm
flow

f low

(13)

The accelerationwith increasingdistancefrom the stagnationpoint for a non-uniform jet is twice

that of the uniform jet. With a reduction in H/d, the passageof the fluid is restricted, leading to
between
differential
Consequently,
the
the
stagnation
point
and
ambient.
pressure
an enhanced
fluid accelerationis increasedleading to a maximum outsidethe stagnationpoint. At intermediate
It
be
H/d,
are
observed.
may
concluded, therefore, that the mass transfer
maxima
no
values of
dependant
impinging
fluid
the
the
are
system
on
of
profile, which dependson the
characteristics
flow,
However,
H/d.
turbulent
conditions
under
of
uniform masstransfer may be observed
value of
H/d
is
diameter
I
not too great or too small.
providing
to
nozzle
up
6.2.2 Mass transfer in the non-submerged jet
Mass transfer datais generally presentedin the form of the Chilton-Colburn analogy, originally
developed for heat transfer studies. The general form for the equation is given by

56

Sh. - Re, Sc

1/3(c

1/2)

Chin and Hsueh'20usedthis equationto derivea form that is applicableto the non-submerged
impingingjet geometry.Local friction coefficientswereobtainedfrom the work by Nakoryakov
et al.
(i) in the impingementregion
C, - 0.662v

112U312XIU

2(d/2)
.

3/2

(ii) in the boundary layer and wall jet regime

0.579u

112U312XIU2
x

(d/2)

1/2

(16)

havethe following forms

Additionally, it hasbeenshownthatthe radialvelocitycomponent
(i) in the impingementregion"'.

U, - gd'

(17)

U, -U

(18)

(ii) in the boundary layer region'20.

By substituting equations(15) (16) (17) and (18) into the Chilton-Colbum equation and averaging
the local masstransfer coefficients over the electrodesurface, a set of correlations for the average
Sherwood number can be calculatedas

57

(i) for the impingementregion

Sh = (0.936/a

*)Re

112SC113

(19)

(ii) for the boundary layer region

5h - 0.767Re
.

112SC 113(r'ld)

-1/2

(20)

The parametera* is a dimensionlesshydrodynamic constantdefined as ad/U, which is a function

height,
H/d.
dimensionless
the
nozzle
of
Most masstransfer characteristicsare defined by such an equation as that derived above and
take the general form of

Sh - aRebSc'I(Hld)

(21)

The derivation of this equationcan be found in the excellent Chapterby Ibl and Dossenbach'23The value for c is generally acceptedto be 1/3. The masstransfer characteristicsare different for
jet
For
former,
it
has
been
found
by
to
the
the
impingement
wall
compared
region.
region
the
Giralt and Scholtz that the value of b is 0.5 for the submergedjet. The value of a is dependenton
but
is
between
0.5
For
degree
1.
turbulence
the wall
the
generally
of
and
and
the velocity profile
jet, b has been determined as 0.75 and is inversely proportional to the radial distance, d'. The
functional relationship betweenthe masstransfer coefficient and the nozzle to substratedistance
is generally expressedas a power relationship
f(Hld)-(Hld)-o

(22)

Valuesfor e' vary. Chin and Tsangfound a valueof -0.054 and -0.057 for the submerged
laminarandturbulentjet flow respectively.However,in a laterstudy,Chin andHsuehfoundthat
for 0.5 < H/d < 5.0, a valueof -0.09 wasappropriate.

58

The basic mathematicalmodel for the non-submergedjet has been determinedby Alkire and
Chen as applicable to electrodepositionsystems.They modelled the current and potential distribution along a cathodesurface in a high speedjet plating cell. The model was based on the
limiting current measurementof masstransfer using the reduction of ferricyanide in an alkaline
solution. They went on to study copper depositionfrom an acid sulphateelectrolyte both with and
is
ferric/ferrous
The
redox
couple
added.
reader
a
referred to this referencefor a detailed
without
description of the derivation of the model. They found that in the impingementregion, correlated
in dimensionlessform, gave the following relationship over the range 3000 < Re < 60000

Sh - 21.03Re

0,448

(23)

This, they claimed, agreedto within 10% of a semi-empirical correlation derived by Chin and
Tsang for a turbulent submergedjet. In this work the H/d was maintainedat a value of 2.0. This
in
impingement
the
transfer
characteristics
the
that
region were essentiallythe same
mass
ensured
jet
For
found
following
jet.
the
they
the
for
wall
region,
relationship
submerged
a
as

Sh., - 0.572Rex

O.5SCO.

33

(24)

Nakoryakov et al also derived a relationship for the wall jet basedon theoretical predictions of
Sh - 0.59Re

0.3scO.

33

(25)

dimensionless
Sherwood
to
the
number
notation.
after converting
Alkire and Chen, basedon both their theoretical and experimentalstudies, went on to establish
jet
From
the
behavioural
their
system.
of
experimentsusing the redox system,
properties
certain
following;
15%
theoretical
the
to
of
calculations
within
they established

59

Low currents led to high selectivity but a low plating rate whilst high currents give high
plating ratesbut low selectivity. Here selectivity is defined as

S-

metal

deposition
total

in

metal

impingement
deposition

region
rate

They claimed that the reasonfor this was that at low currents, the behaviour was controlled
by potential distribution and that as the impingement region was closest to the anode, the
favoured.
high
limiting
At
impingement
in
the
the
currents,
current was
region
was
reaction
by
the
controlled
masstransport.
system
was
achievedand
2.

The electrolyte conductivity influenced the behaviour. Electrolytes with a reduced conductivity led to an improved selectivity at low applied currents but at high currents had no
influence.

3.

Increasingthe reactantconcentrationled to a significant increasein selectivity at large currents

limited
in
impingement
in
jet.
but
transport
the
the
mass
region
not
wall
was
as the system
At lower currents, the systemwasdominatedby chargetransfer and ohmic resistanceeffects.
Increasingthe concentrationled to an increasedexchangecurrent density, causinga reduction
in chargetransfer resistancecomparedto the ohmic resistanceand thus moderately improved
selectivity.

4.

increasingthejet velocity improved the selectivity at large currentsbecausethe impingement

fraction
limiting
higher
the
of
current than the rest of the surface.
at
a
region operated
Increasesinthe rateof agitationthusfavours reactionsin the impingementregion andenhances
low
kinetic
However,
the
currents,
at
as
and ohmic parameterscontrolled the
selectivity.
behaviour, no changein the selectivity was observed.

Whilst they found good agreement between the experimental results and the theoretical
found
high
ie
high
flow
that
under
conditions
selectivities
gave
were
rates,
errors
calculations,
high reactant concentrationsand low conductivity. They put this down to errors in the one
dimensional simplification they used for the theoretical calculations and had underestimatedthe
higher
These
than
predicted
a
selectivity
were actually observed.
errors
rates.
reaction

In the caseof copperdepositionfrom theacidsulphateelectrolyte,the calculationsincludeda

factorto takeinto accounthydrogenevolutionthatoccurredat high currentdensities.In this case,
data
for
different.
Not
behaviour
the coppersystemto
was
enough
given
quite
was
the selectivity
but
low
ferricyanide
for
the
essentially,
appliedcurrentsexhibited
as
analysis
enableascompletean
levelling
increasing
increased
to
current
eventually
applied
with
a constant
which
selectivity
poor

60

value. The reason for this was believed to be the difference in the exchangecurrent densities of
the two systems. During their studies, a dimensionlessnotation was derived to assist in the
mathematicalmodeling of the systemincluding a term t. This was defined as
rFa, d2io
xRT

(26)

where a, is the specific surfacearea and is a volume componentof the electrolyte involved in the
is
in
Its
derivation
given
reference(1) but is not importantto this discussion.The important
reaction.
aspectis the inclusion of the ratio of exchangecurrent densityto the conductivity i,,/x. This played
interpreted
be
in
This
important
the
could
selectivity
achieved.
as a ratio of ohmic
ratio
role
an
If
losses
transfer
this value was greater than unity, the current
to
charge
overpotential.
potential
distribution would be highly non-uniform andthusselectivity would be high. By way of illustration,
three values of t were plotted as selectivity vs total applied current for high rates of flow. These
values were 104,104 and 101.Of these, the intermediatevalue exhibited the poorest selectivity.
At low currents, a large value of k correspondedto ohmic control so that selectivity would be
expectedto be high due to non uniform current and potential distributions. Very small values of
k correspondto charge transfer control and thus a more uniform potential distribution. However,
the charge transfer overpotential must be very high in order to support the required current. Due
to the exponentialnature of the kinetic rate relationship (Butler-Volmer equation)modestpotential
distributions.
for
low
highly
Therefore,
non-uniform
current
currents,
generate
can
variations
is
increased.
For
high
depends
k
through
a
minimum
as
currents,
selectivity
on
selectivity passes
insensitive
in
is
to
t.
thus
variations
transfer
and
mass
Another term defined was r. This dimensionlessterm comprised

I_n2F2

kc"a, d2
xRT

(27)

This term included the ratio kclx and could be interpretedasthe ratio of masstransfer overpotential
dimensionless
limiting
be
Such
term
a
could
viewed
a
as
current. If r had a
to ohmic potential.
be
The
high
deposition
then
than
could
achieved.
very
mathematical
rates
unity,
greater
value much
high
deposition
be
if
both r
that
selectivity
could
achieved
rates
with
good
very
model predicted
and t had values greater than 10.

61

In the caseof copper depositionwith a redox couple, the chosensystemwas more noble than
the copper reduction. Therefore, at low current densities,the reduction of ferric to ferrous predominated.The current efficiency for copperdepositionthereforeincreasedwith increasingcurrent
density. Thus, the current efficiency was highestin the impingementregion. This led to a situation
in which the selectivity was low at low currents increasingto a maximum with increasingapplied
current. At very high applied currents, the selectivity reducedas copper was depositedoutsidethe
impingement region. It was found that by using the redox couple, the maximum selectivity was
increasedtwofold.

62

CHAPTER 7

EXPERIMENTAL STUDIES OF HIGH SPEED SELECTIVE JET

ELECTRODEPOSITION

The following chaptersdescribethe experimentalwork carried out to evaluatethe properties

of electrodepositsproducedby the non-submergedjet plating method. As this techniquewould be
of particular value within the electronicsindustry, the bulk of the studiesconcentratedon gold and
gold/nickel alloys. However, somestudieswere carried out on copper and this is mentionedwhere
applicable in order to support, or otherwise, findings from the gold deposition work.

7.1. EQUIPMENT USED IN THIS STUDY.

For the purposesof relating the depositionconditionsto the depositsproduced, a large number
of deposit spots were produced over a wide range of current densities and flow conditions. To
produce these,it was necessaryto devisea stepand repeatsystemthat was able to move the nozzle
relative to the substrateand switch the plating current on and off for the appropriate times. In
addition, to demonstratethe applicability of the processfor the purposesof selective plating, the
equipmentwas required to move the nozzle at a desired speedwhilst depositing the metal. It was
decidedthat theserequirementscould best be provided by a motion control systemmanagedby a
microcomputer. Additional equipmentwas addedto this for specific requirementsduring the course
of the experimentation.

7.1.1. Computer controHed X-Y drive system

Figure 10 showsa schematicdiagram of the computer controlled X-Y systemdesignedfor this
study. Photograph I showsa photographof the system,with the X-Y Table in place within a fume
cupboard. This was necessaryfor safety reasonsas somefine electrolyte spray was produced. An
enclosed nozzle/substratecontainer was considered but this would have restricted access and
observationduring operation. However, a spray shield (not shown in the photograph)was included
to collect any backspray that occurred. The individual componentsof the system are described
below.

63

r ------------------------------------------------

jr ---------------------------------------------

1286
PC

I!

I Kcrocompuler

LjCo
II

stant curren
power suppty

Stepper motor
Translator card

i L--

Stepper motor
driver supply

Pumpcontroller

Pump

Electrolyte
Reservoir
Heat Exchanger

Figure 10. A schematicdiagram of the computer controlled jet plating system.

7.1.1.1 The nozzle and substmte mount.
The nozzle used for the majority of the experiments consistedof a2 cm long by 0.4 rnm
diameter platinum tube sealedinto a 0.3 nun, high lead content sodaglass tube. About 0.5 cm of
the platinum tube was sealedinto the glass.The exposedend was strengthenedby castingan epoxy
resin block around it and the end of the glass tube. After setting, the end of the strengthenedtip
was charnfered, ground and then polished. The internal diameter of the platinum tube was then
for
ovality and size using a microscope.
checked

The nozzleassemblywasthenmountedonto a supportblock on the X-Y table. The support

distance
blockwasprovidedwith amotorisedZ directioncontrolthatallowedthenozzleto substrate
to be adjusted.
The substratewasmountedon a perspexplateby meansof point contactstainlesssteelspring
for
The
fixed
These
the
the
current.
plating
plate
connection
was
electrical
also provided
clips.
it
housing
to the reservoir.
that
the
and
run-off
returned
collected
electrolyte
onto a perspex

64

7.1.1.2 The pump system.

The electrolyte was pumpedthrough the nozzleusing a Wallace and Tiernan diaphragmdosing
pump, Model No. G SOV. It was capableof providing up to 70 L hour' at pressuresof up to 0.7
MPa continuous flow and 0.9 MPa maximum flow. The pump was provided with two control
mechanisms,onebeing electronicandthe other a mechanicalhandwheelcontroller. The flow could
be controlled to within 2% of the desiredrate by meansof thesecontrollers. Diaphragm pumps
producea pulsedflow and thereforea pulsationdamperwasfitted. This was suppliedby Flowguard
and the chamber pressurewas maintained at 0.44 MPa by an external nitrogen supply. At this
pressure, flow pulsations were eliminated over the electrolyte pressure ranges used during the
experimentation.A pressurerelief valve was fitted and setto divert the flow at pressuresexceeding
0.84 MPa.
An electronic pressuretransducer.model BT'2025GIA, supplied by Sensortechnicswas fitted
downstream of the pulsation damper to monitor system pressure. The output was calibrated in
terms of the electrolyte flow and provided a meansof continuously monitoring the flow rate.

Theelectrolytewaspassedthroughaheatexchanger
placedupstreamfrom thenozzleassembly.
This consistedof a Quickfit glasscondenserwith a spiral internaltube. The outerjacket was
from
hot
water
a separatereservoirdeliveredby a peristalticpump.The electrolyte
with
supplied
temperature
wasmonitoredon emergingfrom thenozzleby a fine thermocouple
wire placed3 cm
impingement
the
point on the substratemountingplate. Adjustmentof the hot water flow
past
control.
providedsuitabletemperature
Immediately upstream from the nozzle, a Titan Enterprises flowmeter, model No. 103 was
fitted to give a direct measurementof the flow asa back-upto the pressuretransducer.The computer
provided the measurementoutput for this meter.
As each electrolyte used in this study had a different viscosity, it was necessaryto calibrate
the flow measuringdevicesfor eachone. This wascarried out by measuringthe volume of discharge
over a range of pump settingsand producing a calibration curve. The computer output from the
flowmeter wasthen compensatedfor anydifferences,aswastheoutput from thepressuretransducer.

7.1.1.3 The X-Y Table

The X-Y tablewascustombuilt by Time andMotion. It consistedof a doublescrewvertical

fitted
horizontal
Fixed
horizontal
the
to
slide
carrier.
was
a
single
screw
onto
which
carrier
slide
carrier wasa mountingplatewherethenozzleassemblywasfitted. Theunit wasequippedwith a

65

pair of homeproximity sensorsandendof travelcut-off switches.X andY motionwasprovided

by steppermotors.The unit wascapableof 2.5 jim/stepanda repeatabilityof 2.5
in half
jum
stepmode.

7.1.1.4 Motion control system.

Ile steppermotors were controlled via the computer. Fitted to the computer was a PCL 738
This
translator
card.
convertedmotion information from the host computerto suitable
steppermotor
signals for the stepper motor driver unit. This driver unit was built "in-house" based on the
SGS-Tbompson296 and 298 steppermotor driver chips. A 40 volt, 4 Amp power supply powered
the steppermotors via the driver. The driver was operatedin half step mode to obtain the motion
resolution describedabove.The nozzle could be moved either from the control program or directly
from the computer keyboard.

7.1.1.5 The plating current power supply.

The plating currentsupplywasdesignedandbuilt in house.It wasa constantcurrentsystem

which wascapableof supplyingup to 100mA at voltagesof up to 60 volts with a resolutionof
by meansof an operationalamplifier controllingthe
0.01 mA. A constantcurrentwasgenerated
magnitudeof currentsuppliedfrom apowertransistorby meansof anadjustablereferencevoltage.
This referencevoltagecouldbesuppliedeitherfrom thecomputeror by meansof internalcircuitry
71e currentcouldthereforebe seteithermanuallyor automatically
controlledby a potentiometer.
in
When
the
manualmode,ashortcircuitswitchwasusedsothattheappropriate
used
via computer.
current could be pre-setprior to deposition.It was also capableof supplyingpulsedcurrents
duration
from
0.01
msecs.
signalsprovidedby anexternalpulsegenerator.This mode
of
upwards
A schematic
diagramof thepulseplatingmodification
wasusedfor all thepulseplatingexperiments.
is shownin Figure 11.71e referencevoltagefor the power supply was deliveredby a pulse
generator.The total plating period was controlledby triggering the pulse generatorfrom the
via thevoltagedrop across
computerfor the appropriatetime. 'Ihe appliedcurrentwasmeasured
a 1.0K resistorin serieswith thecathodicsupplyby meansof onechannelof a storageoscilloscope.
The magnitudeof thepeakpulsecurrentcouldbe setprior to platingby shortcircuitingtheoutput
andsettingthe currentpulsevia a DC input.

66

To computer

Putse
000

generator

Power
-0

supply

00

00

Digital ammeter
Resistor

F -54

Oscilloscope
0

Jet

Figure 11. The modification to the power supply to enablepulsed current electrodeposition.
7.1.1.6 The computer and control program
The computer usedwas an IBM compatible286 processorbasedsystem.The program usedto
following
"in
house".
jet
It
designed
the
the
was
written
unit
capabilities.
plating
was
with
control
1) A Computer aided design (CAD) user interface that allowed the computer to be programmed
to move the nozzle to appropriateplaceson the substrateand producedeposit spotsof the required
be
basis.
duration
interface
This
step
and
could
also
used to program the
on
a
repeat
and
current
jet
"directly
basis,
to
the
to
the
on
nozzle
a
continuous
write" the elecmove
allowing
computer
trodeposit. Figure 12 shows such a design as it appearedon-screen

2) It allowedthe currentsandtimesof depositionto be setautomatically.

3) It measuredthe flow rateof the electrolyte.
4) It allowedtheimportingandconversionof HewletPackardGraphicsLanguage(HPGL)plotter
to be usedto drive the nozzle.
files producedby otherCAD packages

67

10227
max- 25 0 25
ABSX= MEN
ARS V= 12.4250
REL X=8.028
REL Y=A. MO
fI 1`2 1`3 1`4 I'S 1`6 1`7 -

place node
radius 98
reset rel
del last node
terminal node
place spot
change view

f18- step=

0.02S8

polygons
save
merge
text
main menu

Figure 12. The computer "user interface" showing the CAD design screen.
7.1.2 Additional equipment

In orderto carryout fundamental

studiesto establishmasstransfercharacteristics
of thejetting
to establishthe relationshipbetweenoverpotentialandcurrentdensity.
system,it wasnecessary
This requiredadditionalequipmentin differing configurations.This will be describedin Section
7.4.

7.2 EQUIPMENT AND METHODS USED FOR DEPOSIT EVALUATION

The depositsproducedwere evaluatedfor a variety of characteristics.The following techniques
were used for theseevaluations.

7.2.1 Deposit Morphology

All of the depositsproduced were examinedusing an optical microscope. In addition, many
Cambridge
S350
either
a
or a CambridgeS150ScanningElectron Microscope
using
were examined
(SEM). Optical micrographs were preparedusing an offset light source to create a slight shadow
highlighting
features,
thus
them.
surface
around

68

7.2.2 Deposit thickness

Deposit thicknesswas measuredusing either a SloanDektak 11or a Sloan Dektak 3030 surface
profilometer. A5 tLm stylus was used for all measurements.As the depositswere found to have
a gaussianprofile, the maximum thicknessof the deposit at the centre of the spot was recorded.
In addition, surface profiles were constructedby taking measurementsat 100 Itm intervals from
the centre of the spot to the apparentpoint of extinction of the depositprofile. The reproducibility
of measurementwas obtained by taking 12 measurementsof the same spot and obtaining the
standarddeviation of the averagemeasuredvalue. The thicknessmeasurementsobtained by this
methodwere occasionaflYcheckedagainsta microsectionthrough the centre of the spot to confirm
accuracy.

7.2.3 Deposit structure

The internal structureof someof the depositswas evaluatedusing both standardmetaflographic
by
X-ray diffraction. Microsections were made from deposits
as
well
as
methods
microsection
produced on metal substrates.The substrate,with up to 6 spots in a row, were first overplated
backing
20
a
silver
as
coating. Thesewere then mounted in a clear acrylic resin
of
about
with
tLm
and ground until the deposit spotswere exposed.They were then polished until the centre of each
The
for
10
Imastrip*,
then
gold
was
the
was
reached.
etched
seconds
gold
spots
using
of
-15
stripping solution at room temperatureto reveal the crystallite and grain structure.
Glass substrates,1.5 X 1.5 cm, metallisedusing sputteredcoatingsof chromium followed by
A
low
(400A
respectively)were usedtoprepare samplesfor XRD examination. Samples
and
gold
for
deposits
XRD
HSSJE
alloy
examination were prepared over a current density range
gold
of
A
differing
3.0
16.0
between
CM-2
with
and
quantities of nickel and/or addition agent (booster)
of
in the deposit. In the case of HSSJE pure gold, sampleswere produced over a current density
8.0
A
1.0
between
cm-2. The samplesconsistedof an array of 25 identically produced
and
of
range
spotsplated onto the substrates.Prior to XRD examination,the chroniium/gold layers not covered
by the deposited spots were stripped. The gold was removed using Imastrip followed by 20%
hydrochloric acid to remove the chron-durn. As the metallised layers were extremely thin, the
HSSJE
left
The
the
spots
virtually
unaffected.
centre-line thicknessof the spots
operation
stripping
in the array was maintainedabove 15.014mand confirmed by measurementusing a Dektak Surface
Profilometer after the XRD examinationhad taken place.

*Imastrip,suppliedby Enthone-OMI(UK)

69

For comparison, a series of control sampleswere prepared for XRD examination by conventional vat depositionmethods. Oneset were producedfrom a Ronovel N electrolyte containing
1.7 g 1-1nickel over the current density range 3.0 - 40 mA cnr2. A further set of sampleswere
produced over the samecurrent density range from an Auronal MRN bath also containing 1.7 g
1-1nickel, which is identical to the Ronoval N but containsno booster. Thesesampleswere used
to study the influence of the booster. Pure gold sampleswere producedfrom a typical acid citrate
These
density
1.0
20
0.06M
to
crrr2.
of
mA
over
a
current
range
gold,
containing
electrolyte
depositscovered the sametotal surfacearea of the substrateas that covered by the jet plated spot
array.
The X-ray diffraction datawasacquiredusing an SiemensD5000 X-ray Powder Diffractometer
(Bragg-Brentano geometry) equipped with a diffracted beam monochromator ((Cuka).
Measurementsof diffracted intensity were carried out over the 20 range 30* to 90*. Corrections
to the angular positions and breadth of the diffraction peaksderived from the samples, required
to compensatefor various instrumental and physical effects were applied. To determine these
in
dusted
The
fine
layer
(@
Ian
size).
sample
was
with
of
silicon
a
powdered
each
corrections,
bracketed
Widths
Half
Maximum
intensity
Full
(FWHM)
the
at
of
siliconpeaks
which
positions and
those from the gold were usedto calculatethe appropriatecorrectionsto position and width. Using
lattice
it
interpolate
known
to
parameter
of
silicon
was
possible
a correction to the
the precisely
for
lattice
for
thus
the
the
each
and
calculate
parameter
an
accurate
value
gold peaks
position of
line. The correction for line broadeningwas madeby assumingGaussianmodels for the observed
diffraction
instrumental
corrected
and
profiles.
profiles,
Data was derived from an analysis of the position, intensity and FWHM of the first five
diffraction peaksrecordedfrom the gold deposits. In the Bragg -Brentano geometry, the diffraction
from
those crystallographic planes which are essentially parallel to the
only
originates
pattern
derived
from
111,200,220
The
311
therefore
quite
the
reflections
are
and
sample.
of
surface
222
derived
deposit.
Only
III
distinct
the
the
within
reflections
are
and
crystallites
separateand
from the samecrystallites. Considerablecare therefore needsto be exercisedin interpreting data
from sampleswhich do not exhibit a true crystallographic random orientation.

Latticeparameters
werecalculatedfrom the angularpositionsof the first five lines(I 11,200,
220,311 and222) in the diffractionpatternfrom eachof the samples.
For thepurposesof this Thesis,crystallitesizewill bedefinedasa single,coherentdiffracting
D.,
be
below,
is
the
true
the
This
size,
as
will
as
crystallite
explained
same
not always
region.
intensity
half
full
The
for
of the Kcqline corrected
is
maximum
width at
but used convenience.
for instrumentalbroadeningwasusedto calculatethe crystallitesizeusingthe Scherrerequation.

70

(0.9k)
(tcoso)

(28)

where B= the broadeningof the diffraction line measuredat its half width maximum intensity
(radians), t= diameter of the crystal particle X= radiation wavelengthand 0= angular position
in degrees.
It was noted that the crystallite sizevaluescalculatedfrom the broadeningof the III reflections
using the Scheffer equation were significantly greater than the values derived from the 222
reflections. The crystallite sizes calculatedfor the two planes should be the same; that they are
not, suggeststhat the Scheffer model employed, which attributes all the intrinsic line broadening
to crystallite size effects, is an over-simplification. On the basis of this infonmtionsamples were
selectedfor a more detailed analysis in order to separatethe contribution to the observed line
broadening from crystallite size and strain (RMS) effects. This was undertakenusing the method
of Warren and Averbach-121.The successfulapplication of this type of analysisrequires as many
unique orders of reflection as possible. However, for an FCC metal examined using copper
radiation, the number of accessiblereflections with multiple orders is just 2, the 111 (222) and the
200 (400). In this study, line overlap problems combinedwith low peak intensities ruled out the
use of the hOOreflections so that only the 111 and the 222 peakswere used for the analysis.

In orderto accomplishtheanalysis,
a betterdefinedinstrumentalline broadeningstandardwas
by
This
achieved
producinga puregoldpowderandannealingit to thepoint where
was
required.
in
improvement
ka
ka2lines
be
is
It
further
the
the
resolution
of
and
could
achieved.
particularly
no
difficult to obtaina suitablegoldpowdercommerciallyandannealit in this waydueto its tendency
The observed
for grain growth andsintering. Therefore,a powderwas specificallyproduced%
diffractionlineswerecorrectedfor instrumentalbroadeningby dividingthe FourierTransformof
from
derived
lines
diffraction
thesampleby theFourierTransformof theappropriateline from
the

*A 50 g 1-1solution of gold chloride was produced by dissolving pure gold powder in aqua-regia and
Concentrated
dryness.
hydrochloric
to
acid was addedand re-evaporateduntil all oxides
near
evaporating
The
solution was then adjustedto the correct concentration using de-ionised
removed.
were
of nitrogen
in
10
it
to
the
produce
gold
grains
with
a
region
of
size
with
ordered
necessary
a
well
was
water.
jum
had
be
to
nucleated and grown very slowly. It had been shown that such a
structure. This meant they
by
be
100
A
the
temperature.
reducing
gold
chloride
using
acetone
at
room
achieved
ml
could
structure
sampleof the gold chloride was placed on a magneticstirrer at a temperatureof 35 *C and 30 ml of acetone
for
5
hours
Stirring
continued
a
after which the samplewas cooled to ambient
period
of
was
added.
was
3
days.
At
for
layer
the
this
to
a
period
end
of
period,
a
of gold powder was seenat the
stand
and allowed
bottom of the beaker that had merged to form a thin film. A piece of this film was cleaned in de-ionised
X-ray
diffraction
from
film
be
that
the
the
slide
so
pattern
glass
a
could
on
recorded.
mounted
and
water
The resolution of the ka doublet was determinedfor the first five lines in the X-ray diffraction pattern from
the film. The film was then subjected to a number of annealing operations at 350*C until no further
improvement resolution of the doublets was obtained. The total time of annealingto obtain this condition
was 5 hours.

71

It was found necessaryto subtractthe signal derived from

the standardas describedby Stokes.122.
the blank glass substratesfrom that of the samplesprior to calculating the transform, in order to
obtain a level baseline required for an accurateanalysis.

The full application of this analysisyields the mean column length (noa) and its distribution
and the RMS strain and its distribution. The apparentcell size is a3and no, the number of cells
in the averagecolumn length, is determinedby a linear extrapolationof the real part of the Fourier
Transform of the (000) reflection.
The cell size (a) is deterrnined by the angular range over which the diffraction profile is
by:
is
given
and
analysed
-

1- 1/2-

I-

(2a,

(2a,

/X)

1+ 1/2-(2a.

/K)

sin 0,

sin 0.

/k)

sin 02

(29)

(30)

(31)

is
diffraction
is
the
q
the
q
x
the
the
and
end
q
start
of
are
and
profile,
position
of
peak,
where
the wavelengthof theradiationemployedandI is a reflectionorderasin hkl. In orderto simplify
it
is
convenientto choosescanrangesso that a3is the samefor all
calculations,
the subsequent
In
in
2.4
d,,,
this
the
analysis.
study,
used
a
cell
size
of
x
wasused.
reflections
Closeandcarefulexaminationof the diffractionpatternsfrom thesesamplesshowedboth the
III and222 diffractionpeaksoverlappedwith their nearestneighbours,the 200 and 311 peaks
for
determine
This
true
the
to
also
was
specially
reference
gold
sample
used
prepared
respectively.
instrumentalbroadening.In thepresentstudy,datawascollectedoveranangularrangeof 10
311/222
lines.
111/200
the
and
about
centred
In order to obtainadequate
representation
of thediffractionprofilesin the "tails" of thepeaks
(wheremostof the crystallitesizeandstraininformationis contained)a variety of mathematical
dataandtheparameters
for thebestfits usedto calculate
functionswerefitted to theexperimental
Split
Pearson
7
Pearson
7,
different
Voigt
(mixed
diffraction
three
and
pseudo
profiles.
model
Cauchyand Gaussian)type functionswereemployedin the modelling.

72

The modelled III and 222 diffraction profiles were calculated at 1024 data points over an
angularrangeof 16and20" respectively. Fourier transformswere calculatedusing anFFTroutipe.
The instrumentalcontributionto the diffraction datawasremovedby dividing the FT of the samples
by the FT derived from the precipitatedand annealedgold powder describedabove. The Fourier
coefficients of the 000 reflection were calculatedusing the extrapolationproceduresdescribedby
Warren and Averbach.121.This methodenablesthe individual contributions of crystallite size and
strain to line broadening to be evaluated. The contribution to broadening from crystallite size
(column length) is independentof the order of reflection whilst that from strain is dependenton
the order of reflection. Becauseof this, the two contributionsmaybe resolved. The meancrystallite
sizes were calculatedby extrapolating the linear region of the real part of the 000 transform to
obtain no. The mean column lengths (crystallite size) and RMS strains are listed in Table 23.

faultson the III planemayalso

In additionto crystallitesizeandRMS strain,layer sequence
broadening.
Ile
line
to
contributionof stackingandtwin faultsto line broadeningmay
contribute
be identifiedoncethestrainandsizecontributionshavebeenestablished.Ile effectivecrystallite
size,Dff comprisesfor the (I 11)plane

I+I.

Sa+P')F3
)T
a'

(32)

is
is
is
fault
D..
fault
true
the
the
[3
the
twin
crystallite
size,
probability
stacking
a
probability,
where
and a'is the lattice parameter. The stacking fault probability may be establishedby measuring
III
between
the
shift
and the 200 peaks. The probability may then be calculated.
any relative
Twin fault probabilities may be calculatedfrom any asymmetryof the diffraction peaksthat have
beenreconstructedfrom the inverseFourier transform producedduring the Warren and Averbach
it
fault
because
However,
to
the
twin
not
possible
was
accurately
calculate
probabilities
analysis.
the depositwas highly oriented in the III direction. Twin fault probabilities are usually calculated
for the 100 (200) reflections. Due to the high degreeof texture, the 200 signal was very weak and
could not be used for the analysis. Table 23 also includes the stacking fault probabilities where
thesewere significant.

MetallurgicalMicrosectionwas carriedout on a numberof samplesin order to observeany

resolvablemicro-structures.

73

7.2.4 Deposit hardness

Where required, the deposithardnesswas measuredusing a MatsuzawaModel DMH-2 fitted
with a Vickers diamondindentor. The indentorwas appliednormal to the surface.It was established
that using a 25 g masson the indentor and a deposit thicknessof at least 16 14m,the influence of
the substratewas eliminated. For eachset of conditions, 12 depositspotswere produced. A single
hardness measurementwas carried out at the centre of each spot and the results of the 12
measurementswere averaged.

7.2.5 Chemical analysis.

Chemical analysiswas primarily required for the establishingthe nickel content of gold alloy
depositsas well as maintaining the electrolytes at the required gold ion concentration. The nickel
in solution was analysedby X-ray FluoresenceSpectroscopy(XRF), as was the gold. The nickel
in the deposit was analysedby XRF calibrated using samplesadditionally analysedby Atomic
Adsorbtion Spectroscopy(AA). Further details are given in 7.3.2.3

7.2.6 Types of substrate used.

During the early stagesof this work, gold flashed,nickel platedcopperstrips I cm by 5 cm

The
6,
diamond
finish,
to
strips
were
polished
cathodes.
a
cleanedandthenplated
as
um
wereused
They
bright
15
10
nickel.
werethengivena gold flash of about0.2 jurnto prevent
of
jLrn
with forming
by
from
deposits
However,
immersion
the
chemical
gold
replacement
electrolytes.
any
that therewassomevariability
theseprovedto be unsuitablefor two reasons.Firstly, it appeared
in thesubstratethatled to variationsin growthhabitof thejet depositsunderthe sameconditions.
Whilst this was small, it was an undesirablepropertyof the substrate.Secondly,the substrates
flat
to allow accuratemeasurements
of the thicknessandwidth of the spots,
sufficiently
werenot
It
low
decided
40
that
thicknesses.
therefore
was
glass
substrates,
sputtered
at
with
particularly
by
100
followed
be
The
nm
of
gold
would
used.
advantages
of usingthis substrate
chromium
of
nm
fact
layers
flatness
improved
(I
11)
the
that
to
thin
tend
and
sputtered
gold
the
adopt
a
preferred
were
orientationandthusprovidea moreconsistentcrystallographicsurfacethanthe metalsubstrates.
For the analysis of nickel in gold, OFHC copper discs plated with 0.4
of
pure
gold
were
jum
used.

74

7.3 METHODS USED FOR THE PRODUCTION OF EVALUATION SAMPLES.

The purposeof this work was to identify and optimise the conditions under which high quality
gold and gold alloy depositscould be produced at maximurn plating rates. To achieve this, a
large number of deposit spotswere producedunder varying conditions of temperature, flow rate,
electrolyte composition and current density. The exact conditions for eachsamplemay be found
inTables 2 to 15. Puregold depositswere usedfor the initial trials to establishthe generalgoverning
principles of depositionunder high speedjetting conditions. The conditions were then adjustedto
allow the maximum depositionratesthat all9wed good quality depositsto be produced.This current
density is referred to as the maximum useful current density. The optimised electrolyte was then
used to produce samplesfor characterisingthe deposit. The principles establishedfor pure gold
were then applied where possibleto the gold alloy system.
The value of the applied current densitiesquoted in this work were basedon the crosssectional
impingement
is
it
known
deposition
However,
thus
the
that
the
and
exit
occurs
zone.
nozzle
of
area
is
impingement
Unfortunately,
therefore
this
true.
the
zone
and
assumption
strictly
not
outside
there would appearto be no other way to define the current density under these conditions and
therefore this assumptionwill be adopted.Under certain deposition conditions, it is clear that this
but
be
incorrect
discussed
later.
is
this
will
assumption

7.3.1 Pure gold deposits.

in previouschaptersthatto obtainhigh qualityelectrodeposits

It hasbeenestablished
at high
high
(a)
ion
high
it
is
(b)
to
to
provide
concentrations,
provide
rates
necessary
metal
platingrates,
Usingtheseprinciples,a matrixexperiment
of agitationand(c) to operateat elevatedtemperatures.
At
designed
the
these
thesametime,
to
validity
of
conditions.
underjetting
establish
principles
was
the influenceof thesefactorson the selectivityof thejetting processwasexamined.As such,the
for
deposit
this
of
set
of
samples
morphology,plating rate and selevaluation
was
criteria
main
be
defined
in
deposited
The
the
thickness
the
may
or
mass
as
ratio
of
of
selectivity
metal
ectivity.
region.By plottingthethickness
theimpingementregionto thatdepositedoutsidetheimpingement
dimensionless
is
from
distance
defined
distance
R
R,
the
the centreof the
a
as
where
against
impingementregion dividedby nozzleradius,an indicationof the comparativeselectivityof the
processcanbe seen.
that other characteristicssuchas
It was only whenthe optimumconditionswere established
hardnessetc wereevaluated.

75

7.3.1.1 Electrolyte composition

Two types of electrolyte were chosenfor this study, the citrate and the phosphatebuffered
cyanide gold. Table 1 gives full details of theseelectrolytes.Metal ion concentrationswere varied
between0.041M up to 0.28M. The pH values were maintainedat 6.1 for the citrate electrolytes
and 7.1 for the phosphateelectrolytes except where statedotherwise. The viscosity of each electrolyte was measuredat temperaturesat which sampleswere produced in accordancewith BS188.
(1977) using a calibratedOstwald viscometer. The electrolyte conductivities were measuredusing
a Phillips Conductivity meter using O.IM KCI as a standard.The electrolyte was analysedafter
60
had
been
approximately
spots
after
produced. Any deficiencieswere corrected.
up
and
making
Chelating agentssuch as EDTA was not added for this work to eliminate the possibility of any
be
high
Also,
that
effects
may
experienced
under
values
of
polarisation.
at the
surface
unwanted
little
be
of
co-deposition
contaminant
metals
would
expected.
used,
values
pH

7.3.1.2 Experimental method

The experimentalmethodwas similar for all the evaluationsamples.After the electrolyte under
test had beenloadedinto the pump systemthe flowmeters and pressuretransducerwere calibrated.
A freshly preparedsubstratewas clipped into the substrateholder. The flow rate and temperature
The
for
test
the
the
the
conditions
and
nozzle
was
aligned
with
substrate.
appropriate
current
set
were
loaded
initiated.
Each
for
the
test
the
was
conditions
and
experiment
was
substratewas
program
being
increasing
density
18
to
spot
spots,
each
produced
at
an
current
over the range
up
with
plated
0.25 up to 8.0 A CM-2.The time of deposition was adjustedto supply a total of 0.039 0.0004
This
20
Each
to
thickness
was
calculated
give
a
of
about
series of spots
spot.
per
Jim.
coulombs
25oC,
40aC
55oC
temperatures
I 0C and over a wide range
electrolyte
of
at
and
produced
were
of Reynolds number.
As has been mentioned in Chapter 6, in order to maintain a constantpipe flow profile and
therefore a constantmasstransfer accessibility, the ratio of H/d had to be as low aspossible. Initial
trials using H/d =I indicated that the nozzle becameengulfed with electrolyte due to contact
between itself and the hydraulic jump of the electrolyte, particularly at low flow rates. This
jet.
it
deposits
As
differing
to
compare
a
submerged
was
necessary
under
produced
effectively
flow conditions but constantH/d ratios the influence of H/d had to be establishedso that the lowest
be
A
distance
used.
series of sampleswere prepared using a current density of
could
practical
3.0 A crn-2,a Reynolds No. of 10,500 and a temperatureof 40-C using the phosphateelectrolyte.
The H/d ratios were varied between0.625 to 8.25 at 0.625 intervals. The appearance,maximum
thickness and profile was recorded.

76

A further seriesof spotswere preparedat a constantcurrent density, velocity and temperature

but with increasingdepositiontime to establishhow the deposit varied with increasingthickness.
The effects of dissolvedoxygen were examinedby preparing a seriesof spotsboth before and
after bubbling nitrogen through the electrolyte for 30 minutes to de-aeratethe electrolyte.
The influence of pH was also examinedwhen all other factors had beenoptimised. A seriesof
from
bath
5.3
8.1.
the
values
optimised
citrate
at
pH
of
and
produced
sampleswere
The cathodic current efficiency was evaluatedfor an optimised electrolyte over a range of
densities
below
for
long
2.0
A
For
densities.
a
single
spot
a
period of
current
cm-2,
plated
current
time was usedwhilst at current densitiesabovethis an array of 20 spotswas used. The reasonfor
the different methodswas that at low current densities,becauseof the long plating times involved,
there was somechemicalattackof previously plated spotsby the electrolyte run-off. Using a single
losses
due
likelihood
to chemical attack.
the
of
spot reduced
The mass of deposit produced by either method was low ( about 10 mg) and therefore the
both
The
before
7
taken.
times
and
average
value
and
after
plating
an
weighed
was
substrate
by
Faraday's
Laws
calculated
comparingthe theoretical mass
was
using
efficiency
current
cathodic
depositedfor the number of coulombspassedto the actual massmeasuredand expressingthe result
as a percentage.
Using the optimised electrolyte, a fimher series of depositswere produced using nozzles of
different diametersbetween0.1 mrn and 0.54 nun to establishwhether the nozzle size influenced
the deposition rate, structure etc.

To examine the influence of pulsed current, a series of deposit spots were produced over a
duty
from
0.02
The
cycles.
on-times
msecs.to 10.0 msecs. and
and
ranged
of
on-time
wide range
duty cycles between 5.0 and 90%. The averagecurrent densities used were between 6.0 A CM-2
A
10.0
Cm-2.
and
7.3.2 Gold alloy deposits

As has beenpreviouslymentioned,gold may be alloyedwith small quantitiesof transition

Nickel
deposit.
the
the
andcobaltarethepreferredchoices
thus
properties
of
altering
groupmetals
for this purposealthoughiron has beenused.It was decidedthat it would be better to use an
high
for
designed
speedoperationasthis would reduce
available
electrolyte
existingcommercially
disadvantages
decision.
The
for
There
to
this
development
time
were
required
optimisation.
the

77

is
electrolytes
often a closely guardedsecret and it was not possible
composition of proprietary
to control all the compositional variables. However, despitethis, three electrolytes were chosen
to representthe three commonalloy systems.The cobalt and nickel electrolyteswere Ronovel CM
and Ronovel N, supplied by Lea Ronal. The gold/iron electrolyte was the Aurtma 7000 supplied
by Degussa.A seriesof plating trials were carried out on all three electrolytesin order to establish
which electrolytewasthe mostsuitablefor optimising forplating underhigh speedjettingconditions.

7.3.2.1 Initial trials for electrolyteselection.

Each of the electrolytes were made up with three different concentrationsof gold, 0.05M,
0.076M and 0.1M. The recommendedoptimum quantity of the alloying metal was addedto each
initial
depositing
from
The
trials
consisted
of
a
series
of
spots
each electrolyte
the
electrolytes.
of
(approx.
Re.
density
between
11,000)
highest
obtainable
over
a
current
of
range
the
velocity
=
at
3.0 and 10 A Crn-2.The resulting depositswere examinedand the electrolyte giving the best deposit
for
density
indicated
N
Results
Ronovel
highest
that
the
chosen
optimisation.
was
the
current
at
was the most suitable and this electrolyte was used.

7.3.2.2 Optimising the gold/nickel electrolyte.

The criteria for obtainingan optimumgold/nickelalloy was basedon severalfactors. The

deposithad to containthe appropriatequantityof alloying constituent.It had to havea suitably
high hardness,it hadto havea similarmorphologyto conventionalhigh speedgold alloy deposits
,
Finally
it
had
be
it
had
to exhibitthesequalitiesat
existing
to
with
specifications.
compatible
and
the highestpossibledepositionrate. The optimumconditionsof depositionfor pure gold under
jetting conditionswere appliedto the plating trials for this electrolyte.The variablesthat were
In
density.
to
the
the
the
of
nickel
added
and
current
electrolyte
concentration
adjustedwere
boost
to
the maximumcurrent
use
of
this
made
an
organic
agent
addition
electrolyte
addition,
density.Unfortunately,the recommended
quantity wasalreadyaddedto the make-upsolutionas
its
it
be
However,
This
that
concentration
could
reduced.
couldbe increased
not
meant
supplied.
and this was includedas a variable.The nickel contentwas variedover the concentrationrange
(0.5
3.0
1-1).
The
0.05M
0.0085M
between
to
standardadditionagentconcentrationwas
g
and
of
increasedfrom 60 ml 1-1to 80 ml 1-1.

78

7.3.2.3 Experimental method.

As with the pure gold electrolyte, a seriesof depositedspotswere producedfor morphological
as well as structural examination. Spotswere depositedover the current density range of 0.25 to
16.0 A Crn-2.Becauseit was found that the overall depositionrate was significantly lower than that
increased
0.07876
0.0001 coulombs
to
the
the
of
coulombs
passed
was
number
gold,
of
pure
Reynolds
55
deposits
I
The
temperature
oC
and
at
a
of
at
a
number of
were
produced
per spot.
about 11,000. The pH of the electrolyte was maintainedat a value of 4.6 for all the experiments.
The cathodecurrent efficiency was measuredin the sameway as with the pure gold deposits.
Chemical analysisof the Mckel contentof the depositswas carried out by X-ray Fluorescence
Spectroscopy(XRF). For each concentrationof nickel in the deposit, an array of 90 deposited
densities
2.0,4.0,6.0,8.0,12.0
16.0
A
An
current
of
at
and
Cnr2.
oxygen
produced
was
spots
free high conductivity (OFHC) copper substratewas used, pre-platedwith 0.4 Jim of gold. A pure
blank.
The
in
XRF
deposit
the
as
a
sample
was
used
placed
was
spectrometerwith only
array
gold
the array exposedto the X-rays.
The XRF spectrometerwas calibratedby measuringthe nickel contentof 6 array samplesusing
AA analysis. The count rate from each of the sampleswas first determined using the XRF. In
The
the
the
surrounding
substrate
array
was
cut
off.
array and remaining
to
errors,
minimise
order
foil
in
left
50%
dissolve
This
to
thin
the
then
nitric
acid
a
gold
substrate.
placed
substratewere
deposit
initial
it.
foil
The
0.4
the
the
with
array
of
was weighed to
spots
on
jAm
consisting of
initial
deposit
Prior
to
the
the
thickness
the
total
was
plating
array,
the
of
gold
mass.
establish
determinedover the array depositionareausing anX-ray 1000XRF thicknessmeasuringinstrument.
The massof this initial deposit was calculatedand subtractedfrom the total massof the gold foil
in
dissolved
The
foil
The
then
the
and
analysed.
array
results
aqua-regia
was
the
plus
array.
with
for
XRF
to
the
then
curve
and all subsequent
used
produce
a
calibration
of this analysis were
data.
from
It
be
this
should
noted that the nickel concentrationsobtained
evaluated
were
samples
by this method gave only the averagenickel content of the depositedspots and did not give any
indication of the distribution of nickel within the individual spots.

The methodsusedfor structuralanalysisandhardnesshavebeendescribedin sections7.2.3

and7.2.4.

79

7.4 MASS TRANSFER STUDIES.

In order to examine the validity of the various Sherwoodnumber to Reynolds number relationships that had been suggestedby other workers, it was necessaryto obtain masstransfer data
for the gold system. Information concerning the mass transfer characteristics of the various
electrolytes under jetting conditions was carried out by evaluating the current/overpotential relationships by plotting polarisation curves and detennining where possible the value of 'L* It Was
immediately obvious that significant difficulties would be encounteredusing conventionalvoltage
or current scansover the potential and current range of interest. This was becauseat such high
current densitiesas thoseusedin jetting, the depositgrew so rapidly that the effective surface area
due
Initial
to
crystalline
growth.
experimentsconfirmed this. In addition, there
changed
quickly
in
difficulty
the
of
placing
a
reference
electrode
such a position as to avoid interference with
was
the electrolyte jet. These problems were overcomeby using a specially designedworking electrode/reference electrode assemblyand by using two techniqueswhich will be termed Sampled
Current Pulse Voltammetry (SCPV) and Sampled Voltage Pulse Amperometry (SVPA). The
by
technique
the
was
established
using a copper sulphate electrolyte, a well studied
validity of
identifying
jet
factors
from
in
the polarisation
the
and
appropriate
unit
electrochemical
system,
curves obtained.

7.4.1 Principles of SCPV and SVPA.

Both of thesenovel techniqueshave been adaptedfrom the method of sampledcurrent voltametry, which is the basis of polarography. Ordinarily, polarisation data is recorded as described
in section 3.2. However, depositgrowth did not allow such steadystatemeasurementsto be used.
it was therefore necessaryto minimise deposition times for eachvalue of overpotential or current
SVPA
SCPV
difference
being
both
As
the
the controlled
are
and
essentially
similar,
applied.
described.
A
40
be
SCPV
short
period,
say
mseconds,single voltage pulse of small
will
variable,
is
100
(50
applied to the working electrode. The current transient is recorded
mV)
or
magnitude
on a storageoscilloscopeor similar recording device and the processis repeatedwith an increasing
desired
the
potential range. A typical current transient is shown in Figure
over
magnitude pulse
13. As the potential is first applied, a large current flows. This consistsof the double layer charging
becomes
is
increase
in
layer
faradaic
double
As
there
the
the
an
charged
so
proportion
of
current.
current as metal ions in the vicinity are discharged.However, theseare rapidly consumedand the
layer
decreases
further
develops,
diffusion
falls.
As
the
current
gradually
a
with increasing
current
time as the diffusion layer thickens. By choosing a time period, -r, within the transient at which
its
is
to
the
at
close
minimum
current
value,
-c used for the polarisation curve.
the current stabilises
If the value of -cis too short, then the current will include the double layer charging current. If -c
is too great, the current will be influenced by the effects of deposit growth. The ideal situation is

80

to choosea value of -r which correspondsto the point at which a steadystate diffusion layer has
formed. The value of -r will be dependenton the magnitudeof the potential and the current flowing
as this will influence the magnitudeof the diffusion gradient. The greater the current, the faster
the influence of diffusion. Also, at high overpotentialsand currents, depositgrowth becomesrapid
and this influences the surface areaof the electrodeleading to enhancedcurrents.

Charging
current
Deposit
growth
bi
ry
ry
D
u

Steady
state

rTIME
Figure 13. A typicalcurrenttransientproducedduringa singlepulseusingthe SCPVmethod.A
been
deposit
has
the
high
to
chosen
effect
of
growth.
show
overpotential
relatively
Below the limiting current density, the metal ions are not completely consumed. They are
however, lower than the bulk concentration of metal ions. At the limiting current density, the
increases
in
ions
be
further
lead
to
will
zero
and
potential
will
not
metal
of
surface concentration
This
in
further
technique should
a
secondary
reaction
unless
electrode
occurs.
current
rise
any
density
'LP
limiting
Tafel
identification
the
the
parameters
as
current
such
slope and
of
the
allow
the exchangecurrent density.

7.4.2 The worldng electrode/reference electrode assembly.

In order to producea valid currentdensity/overpotential

relationship,the surfaceareaof the
beyond
impingement
jetted
deposits
be
known.
As
has
the
to
spread
regionand
working electrode
dependent,
fixed
diameter
found
be
density
been
has
to
degree
a
conductive
current
the
of spread
diameter
fashioned.
This
the
copper
wire,
same
an
enamelled
of
consisted
working electrodewas
block.
A
into
(0.4
gold wire referenceelectrode
epoxy
an
mounted
vertically
nun)
as the nozzle
it
from
by
distance
to
the
a
of approximately
working electrodeseparated
wasmountedadjacent

81

0.1 mm. The face of the block where the electrodesemergedwas polished flat to a mirror finish
thus providing a pair of flush mountedelectrodes.Severalof theseelectrodepairs were mounted
in the sameblock. A schematicdiagramof the electrodeblock is shownin Figure 14. The advantage
of this method of electrodearrangementwas that the referenceelectrodedid not interfere with the
jet. The gold wire referenceelectrodewas not ideal becausethe gold systemsused in thesetrials
were electrochemically irreversible. An ideal referenceelectrode should show complete reversibility with the ions in the electrolyte or there is the dangerof somecurrent flowing through it and
influencing the results. This was offset by ensuring that the potentiostathad an extremely high
input impedance.

Gold ref erence

etectrode

Epox

lotock

Figure 14. The electrodeblock usedfor polarisationmeasurements.

A further difficulty with this electrodearrangementwasthat of the IR drop betweenthe working
Despite
between
the
them, there was still an IR drop
the
close
electrodes.
spacing
reference
and
between them due to the low conductanceof the thin radial wall jet. In order to compensatefor
this, the SVPA method was used. With this method, it was thought possible to measurethe IR
drop between the two electrodesby means of the magnitude of the initial potential rise of the
voltage transient.

To allow the evaluationof the techniqueof SCPV,a copperelectrolytewasused.A similar

electrodesystemwasusedto thatof thegoldexceptthatthereferenceelectrodewasa copperwire.

82

7.4.3 The equipment used.

A schematicdiagram of the equipmentused for thesestudies is shown in Figures 15 (a) and
(b). Figure 15 (a) shows the SVPA system. It was similar to that used for pulse plating. In this
casea single voltage pulse was supplied from the pulse generatorto the power supply which then
by
drop
The
the
the
recorded
voltage
current
was
acrossthe 1.0 K resistor
current
pulse.
generated
by one channelof the storageoscilloscope.The voltage difference betweenthe working electrode
The
the
the
on
second
channel
of
the
was
recorded
oscilloscope.
magnitude
electrode
reference
and
by
be
The
the
of
circuiting
the
pre-set
means
short
output.
could
recordedcurrent
current
pulse
of
Bryants
X-Y
for
downloaded
then
to
a
recorder
a permanentrecord of each
was
and voltage pulse
levels
low
At
there
significant
currents,
were
of 50 Hz noise on the potential signal.
applied
pulse.
This was reducedby placing a 0.1 jiF capacatoracrossthe output terminals of the power supply.
Figure 15 (b) showsthe equipmentused for the SCPV technique. A standardWenking HP72
in
The
generator.
conjunction
with
a
pulse
current and applied potential was
used
was
potentiostat
downloaded
X-Y
to
oscilloscope
and
a
storage
an
recorder.
using
measured

7.4.4 Experimental technique.

The methodof obtaining polarisationdatawas similar for both the SCPV and SVPA techniques.
The electrodes were first lightly abradedusing 1200 grade emery paper. The jet was carefully
distance
I
A
to
with
a
nozzle
the
electrode
electrode
of
nun.
small current
working
with
aligned
for
30
deposit
layer
0.03
thin
to
seconds
a
of gold onto the electrode.
applied
was
mA
of about
The current was switchedoff andthe systemmaintainedat the current free for 2 minutesto establish
the rest potential. With the SCPV method, a potential pulse of between50 and 100mV was applied
The
the
current
recorded.
and
electrode was then abraded with 1200
the
potential
rest
above
The
50
100
the
to
gold.
was
process
repeated
using
remove
or
mV pulse
paper
emery
grade
incrementsabovethe previous level up to 4.0 volts. With the SVPA method, a single current pulse
density
between
0.04
A
50
A
The
The
range
used
was
cm-2
and
Cm-2.
current
voltage
used.
was
In
jump
from
the
was
recorded.
addition,
pulse
potential
each
was recorded as a measure
obtained
between
drop
IR
the working and referenceelectrodes.
the
of

83

00
Putse generator
00
0

Power

suppty

00

04?

D.q. tal

X-Y chart
recorder

Res.stor

IK

ommet r
1254

Oscitloscope
0

Yorking
tiectrode

I
Reference
etectrcWt

(a)

Putse

generator
00
00
V in

RE

99Y

WE

CE

e
Oscittoscape

I ou

Potentiostat
00
X-Y chart
recorder

=: I-j-e-t-71
Reference
etectrocle

Working
etectrocle

(b)

Figure 15. (a) The equipmentusedduring the SVPA experiments.(b) The equipmentused during
the SCPV experiments.

84

The resultsof this work will be presentedmainly in the form of graphsand micrographs.Where
in
form
Tables
is
data
towards the end of the Thesis.
the
the
of
shown
collected
relevant,

8.1 PURE GOLD DEPOSITS.

Whilst both the citrate and phosphatebuffered gold electrolytes had some different chardeposits
in
the
the
the
of
produced,
morphology
general principles of the
particularly
acteristics,
influence of the deposition conditions hold for both types. They will therefore be treated together
differences
the
are significant.
where
except
The electrodepositedgold spotsproducedby this jetting technique were generally gaussianin
depending
density
flow
the
on
current
rates used.
and
electrolyte
symmetrical
profile and were
However, at low flow rates and high current densities, the deposit quality deteriorated with the
dendritic
These
deposits
longer
the
or
structures.
showed
no
nodular
of
powdery,
production
factors
deposit
deposition
influencing
The
the
controlling
structures
and
rates
gaussianprofile.
in
following
detailed
the
DC
sections.
conditions are
under

8.1.1 The effect of nozzle to substrate distance.

By varying the nozzleto substratedistance,or the H/d ratio, a number of effects were observed.
At ratios in excessof 4.375, radial needle structures were seentowards the edge of the deposit.
Photograph2 shows such a structure. Below this value under the conditions used, no such forms
increasing
H/d
16
Figure
the
the
shows
of
effect
ratio on the selectivity of the
were observed.
deposits produced. It can be seen that at H/d below 1, the deposit showed a greater selectivity,
being
impingement
deposited
Between
1.25
the
of
gold
within
region.
proportion
greater
a
with
distance.
H/d
8.75,
did
deposit
At
the
the
vary
4.375,
not
with
selectivity
the
=
selectivity
and
H/d
below
be
1,
Whilst
the
at
ratio's
of
selectivity
could
achieved
problem
a
greater
reduced.
was
its
basis
flow
On
the
interaction
the
the
across
substrate
precluded
general
use.
of
with
of nozzle
for
400
1.25
distance
lmm
H/d
the
trials
the
information,
used
all
of
was
with
or
a
of
ratio
a
this
interaction
became
With
the
the
the
with
of
electrolyte
nozzle
nozzles,
effect
smaller
pm nozzle.

85

increasingly influential as the hydraulic jump occurred much closer to the nozzle exit. By maintaining the H/d value between I and 4, a constantselectivity could be ensuredeven when using
small diameter nozzles.

20

10

02
Dimensionless
distanceratio
Figure 16. The effect of the H/d ratio for a 0.4mm nozzle on the selectivity of the deposit.

8.1.2 The effect of current density.

As would be expected,the magnitude of the current density influenced the deposit structure
had
influence
It
a
significant
also
on the selectivity, the current efficiency and
and morphology.
the hardness.

8.1.2.1 Generalobservations
At a currentdensityof 0.25 A CM-2,
thedepositcouldnot be measured
within the impingement
difficulty
deposit
leading
differentiating
deposit
Dektak
the
to
the
thin
the
as
of
was
regionusing
from thebackgroundnoiseof thesubstrate.However,theexistenceof somedepositionwasvisible
in
4
diameter
was
observed
comparisonto the rest
change
as
a
colour
about
nun
subtle
to
of
up a

86

of the substrate.At a current density of 0.75 A crn-2,a thin, sub-Microndepositcould be measured

in the impingementregion but it was difficult to measurethe overall spread asthere was no clearly
definable edge. However, the spread of the deposit was visible up to 8 nun in diameter. The
found
be
to
translucentwhen viewed with a strong
were
used
as
substrates
slides
sputteredglass
backlight. Low current density depositswere produced on such a substrateand viewed under a
low power microscope fitted with an eyepiecemicrometer. Where deposition had occurred, the
transmitted backlight disappearedand the spread of the deposit could be measured. Figure 17
density.
function
It
be
the
the
of
current
as
a
can
seen
widths
optically
measured
shows a plot of
that the deposit spreadpassesthrough a maxima at a current density of 0.75 A CM-2but becomes
3.0
A
densities
above
CM-2.
current
at
constant

Width measuredoptically

II

Temp. 55 C

11

:3:

Velocity 18 m/sec

Efl
5

I)i

3
s
I

01

34
CurrentDensity A/cm sq

Figure 17. Currentdensityvs depositwidth measuredopticallyshowingthe maximumspreadof

0.17M
from
deposit
a
citrateelectrolyte.
produced
spots
the
It was also notedthat althoughthe numberof coulombspassedper spot was constant,the
thicknessof the depositsincreasedwith increasingcurrentdensity.The reasonsfor this will be
discussedat a later stage.

87

It was found that the presenceof dissolved oxygen had the effect of reducing the deposition rate
at current densities below 3.0 A crrr2. With the dissolved oxygen removed by de-aeration, the
deposition rates at theselow current densitiesincreasedby up to 60 %. In addition, the selectivity
30%.
by
around
reduced
was

8.1.2.2 Deposit topography.

Current density influenced the topography and morphology of the deposit significantly. The
depended
densities
topographical
changes
occurred
strongly on theprevailing
at
which
actualcurrent
ion
However,
temperature,
concentration.
velocity
and
metal
a general
electrolyte
of
conditions
be
described
flow
A
the
typical
where
will
conditions corresponded
example
pattern was observed.
to a ReynoldsNo. of approximately 12,000 and a temperatureof 55oC.At current densitiesbelow
1.0 A Cm-2,deposits were similar in appearanceto those produced by conventional deposition.
Photograph3 showssucha structure. Increasingthe current density led, initially, to a very smooth
features.
As
density
increased
4.0
A
few
the
current
was
surface
Cm-2,the
above
with
structure
deposit exhibited small, hemisphericalfeaturessimilar to thoseobservedby Nakaharain hard gold
deposits. These can be seenin Photograph4. Above a current density of 6.0 A cm-2,a nodular
in
10
densities
dendrite-like
A
Finally,
formed.
excess
of
CM-2,
at
current
a
wide
variety
of
structure
in
direction
jet
from
formed,
the
to
the
radial
needles
growing
non-diof
wall
ranging
structures
high
densities,
became
highly
Ultimately,
very
current
at
growth
growths.
rectional organic-like
field orientated as the deposit grew along the free jet, producing tree-like structures. Typical
in
Photographs
5,6,7,8
9.
Reducing
flow
be
the
and
these
rate and/or the
seen
can
examplesof
in
density
led
the
to
current
at which the morphological changesoccurred.
a
reduction
temperature

Figures 18to 23 showmorphological/topologicaldiagramsof the 0.041M andthe 0.28M citrate

function
deposit
density,
diagrams
These
temperature
deposits.
a
current
relate
structures
as
of
gold
identify
These
to
trends with which to establishan optimum electrolyte
flow
used
were
rate.
and
The
behaviour
conditions.
phosphate
electrolyte
showed
a
similar
except
operating
and
composition
that the transition from smooth to nodular depositsoccurred at a lower current density than the
equivalent citrate electrolyte.

88

10

Temp.25C

Li
Needle
type

Nodular

-----4=3-

Smooth

0
0

2000

4000

6000
No.
Reynolds

8000

10000

12000

Figure 18. Morphological diagram for the 0.041M citrate gold at a temperatureof 25oC.

40-C.
for
0.041M
diagram
temperature
the
at
a
Morphological
gold
of
19.
citrate
Figure

89

10

Temp.55C

Nodular

Smooth
0
0

2000

4000

6000
No.
Reynolds

10000

8000

12000

Figure 20. Morphological diagram for the 0.041M citrate gold at a temperatureof 55oC.

10

Temp.2SC

Fieldorientated

C.

C-,

Needletype

Smooth

0
0

2000

4000

6000
No.
Reynolds

10000

8000

12000

for
0.28M
diagram
25oC.
temperature
the
Morphological
gold
at
a
citrate
21
of
Figure

90

10

cs

0
0

2000

4000

6000
Reynolds
No.

10000

8000

12000

Figure 22. Morphological diagram for the 0.28M citrate gold at a temperatureof 40-C.

10

C.,

0
0

2000

4000

6000
Reynolds
No.

8000

10000

12000

for
0.28M
diagram
the
Morphological
citrategold at a temperatureof 55-C.
23.
Figure

Althoughthesediagramsshowa fixed transitionpoint betweenstructures,it shouldbe noted

lines
The
deposit
had
transition
the
were
placed
at
positions
where
gradual.
transition
was
that the
low
by
type
visual
assessment
using
definite
evidenced
powermagnification.
as
structure
adopteda
depended
type
growth
the
of
needle
on the flow rateand
Whereneedletypestructuresarestated,
led
in
both
flow
low
to
High
the radial and
needles
growing
temperatures
rates
and
temperature.

91

axial direction. Suchstructureswere difficult to distinguish betweenfield oriented growth and the
recorded structure dependedon the relative magnitude of the axial and radial components.Low
temperaturesresulted in purely radial growth. High flow rates with low temperaturesincreased
the thicknessand regularity of the needlesfor the sameapplied current density. For the samelow
temperature and flow rate, increasingthe current density led to a finer, more filamentry type of
field
In
the
of
orientedgrowth, the structuresobserveddependedlargely
case
needle
growth.
radial
densities,
field
At
high
density.
orientedgrowths were nearly always
the
current
on
applied current
precededby needlegrowth.
From the above results, it was clear that the limiting factor to high speeddeposition was the
deterioration of the depositby nodulationor dendritic growth of various kinds. In order to establish
how such structures initiated and grew, a series of sampleswere prepared above the maximum
deposition
Each
for
density
the
conditions.
sample was prepared by
prevailing
useful current
incrementing the time of deposition slightly so that a picture could be built up of the mode of
deposits
(f)
density
10(a)
Photographs
to
show
a
series
of
produced
at
a
current
of 7.0 A
growth.
Photographs
II
(a)
(d)
3335.
but
to
Reynolds
the
show
some
of
of
same
no.
at a higher
CM-2at a
initiation
deposits.
These
the
of
show
and
growth
nodular
samples
magnification.
After a deposition time of 0.8 seconds,the substratewas fully covered with small nuclei
interspersedwith small nodules about 3.5 Am in diameter (Photograph 10a). Close examination
inhibition
larger
there
the
that
signs
surrounding
were
of
nuclei
this
nodules
revealed
sample
of
(Photograph Ila). After 1.5 seconds,the nuclei had grown to a size of about 2.5, um in diameter
having
7.5
(Photographs
10
b).
II
larger
Most
to
grown
about
and
nodules
Am
the
original
with
50
It
larger
the
a
outside
region,
presumably
stagnation
were
Am
these
zone.
nodules
was also
of
defects
After
2.5
larger
on
surface
such
as
scratches.
grew
that
nodules
seconds, there
noticed
larger
in
these
nodules
with
a
cluster
of
the same 50 Jim
of
appearing
number
were a greater
by
3
dimensional
be
that
It
growth
was
occurring
means
of
seen
nucleation, the
region. could
10c
I
Ic).
(Photographs
Deposits
and
appearance
taking
a
cauliflower
produced at a
on
nodules
time of 3.5 secondswere now distinctly nodular over the entire impingementregion with the fastest
(Photographs
10d
II
d).
the
By
5 seconds,
outside
stagnation
zone
and
occurring
of
nodules
growth
in
25
diameter
(Photograph
l0e). The growths in the stagnation
had
about
Am
the nodules
attained
but
their
distinct
3-dimensional
had
as
neighbours
growth
showed
the
size
a
more
same
attained
zone
forming
After
6
them.
on
and
growing
nuclei
seconds,whilst all the
mechanism with numerous
fastest
larger,
the
the
had
growth
occurred
at
centre of the spot, with these
slightly
grown
nodules
displayed
habit.
These
distinct
central
nodules
axial
a
columnar
a
powdery texture
nodulesadopting
(Photograph 10f). Some nodules towards the edge of the impingement region were obviously
influenced by the radial flow of the electrolyte as it enteredthe wall jet and had adopteda slightly
flow.
direction
following
the
the
of
elongated shape,

92

A secondseriesof sampleswere used to identify the mode of growth of dendritic deposits.A

current density of 10 A cm-2was usedat a ReynoldsNo. of 12078. Photographs12 (a) to (f) show
this series. The depositproducedat a time of 0.6 secondsshoweda high coverageof nodulesabout
3,urn in diameter. In addition, as Photograph12 (a) shows,there was a small, needlelike structure
about 30 Am long that had grown in the radial flow direction. Also visible were 2 larger nodules
impingement
At
in
diameter,
7
to
the
the
edge
of
region.
a time of 1.5 seconds,
close
of about Am
7
10
In
had
to
some
were
about
about
although
addition, a
the
grown
Am
Am.
nodules
of
most
(Photograph
b).
With
from
12
had
nodule
a
enlarged
particularly
grown
multiple needlestructure
increasing times of deposition, several needle type structureshad grown, all appearing to have
deposition
3.5
At
fast
from
time
a
of
seconds,growth pregrowing
nodule.
a single,
emanated
dominancechangedfrom the radial direction to the axial direction of the free jet. Thesestructures
then grew along the jet core producing feathery needlesin the direction of the flow (Photographs
12 (d), (e) and (f)). These structureswere undoubtedly causedby the interaction of the deposit
be
discussed
further
in
jet.
free
This
Chapter
10.
flow
hydrodynamic
the
the
will
of
with
growth

CurrentDensityvs Plating Rate- Different GoldConcentrations

4
C,)

CD

CX,.

0
01

345
CurrentDensityA/cmsq

citrateelectrolyte.The
Figure24. Currentdensityvs platingratefor differentgoldconcentrations,
No.
12,000.
Re.
to
of
a
exit velocity corresponds

93

8.1.2.3 Deposition rate

Figure 24 showsthe effect of current density on the depositionrate for different concentrations
of gold in the citrate electrolytes at a Reynolds No of 12,000. Tlere are several points to note.
Firstly, the rate bearsa linear relationship with the current density at current densitiesbetween I
and 5A cm-2.Above this upper value, the apparentrate varied, presumablydue to the increasingly
coarse deposits produced at these current densities. Ibis led to non-representativethicknesses
being measureddue to void and porosity formation. Secondly,the rate curves do not passthrough
the origin of the graph, indicating that at low current densities, the rate no longer has the same
linear relationship with current density. Similar results were observed with the phosphateelectrolyte.
It was found that the maximum deposition rate allowing smooth, high quality depositswas
obtainedfrom a 0.17M citrate electrolyte at 55-C and a ReynoldsNo. of 12,000. Ile rate obtained
from this electrolyte was 3.4, um/second.Photograph 13 shows a deposit 18
thick
produced
jum
deposit
14
By
these
of
comparison,
photograph
shows
a
of the samethickness
way
conditions.
under
be
It
deposit
that
the
can
seen
conventional
plating
conditions.
conventional
vat
under
produced
has an angular structure whilst the sample produced by jetting is comparatively smooth with a
hemispherical
mounds.
of
small
consisting
surface

8.1.2.4 Cathodic current efficiency

The effect of the current densityon the current efficiency was establishedonly after the
Consequently,
it
be
had
been
increased
been
had
the
that
to
will
noted
pH
optimised.
electrolyte
8.1 comparedto 6.0 asshownin Table 1. for this setof experiments(seesection8.4)
Figure 25 showsthe relationship betweenthe current density and the current efficiency of the
0.17M citrate electrolyte produced at 550Cand a Re. No. of 12,000. It can be seenthat at current
densitiesabove2.0 A cm-2,the efficiency is in the region of 70%. Below 2.0 A cm-2,the efficiency
is reducedto 40% at a current density of 0.25 A cnr2. Experimentscarried out to remove dissolved
oxygen in the electrolyte revealedthat whilst oxygen, whenpresent,was electrochemicallyreduced
leading to a reduction in efficiency, this only accountedfor about 10%, averagedover the entire
current density range.

94

100

90
80
:2 70
Z::
L-3
60
so

40
30
0

34
CurrentDensityA/cmsq

Figure 25. Current efficiency vs current density for the optimised 0.17M citrate gold electrolyte.

8.1.2.5 Hardness of deposits

Hardnessmeasurementswere carried out on depositsproducedfrom the optin-dsedcitrate gold
density
between
hardness
26
Figure
the
the
the
current
and
shows
relationship
of the
electrolyte.
deposit. It can be seenthat the hardnessincreasedwith increasing current density, being in the
6.0
is
density
A
This
kg
200
the
at
maximum
useful
of
CrO.
current
value
mrrr2
region of
deposited
Even
lower
densities,
the
that
twice
of
conventionally
gold.
at
current
pure
approximately
increase
hardness
a
significant
over that obtained under conventional deposition
the
represents
conditions.
A
9

95

220

200

HI

180
cn
Ul

160

140

HI

120

100
0

3456
Current density A/cm sq

10

Figure26. Hardnessvs currentdensityfor the optimised0.17M citrategold electrolyte.

8.1.2.6 Selectivity of the deposit
Figure 27 shows a typical selectivity plot as measuredwith the Dektak. This shows deposits
from the 0.17M citrate electrolyte produced at a constanttemperature and velocity at different
function
dimensionless
They
distance
(see
densities.
thickness
the
plots
of
are
as
a
of
ratio
current
7.3.1). A dimensionlessdistanceratio of I representsthe edge of the impingement region. This
Dektak
Comparison
limitations
the
the
of
as
a
of
measurement.
means
profile
of this
shows
graph
it
deposits
Figure
16
to
that
the
the
was
not
possible
measure
maximum
width
of
using
shows
with
the Dektak due to the asymptoticnatureof the depositspread.It was found that the limit of thickness
determinationsin the edgeregion of the Dektak were limited to approximately 0.15 jum. This was
due mainly to the variation in flatnessof the substrates.However, this graph doesshow that within
the measurementlimitations of the instrument, no significant thicknessof deposit greater than 0.15
between
3.0
3.5.
As
Figure
dimensionless
16
beyond
the
and
a
ratio
of
shows,
was
produced
pm
density
3.0
increase
influence
A
does
density
to
the
up
a
current
of
selectivity
cm-2,
with
an
current
in the deposit spread from 0.25 A Cm-2up to a maximum at 1.0 A CM-2after which it falls to a
by
found
Dektak.
It
the
This
that
to
that
was
other
measured
close
value
was
value.
constant
deposition conditions did not significantly influence the selectivity as a function of current density.

96

20

k-

10

2
R Dimensionless
distance

Figure 27. A typical selectivity plot showing selectivity as a function of current density measured
using the Dektak.

8.1.2.7 Crystal structure and residual strain.

Examinationof depositsproducedfrom theoptimised0.17McitrategoldelectrolyteusingXRD

be
determined.
Figure
lattice
to
crystallite
the
size
and
orientation
parameter,
preferred
enabled
28 showsthe latticeparameters
andorientationof themajorfirst andsecondorderreflectionsfor
identical
The
deposit
to the citrate
conventional
conditions.
electrolyte
under
was
produced
a
in
0.06M.
The normaloperating
that
the
this
study
except
gold
concentration
was
used
electrolyte
for
between
3
7
The
degree
density
this
electrolyte
was
and
cm-2.
mA
of preferred
range
current
for
been
has
eachof the reflectionsas a percentageof the sum of those
expressed
orientation
Because
be
In
the
this
preferred
orientation
may
quantified.
of thecrystalstructure
way,
measured.
intensity
be
in
For
deposit,
the
the
of
various
there
always
a
variation
crystal
the
will
planes.
of
200
III
in
FCC
than
there
andthereforeamaterialpossessing
are
more
planes
material,
example, a
intensity.
The
intensity
III
signal
will
show
a
greater
of thereflections
totally
orientation
random
a
for a totally randomlyorientedsainplehavebeencalculatedandareshownon thegraphas parallel
lines for eachof the crystalplanesmeasured.

97

4.1

I
11
-*-*.-200
220
-m-311

4.09

4. OB

4.07

4.05

r-

..&

222

a)
4.05
05

10

15

23

25

30

35

40

C.O. ffA/cm sq

100
goI
go
70

-*-III
-+-200
220
-311

60

40

t7
t: 7

loot=

10

113

20

30

25

35

C.D. ak/cmsq

Figure 28. The relationshipbetweencurrentdensityandstructuralcharacteristics

as determined
by X-ray diffractionfor a conventional
puregold depositin termsof (a) Latticeparameterand(b)
preferredorientation.
Analysisof the datafrom Figure 28(a)showedthat all planesgenerallyexhibitedthe same
latticeparameter,althougha slight increasewas observedwith increasingcurrentdensity. The
4.077
is
lattice
to
that
of
was
close
of
gold,
which
generallyacceptedas
pure
parameter
average
A
4.0786
being
at 25-C. It is thoughtthatthesinglepoint of the220planethatdeviatesfrom this
is dueto experimentalerror.
it was noted that, on calculating the crystallite size using the Scherrer method, a significant
depending
higher
This
the
the
on
was
particularly
evident
at
reflection.
observed,
variation was
line
broadening
has
been
is
difficult
An
densities.
this
the
observed
assumed
as
of
analysis
current
to be purely due to crystallite size and ignores the existenceof strains and faults that may also
indicated
Warren
Averbach
III
that
the
Analysis
the
and
using
method
reflection
of
contribute.
found
be
(See
invalid
to
the
crystallite
size
was
considerably
greater
as
was
such an assumption
Table 23). The actual crystallite size after correcting for strain was in the region of 0.23 pm. No
evidence of faulting was observed.

98

Figure 28(b) showsthe degreeof preferred orientation of the deposit. It can be seenthat by
comparison with the expectedratios of the various planes (parallel lines) that there is a distinct
311 texture over the normal current density range of 1-7 mA CM-2.Above this, the deposit tends
towards a more random orientation.
The RMS strain of the conventionaldepositswas independentof current density over the range
analysedand was comparatively low, calculatedto be < e2>=0.000035.
The above measurementsof a conventionaldeposit were necessaryto compare and contrast
be
jetting
direct
Whilst
those
comparison
cannot
under
conditions.
a
made due to
produced
with
the orders of magnitudedifference in the current densitiesapplied, in terms of the morphological
increasing
density,
ie
the
that
current
a comparison
structural
changes
occurred
with
characteristics
was consideredto be valid. Figure 3 showssimilar graphsfor samplesproduced from the 0.17M
density
deposits
No.
12,000.
The
Re.
which
useful
of
maximum
current
under
a
using
gold
citrate
found
be
lattice
6.0
A
The
be
to
was
parameterof each of the crystallites
Crn-2.
produced
could
A.
bulk
in
4.075
However,
value, with an averagevalue the region of
was slightly smaller than the
below
2.0
lattice
A
densities
the
Cm-2,
parameterexhibited a smaller size.
at current

of

The crystallite size of thejetted samplecalculatedusing the Scherrerequationwas in the region

A.
A
300
It must be remembered
but
111
for
200
the
plane which showeda size of around
all

that this methodof estimatingthe crystallite size assumesall line broadeningis attributable to grain
indicate
222
III
fact
The
the
that this assumption
the
the
that
planes
were
not
same
as
planes
size.
line
broadening
difference
due
Further
incorrect.
the
to
that
this
of
analysis
was
revealed
was
density
0.0001275.
<e2>
the
current
over
measured
averaged
which
range
=
strain,
residual
There was no evidenceof either twin or stacking faults, except for a very low probability of a=
0.007 at a low current density. The crystallite size of the III plane as determinedby the Warren
A.
found
be
between
320
350
to
to
and Averbach method was
The preferred orientation of the jetted sarnplewas found to be strongly 220 above a current
density of 2.0 A crrr2. Below this value, aIII orientation predominated.

TheRMS strainobservedin thesesamplesgivenin Table23 wasnearlyanorderof magnitude

There
however,
deposits
for
was,
under
conventional
conditions.
than
produced
no clear
greater
density.
current
with
relationship

99

4.1

4.09

COB
4.07

-*-III
-+-203
--o-220
-311
-222

M6

a)

4.05

too

456
C.D. A/cmsq

10

90

-*-lll
-o-200
220
-4w-311

80
70
60
50
40

30
20

.0

loor

b)

456
C.D. Alcm sq

Figure 29. The relationship betweencurrent density and structural characteristicsas determined
by X-ray diffraction for a pure gold depositproducedby jetting in terms of (a) Lattice parameter
Reynolds
No.
Temp.
55-C.
12,000,
(b)
orientation.
preferred
=
=
and

Polishedand etchedmicrosectionsofjetted samplescan be seenin Photographs15,16,17 and

18. These showed that there were few structural featuresapparentat current densities below 6.0
A Crrr2.Above this value, fan shaped,cell-like structurescould be observed. Thesecells became
8
had
been
Photograph
18
thickness
about
of
achieved.
shows examplesof
a
jim
after
apparet
integral
deposit
8
but as the
Below
the
the
the
cell
structure
was
with
rest
of
these cells.
14m,
thicknessincreased,the cell "wall" exhibited a discontinuity. Extrapolation of the wall line showed
Topographically,
to
the
thesecells appearas nodules,
substrate
surface.
close
point
a coinciding
increasing in size with increasing current density as well as deposit thickness. These structures
described
by
Nakahara,
"rounded
77the
mounds"
who studied the structure and
resemble
clearly
formed
deposits.
He
that
structures
such
as a result of an
concluded
alloy
gold
of
morphology
inhibition processthat forced a small crystallite size to be producedas well as forming the rounded
mound structure.

100

8.1.3 The effect of electrolyte velocity

The velocity of the electrolyte played an important role in the morphology of the deposits
produced. As the velocity wasincreased,so the depositbecamesmootherfor any particular current
density and temperature.This effect canbe seenclearly in Photographs19,20 and 21. The overall
influence of the ReynoldsNo. can be seenclearly M the morphological diagrams in figures 18 to
23. However, the depositsproducedat a temperatureof 25-C did not follow this trend particularly
for the samplesproducedfrom thephosphateelectrolyte.The citrateelectrolyte exhibiteda reduction
in the value of the current densitiesat which smooth depositswere produced at high velocities at
this temperature.The morphological diagramsalso revealedthat the velocity modified the growth
behaviour of the deposits at current densities above those at which the deposit was no longer
smooth. This was particularly evident at the higher metal ion concentrations.
The velocity did not appearto have any significant influence on the selectivity.
8.1.4 Temperature effects.
It can be seenfrom the morphological diagramsthat for any particular current density and flow
increased
density
deposits
the
temperature
generally
the
current
at
which
smooth
were
rate,
between
deposits
For
transition
the
smooth
and
nodular
at a temperature of
example,
obtained.
25oCand a ReynoldsNo. of 6000 was in the region of 3.0 A CM-2for the 0.28M citrate electrolyte.
At 40oC, this increasedto about 3.8 A Crn-2and at 55-C to 4.0 A CM-2.The temperature also
influenced the type of growth of deposits above this transition. The 0.28M citrate electrolyte
from
deposits
25oC
but
55-C,
to
type
the transition was
transition
smooth
needle
at
at
a
produced
from a smooth to a nodular structure. Similar effects could be seen for deposits produced from
the other electrolytes used.

8.1.5 The influence of the gold concentmtion.

As the gold content of the electrolyte was increased,so the maximum useful current density
However,
in
increased.
0.17M
the
deposition
a
maximum
was
reached
region
of
where
rates
and
increasing the concentrationled to a slight reduction in the maximum useful current density. The
deposition
densities
deposition
the
and
rates
achievable
over
range
of
current
useful
maximum
in
listed
Table
24
tested
are
conditions

From theseresults,it is evidentthatthe type of supportingelectrolyte,aswell as its pH, has

density
influence
the
andplating rate.
on
current
maximum
a significant

101

8.1.6 The effect of pH

It was found that the deposit structuresof the citrate electrolytes improved by increasingthe
pH to 8.1.71is allowed a greaterdepositionrate to be achieved.Photographs22,23 and 24 show
depositsfrom the 0.28M citrate electrolyte at pH values of 5.3,6.1 and 8.1 respectively.

C.D.- 4.0A/cmsq
Temp.
- SSC
Re.
No- 12000
0.28M
Citrateelectrolyte
K- 48.8mS/cm
Phosphate
A 0.27M
electrolyte
K- 90.02mS/cm
Citrateelectrolyte
v 0.28M
K- 97.6mS/cm
0.17M
Citrateelectrolyte
K- 88.2mS/cm

E
(I,
U,
C)

234
Rdimensionless
distance
ratio

Figure30. Theeffectof a reducedconductivityon theselectivitycomparedwith equivalenthigher

conductivityelectrolytes.

8.1.7 The role of electrolyte conductivity.

Ile low conductivityelectrolytein Table I was usedto examinethe effect of electrolyte

in
30
Figure
the
the
the
effect
shows
of
reduced
selectivity
conductivity
on
comparison
conductivity.
is
Also
lower
It
0.17M
the
shown
citrate
concentration
electrolyte.
electrolytes.
with equivalent
is
improvement
in
be
the selectivityfrom the low conductivity
there
that
a
noticeable
can seen
is
In
improvement
17
%
the
there
others.
with
particular,
a
overtheequivalent
compared
electrolyte

102

higher conductivity citrate electrolyte. However, the depositquality deterioratedat a much lower
current density of about 3.75 A Crn-2.Despitethis, reasonablygood depositscould be producedat
a plating rate of 2.3 kLnVsecond.
8.1.8 The influence of nozzle size.

The sizeof the nozzlehasa markedinfluenceon both theselectivityof the depositaswell as

themaximumdepositionrateobtainable.Two othernozzlediameterswerebriefly examinedduring
this study,a 100jim and54014m.
8.1.8.1 Increased nozzle size.
Little work was carried out with the 540,um diameter nozzle. Results indicated that both the
deposition rate and selectivity were similar to the 400jum nozzle.
8.1.8.2 Decreasednozzle size.

Usingthe 100Amnozzle,a Reynoldsnumberof just 3233couldbe obtaineddueto pressure

limitationsof the pump.Comparisonof Figure31 with Figure27 showsthat the depositionrate
400Am
Inaddition,
densities
to
the
equivalent
current
using
nozzle.
compared
when
wasreduced
in
have
influential
important
factor
been
One
may
experimental
the selectivitywasnot asgood.
interfering
flow
Due
to
the
the
at closeproximitiesto the
with
nozzle
the reducedselectivity.
in
H/d
1.25
it
to
theexperimentswith the other
maintain
an
as
ratio
of
substrate, wasnot possible
had
10
be
becomes
H/d
It
Instead,
to
that
of
selectivity
used.
was
observed
reduced
a
ratio
nozzles.
for
No
Section
behaviour.
(see
8.1.1.
)
H/d
this
increasing
this
accounts
and
probably
ratios
with
further experiments
werecarriedout to verify this asusinglower ratioswould be impracticalfor
in
for
is
harder
deposition
The
terms
to
of experimental
rate
reduction
account
use.
commercial
later.
discussed
be
this
will
and
procedures

103

20
0.17MCitrate goldelectrolyte
100um nozzle
Currentdensity A/cm sq
0 4.0
Z 5.0
v 6.0
0 8.0
Temp.55 C

E
co

10

Re.- 3233

2
R Dimensionless
distanceratio

Figure 31. The selectivity of pure gold using a IOOIAmnozzle.

8.1.9 Pure gold deposition using pulsed current.

The application of pulsedcurrent hasbeenshownto improve depositquality under conventional
deposition conditions. Having establishedthe factors that gave the highest deposition rates under
DC conditions, the influence of pulsed current was established.The conditions of deposition are
Examination
18.
in
16
Tables
to
of the depositsproducedenableda detailed morphological
given
diagram to be producedfor an averagecurrent density of 6.0 A Cm-2.This is shown in Figure 32.
Figure 33 shows a morphological diagram of depositsproduced at an averagecurrent density of
8.0 A CM-2.However, this is lessdetaileddue to the fewer samplesproducedat this current density.
From figure 32, it canbe seenthat there were a wide variety of morphological structuresproduced.
Typical structures can be seen in Photographs25,26,27,28 and 29. For both average current
densities, it can be seenthat there is a narrow region of both low duty cycle and short on-time at
deposits
None
deposits
the
smooth
were asgood asthoseproduced
of
produced.
were
which smooth
by DC as can be seenin Photograph28 with obvious gapsbetweenthe surface nodules. Deposits
deposited
by
DC
lower
deposition
did
those
were
produced
at
structures
as
good
that
exhibit equally
rates.

104

Diagram

Morphologicat
Dn-Time

vs

Duty

of

CycLe

Pulsed
AverQge

Temp. = 55 C

Rated

Jet

Gold

C.D. = 6.0 A/cm

sq

Re. No. = 12000

100
nodular

slightly

80
60

very
nodutor

40

20

nodular

smooth

'rose'

0.1

0.02

0.2
(In-Time

0.5

1.0

20

5.0

10.0

mseconds.

Figure 32. Morphological diagram of on-time vs duty cycle at an averagecurrent density of 6.0
A Cm-2.

Diagram

Morphological
On-Time

Duty

vs

of

Cycle

Temp. = 55 C

Pulsed

AverQge

Jet

Plated

Gold

C.D. = 8.0 A/cm

sq

Re. No. = 12000

100
very

80

noclutor

>1

60
noclutar
40

20

crown
t
--sr, o-o--

f ield
orientate
0.02

unknown

0.1

0.2

On-Time
Figure 33. Morphological

0.5

1.0

2.0

5.0

10.0

mseconds,

diagram of on-time vs duty cycle at an average current density of 8.0

A Cm-2.

105

8.1.9.1 Variation of the average current density.

Increasingthe averagecurrent density led to a decreasein the size of the smooth window. An
increase in the plating rate was also observed, up to a maximum of 5.5
at
an
average
jum/sec.
current density of 9.0 A Cm-2.Increasingthe averagecurrent density further reducedthe plating
rate to lessthan 3.0 jAm/sec.However, SEM examinationrevealedan evengreaterlevel of porosity.
Examination of all the samplesshowedthat a depositionrate of 3.5 lirrL/sec.could not be exceeded
inter-granular
introduction
deposition
Overall,
the
there
of
without
porosity.
current
pulsed
using
dendritic
deposits
increasing
increased
towards
tendency
with
nodular
and
averagecurrent
an
was
density.

8.1.9.2 Variation of the on-time.

Increasing the on-time led to an increasednumber of nodules formed and an increase in the
in
increase
dendritic
formation
A
the
rate
of
structure
was also seenespecially at
nodules.
of
size
duty cycles below 60%.

8.1.9.3 The effect of increasing the duty cycle.

Low duty cycles produced dendritic, needlelike, crown shapedor rose shapeddeposits, particularly with increasingon-times.High duty cyclestendedto producenodular depositsirrespective
duty
%.
between
20
40
The
suitable
cycles
were
and
most
the
on-time.
of

8.1.9.4 The influence of pulsed deposition on selectivity.

Figure 34 showsa selectivity plot comparinga DC and a pulseplated spot. The averagecurrent
density of the pulse plated spot is the sameas that used for the DC plated sample, that is 6.0 A
improvement
is
in
in
be
The
It
there
the
that
the
an
selectivity
pulse
plated
sample.
seen
can
CM72.
be
densities
high.
behaviour
In
for
to
that
the
this
seem
this
would
peak
current
pulse
were
reason
density
30
A
Under
field
intensity
these
the
the
Cm-2.
conditions,
was
electric
current
peak
example,
during
DC
higher
jet
the
than
on-time
under
conditions thus enhancingthe
the
much
was
within
deposition
impingement
This
led
less
lateral
distribution.
to
the
outside
region.
primary current

106

20
0 DCsample6.0 A/cm sq
A pulsesampleAUP4/22
Duty cycle= 20%
On-time= 0.02 sec.
AverageC.D. - 6.0 A/cm sq
Temp.z 55 C
Re.- 13545

C,,

e
10
-0

2
R dimensionless
distancefactor

Figure 34. A selectivity plot comparing a pulsed current deposit with the equivalent DC deposit.

8.1.10 Examinationof the limiting factors controlling maximum depositionrates.

Having established
the electrolyteandthe depositionconditionsthat gavethe greatestplating
deposits
by
the
of
acceptable
quality
together
and
selectivity,
mechanisms
with
which the
rates
by meansof bothelectrochemical
depositdeterioratedcouldbeexamined.Thesewereestablished
andstructuralobservations.

8.1.10.1 Mass transfer studies.

Becausethe limiting currentdensitycontrolsthe maximumrate at which electrodeposits

can
be produced,polarisationcurveswerepreparedto identifythis valueandthe ratio of "'L at which
jetted depositsbeganto deteriorate.As describedin Section7.4. two techniqueswere applied,
SampledCurrentPulseVoltametry,SCPVandSampledVoltagePulseAmperometry,SVPA.

107

8.1.10.1.1 Sampled Voltage Pulse Amperometry.

This methodwastried initially as it was simpler to setup and operate.In addition, as mentioned
in Section 3.2.1.2. there was less likelihood of problems with surface roughening with galvanodynamic methods as with potentiodynamicmethods. Figure 35 shows a polarisation curve of
the 0.17M citrate gold system.No compensationfor the IR drop betweenthe referenceand working
is
limiting
However,
large
be
It
that
there
clear
current
plateau.
can
seen
no
a
used.
was
electrode
Tafel region is visible. The slope of the Tafel line was calculated to be -330 mV/decade. The
maximum useful current density for theseconditions was in the region of 3.0 A crn-2.This lies
beyond the Tafel area in what would appearto be a mixed activation/diffusion controlled region.
At the high current density end, the slope of the curve alters. This could indicate the post limiting
current region but there was no evidenceto confirm this.

CD

.11
AppliedcurrentdensityA/cmsq

10

100

Figure 35. Polarisation curve for the 0.17M citrate gold electrolyte using SVPA
Oneproblem with obtaining information using this techniquewas the influence of superimposed
5OHz noise on the signals, particularly at low applied current densities. The source was from
isolate
despite
but
the
to
and
cell and sensingresistors this
shield
efforts
equipment
surrounding
be
eliminated.
not
could
problem

108

8.1.10.1.2 Sampled Current Pulse Voltametry.

It was found that using SCPV, the noise problem encounteredwith the other techniquecould
be reducedalthoughnot eliminated.This madesignal measurements
much easier.Figure 36 shows
the polarisation curves for the 0.17M citrate gold electrolyte at three different values of Reynolds
No.

0
4-JA

-Z:

C-)

1590
Csz

-I

L:::]

C,,

"411.
Z-'k .

4-.
C)
4-,

4-2

NY

-T-l

ZIA 'VIJU'

C] Re.No.= 13545
Re.No.= 3355
Re.No.= 1342

X\

_TZ

all 'I;?-119-1
EN

w
7

Temp.55 C
IN

-3

rsi

IN

kz-N
lu
V

/N

-4
001
.

LXI
w
P

01
.

.11
CurrentDensityA/cm sq

10

100

Figure 36. Polarisationcurvesfor the 0.17M citrategold electrolyteusingSCPV.

once again, no clearly defined limiting current density plateau could be seen. In order to
factors
function
due
if
to
this
purely
electrochemical
or
was
a
of the measurement
was
establish
technique, the method was applied to a copper sulphateelectrolyte. The electrolyte chosen was
formulation was 0.014M
for
The
been
transport
has
studies.
mass
previously'25.
used
that
one
Cuso4 with 1.5M H2SO4as supporting electrolyte. The methodwas applied to this electrolyte and
it
be
With
in
37.
Figure
this
can
seenthat a definite
electrolyte,
as
produced
the polarisation curves
limiting current plateau can be seen for all three values of Reynolds No. The limiting current
densities were found by calculating the mid-point betweenthe lowest point on the plateau and the
highest. These are listed below.

109

Reynolds No.

Lin-itingcurrent density

1843

0.367 A

CRr2

5252

0.470 A

Cnr2

7538

0.591 A

Cnr2

0.0

4-.

C,
4-.

[Z
-

-1.0

01
.

.1
Current density A/cm sq

10

Figure 37. Polarisation curves for a 0.014M CUS04electrolyte at 25oCusing SCPV

It can be concludedthat whilst the data points on thesecurves are subjectedto some individual
better
be
10%.
do
to
than
to
a
valid
and
were
repeatable
within
variance
of
they
appear
variations,
It should be noted that although there appearsto be a linear region prior to the limiting plateau,
is
in
for
direction
Evidence
Tafel
this
that
the
be
slope
varied
a
positive
is
the
region.
to
this unlikely
The onset of turbulent flow occurred for
7000.
No.
between
1500
Reynolds
increasing
and
with
linear
in
fact
indicate
This
2000.
that
this
in
apparent
region
was
would
this system the region of
in
In
domain.
as
copper
addition,
a sulphateelectrolyte
controlled
the mixed activation/diffusion
is highly reversible, it has a low activation energy for deposition and a well defined Tafel region
be
expected.
not
would

110

The limiting current densitiesobtainedwere usedto obtain the Sherwoodnumber relationship

with the Reynoldsnumber. As the diameterof the cathodewas the sameas that of the nozzle, an
impingement correlation was deemedmost suitable for analysis. It was found that by using the
Chen.
by
Alkire
108and
obtained
correlation
Sh - 21.03Re

0.448

(29)

the data from the turbulent flow experimentsagreedto 10% and 20% for Re = 7000 and Re =
10800. If it is consideredthat some deposit growth was experiencedduring the measurements,
if
be
Additionally,
a complete, steadystate equilibrium was not
expected.
some variations could
densities.
limiting
higher
lead
be
to
to
current
of
this
values
expected
would
achieved,
Other workers who have attemptedto measurelimiting current densitiesfor pure citrate gold
in
described
Chapter
2,
However,
been
have
the addition of a
as
unsuccessful.
also
electrolytes
few pprn of lead has been shown to interfere with the hydrogen evolution reaction and allow a
limiting current plateau to be observed. However, the addition of lead to the electrolyte was not
bythis
density
limiting
methodwould not necessarilybeapplicable
obtained
current
considered,asa
lead
lead.
has
been
described
As
in
the
and other metallic
earlier,
of
absence
to the results obtained
bonding
lead
to
performance.
wire
gold
poor
can
gold additives

8.2 GOLD ALLOY DEPOSITS.

Having establishedthe basic controlling factors with the pure gold electrolyte system, these
factors were then applied to the production of alloy gold deposits.Three commercial electrolytes
CM,
N,
Ronovel
Ronovel
for
initial
containing cobalt and
containing
nickel,
studies,
were chosen
in
described
Section
8.3.2.1. As was
iron.
Samples
7000,
as
were
prepared
Auruna
containing
deposition
the
maximum
rates at
the
all
electrolytes
exhibited
samples,
gold
pure
observed with
densities
The
found
and
current
higher
maximum
useful
rates
are
plating
gold concentrations.
the
listed in Table 25.

Whilst the Auruna 7000 solution gave the greatestdeposition rate, examination of the deposits
fracturing
high
the
the
these
spots
were
underlying glass
rates,
that
plating
at
showed
produced
internal
high
levels
For
Auruna
indicating
tensile
this
of
stress.
reason,
substrateand exfoliating,
7000 was not used for further trials. In addition, whilst the cobalt and nickel alloy golds are
iron
the
are
golds
relatively
alloy
new
and
would
specifications,
existing
within
accepted
generally
Ronovel
The
CM
in
difficulty
commercially.
electrolyte
acceptance
gaining
present a greater

III

showedsignificant evidenceof instability, with what appearedto be singlegold cyanideprecipitating

on the container walls after several hours use in the jetting equipment. For these reasons, the
Ronovel N electrolyte was chosenfor further exan-driation.
As Ronovel N was a proprietary electrolyte, the composition was not disclosed. However, it
was known from the safety data supplied that the basic electrolyte was composedof an oxalic
acid/alkali metal oxalate/phosphonatemixture. As supplied, the basic electrolyte also contained
an addition agent referred to as "booster". This was a solution of nicotinarnidewith some oxalic
acid. The purpose of this addition agent was claimed to allow operation at an increasedcurrent
density and plating rate.
8.2.1 The influence of deposition parameters for the Ronovel N electrolyte with no nickel.
In order to establish the basic deposition parameters for-this electrolyte, a series of trials were
initiated using the basic electrolyte and a gold concentration of 20 g 1-1but with no nickel added.
As was found with the pure gold, the maximum useful current density was influenced by the
electrolyte velocity. At a Reynolds No. of 1000, the maximum useful current density was found
to be 2.0 A Cm-2,at a Reynolds No. of 2600 it was 3.5 A cm-2, whilst at a Reynolds No. of 10,600
it was 4.25 A crn-2. On the basis of these results, it was again evident that to obtain the highest
deposition rates, high electrolyte velocities would be required. A temperature of 55oC was chosen
for the remaining trials in accordance with the manufacturers recommendations. Tables 19 to 22.
give ftill details of the conditions used.

The basic Ronoval N electrolyte containing no nickel but with 60 n-J 1-1"booster" produced
semi-bright deposits.Optical examinationrevealedthat the deposittopographyexhibited a rounded
density
a
wide
current
over
range, the size of the mounds increasing with
appearance
mound
increasing current density. The nodules were approximately twice the size of the equivalent
thicknessof pure gold depositedunder identicaljetting conditions. As with the pure gold samples,
it was clear that surfacefeatureswere amplified asthe plating time and thus the thicknessincreased.
Photograph 30 shows an optical micrograph of a 17.2,um deposit from this electrolyte produced
Photograph
8.0
A
31
density
Cr1r2.
of
shows a microsection of a similar deposit but
current
at a
density
9.0
A
It
be
of
CM-2.
can
seenthat unlike the pure gold electrolytes,
a
current
at
produced
the nodulation would seemto have commencedas deposition proceededand not during the initial
density
9.0
A
Above
current
of
a
CM-2,the nodule size was reducedbut with an
of
growth.
stages
increasein the number of nodules.

112

Photograph32 shows a typical microsection of a gold/nickel alloy produced from a Ronoval

N electrolyte that containednickel as well as booster. This particular samplecontained 3.0 g 1-1
and 60 ml 1-1booster. An "inverted cone" structure associatedwith one of the surface rounded
mounds can clearly be seen. In the caseof nickel containing deposits, the roots of the mounds
originated at or near the substratesurface.

lessthanthatof thepuregold for the equivalentcurrent

Thedepositionratewasconsiderably
densitiesalthoughhighercurrentdensitiescouldbe obtainedwithout seriousdegradationof the
deposit.
Increasingthe boosterconcentrationto 80 n-d1-1reducedthe plating rate by a further 20 % with
no observableimprovement in the deposit topography.

8.2.2 The effect of the addition of nickel to the basic Ronovel N electrolyte.
The following additions of nickel additive were madeto the basic electrolyte; 0.5 g 1-1,0.7 g
1.1 g 1-1,1.5 g 1-1,2.2 g 1-1,2.5 g 1-1and 3.0 g 1-1.With each increment, deposit spots were
for
deposit,
hardness
topographical
the
examination,
nickel
content
of
and XRD
produced
examination. Two setsof sampleswere produced. The first set were plated to a thickness of >
16 jArnso that comparisonswith pure gold could be made. In addition, thick depositswere required
for the testing of the physical characteristicsof the deposit.The secondsetwere platedto a thickness
for
in
These
from
2.5,
:
value
use
realistic
production.
a
more
were
produced
an electrolyte
of
um,
1-1
1.9
g
nickel.
containing

8.2.2.1 Relationship betweennickel in the deposit, nickel in the electrolyte and current density.
Figure 38 shows the relationship between the nickel in the electrolyte and the nickel in the
deposit over a rangeof current densities.A linear regressionhasbeenapplied to the datapresented.
it can be seenthat a linear relationship exists for all concentrationsof nickel used. The error bars
indicate the analytical error of 6% of the nickel in the deposit. A further 5% error, not shown
for
in
the
solution.
analytical
error
nickel
the
represents
graphs,
on

113

.5

CurrentdensityA/cm sq
0 2.0
V 6.0
+ 12.0

Z 4.0
0 8.0
X 16.0

I Plotsdonot include
.3
5%error in Ni in soln.
determination

.2

0.0
2
Ni in solutiong/I
Figure 38. The relationshipbetweenthe nickel in solution and the nickel in the deposit for different
applied current densities
Figure 39 shows how the nickel in the deposit varied with the applied current density. A
data
best
has
been
fit.
Whilst
to
the
to
the
this
applied
provide
curve
analysis
regression
geometric
in
its
lower
is
for
be
the
concentrations
validity
of
nickel
solution,
quite clear at
questionable
may
believe,
is
be
different
There
to
therefore,
that
higher
such
a
relationship
will
no
reason
values.
the
for low values of nickel. The graph indicates that at low current densities, a greater quantity of
is
This
high
in
deposit
densities.
incorporated
the
than
understandableconat
current
nickel was
is
in
it
is
than
the
a
citrate
considerable
more
noble
that
electrolyte
gold
unless
nickel
sidering
strongly complexed.

114

68

10

12

14

16

18

20

Current densityA/cm sq

Figure 39. The relationshipbetweenthe nickel in the depositand currentdensityfor different

in
the electrolyte.
nickel
of
concentrations

8.2.2.2 Deposit topography.

The addition of nickel significantly affected the surface topography particularly for thick
deposits. Concentrationsof nickel in solution greater than 0.7 g 1-1reduced the nodule size and
from
deposit
those
the
compared
when
with
produced
electrolytesnot containing nickel.
smoothed
An increase in the nickel content produced deposits with a marginal reduction in the size and
frequency of surface features. Comparison between Photograph 30 and Photographs33 and 34
However,
high
internal
the
thicker
samples
showed
evidence
of
these
clearly.
stresses
effects
show
1-1
deposit
2.2
>
these
of
showed
signs
as
some
of
cracking or
of
g
concentrations
at nickel
fracturing of the glass substrate.

35 and36 showdepositsabout2.5 um thick. It canbe seenthat thereare few

Photographs
becoming
features,
apparenton thosesamplesproduceabovea current
small
nodules
with
surface
By way of comparison,Photograph37 showsa 2.5 14mthick gold/nickel
densityof 10.0A Cm-2.
depositproducedunderconventionalconditions.

115

8.2.2.3 Deposition rate.

Figure 40 showsthe depositionrates obtainedfrom electrolytesboth with and without nickel.
boosterandthosecontainingnickel showroughly thesamedeposition
Thesampleswith only60n-A1-1
ratesandit maybe concludedthat the additionof nickel doesnotaffect the depositionrate. Increasing
the booster concentrationin the absenceof nickel does reduce the deposition rate significantly.
Comparing Figure 40 with Figure 24, it can be seenthat the presenceof the booster reducedthe
deposition rate considerably.
It wasfound that a maximumdepositionrateof 2.8,um sec-1could be obtainedfrom an electrolyte
containing 60 ml 1-1booster and - 2.0 g 1-1nickel at a Reynolds No. of 10600 and a temperature
of 55-C. These conditions also provided a similar hardnessto those producedunder conventional
deposition conditions.

4
w
E

C>

N 60 ml/I boosternoNi
E] Ronovel
80
booster
Ronovel
N
Ni
ml/I
no
,0
Ronovel
N 60 mi/I booster
2.2g/l Ni
Ronovel
N 60 ml/I booster2.5g/l Ni
3.0 g/l Ni
N 60 ml/I booster
+ Ronovel

0
0

10

is

20

Currentdensity A/cm sq
Figure 40. Current density vs deposition rate for various concentrationsof nickel and booster in
the Ronovel N electrolyte.

116

8.2.2.4 Current efficiency.

The current efficiency was measuredfor an electrolyte containing 1.9 g 1-1nickel and 60 n-d1-1
booster. Figure 41 showsthe relationshipbetweenthe current density and the current efficiency.
As with the pure gold, low current densitiesgave rise to low efficiencies in the region of 30%. At
a current density of 3.0 A cnr2, the maximum efficiency of about 60% was achievedafter which
it fell.

100

90
80
e
.,.
>1
Iv

ZZ-3

60
so

40
30

10
Current density A/cm sq

is

20

Figure 41. Current efficiency vs current density for the Ronovel N electrolyte containing 1.9 g 1-1
Ni and 60 ml 1-1booster.

8.2.2.5 Hardnessof the deposits.

Figure42 showstheinfluenceof nickelandboosteron thehardness
of thedepositsat different
from
60
1-1
booster
The
densities.
the
produced
electrolyte
containing
ml
samples
only were
current
hardness
deposits.
An
increase
in
being
to
the
hardest
pure
gold
the booster
equivalent
the
of all,
deposits
Additions
hardness
the
the
to
of
nickel
produced.
electrolytecontaining
of
the
reduced
boosterreducedthehardness
60 ml 1-1
proportionately.Referringto Figure38 togetherwith Figure

117

42, it is clear that at lower current densities,where the nickel in the deposit is greater, a lower
hardnessresults.This is in conflict with the well known effect of the hardnessincreasingwith the
addition of nickel seenwith conventionalgold nickel alloys.

34567

10

CurrentdensityA/cm sq

Figure 42. Deposit hardnessvs current density for different concentrationsof nickel in the electrolyte.
Figure 43 shows how the nickel in the deposit influenced the hardnesswhen depositedat
different current densities.It is evident from this graph that the quantity of nickel in the deposit
%)
hardness.
Low
(<
0.1
factor
the
the
contents
nickel
showedroughly the
affecting
only
was not
samehardnessvaluesirrespectiveof the current density. This did not vary by much for samples
below
increased
5.0
densities
A
However,
cm-2.
current densitiesexhibited
at
current
produced
different hardnessesfor the samevalue of nickel in deposit.The relationshipbetweenthe nickel
in deposit,current densityandhardnessis summarisedin Figure 44, which showsa 3-dimensional
surfaceplot of eachof the parameters.

118

220
Currentdensity
A/cm sq

200
cr

160

140

120

loo I
0.0

.1

.2
Ni in deposit

.3

.4

Figure 43. The relationshipbetweennickel in the depositand the hardnessfor different valuesof
applied current density.

Figure 44. A 3-D surfaceplot surnmarisingthe relationshipbetweencurrent density, nickel in the

depositand hardness.

119

8.2.2.6 Selectivity of the deposits.

Figure 45 showsa selectivity plot of depositsfrom the Ronovel N electrolyte without nickel
but containing60 ml 1-1of booster.It can be seenthat the selectivity was not as good as the case
of the pure gold depositsfrom the non- commercialelectrolytes.In particular, therewas a greater
thickness of deposit in the wall jet region than was previously seen, especially at low current
densities.With the addition of nickel, the situationwas improved. Figure 46 showsthe selectivity
1-1
With
1.5
N
from
Ronovel
deposits
the
g
nickel.
nickel, the selectivity
containing
produced
of
approachedthat of pure gold.

20
Current density A/cm sq

No nickel
e-_

0 2.0
5.0
7.0
9.0
+ 16.0

lc-zzll

%\

Temp55 C

Re. - 10600

NQ-K-ll

14
0

23
R Dimensionlessdistance ratio

Figure 45. Selectivity of depositsfrom a RonovelN electrolytecontainingno nickel

An increasein the nickel concentrationto 3.0 g 1-1marginally worsenedthe selectivity with a
Figure
47
jet
However,
deposit
in
thin
the
as
shows.
region
wall
very
a
slightly greaterspreadof
Figure
interesting
48
A
2.0
below
densities
observed.
cm-2,
effect
was
shows the
an
at current
1.0
A
It
be
density
deposit
crn-2.
of
can
clearly
produced
at
a
current
selectivity of a gold/nickel
in
in
increase
the
thickness,
R=4,
the
effect
an
not
observed
there
an
was
that
of
value
at
a
seen
increase
in
by
local
This
transfer,
a
or
caused
mass
was
presumably
measured.
samples
pure gold
it is a result of the variation in current efficiency with current density.

120

E
=
C,,

23
R Dimensionless
distanceratio

Figure 46. Selectivity of depositsfrom a Ronovel N electrolyte containing 1.5 g 1-1nickel.

E
La
(I)
-d

23
R Dimensionlessdistance ratio

Figure 47. Selectivity of depositsfrom a Ronovel N electrolyte containing 3.0 g 1-1nickel

121

E
=
I,

-C

i-1

0
0

34
R Dimensionless
distanceratio

Figure 48. Selectivity of a deposit from a Ronovel N electrolyte containing 3.0 g 1-1produced at
1.0 A CM-2.

8.2.2.7 Crystal structure.

As with the pure gold, samplesof gold nickel alloy were examinedusing XRD. In addition, a
deposition
conventional
conditions
alloys
were
under
gold
nickel
produced
of
number of samples
for comparison. Figure 49 showsthe resultsobtainedfrom theseconventionaldeposits.In addition,
from
booster
N
the suppliers.
Ronovel
obtained
containing
was
not
electrolyte
a sample of a
Unfortunately, it cametoo late for the production of jetted samplesbut it was possible to observe
deposition
These
in
be
booster
conventional
conditions.
results
the
under
can
seen
the effects of
figure 50. Figures 51,52,53, and 54 show the results obtainedfrom electrolytes containing 60 ml
1-1booster only, 80 ml 1-1booster only, 60 ml 1-1booster and 1.9 g 1-1nickel in solution and 60 nil
1-1booster and 3.0 g 1-1nickel in solution respectively.

122

103

4.1

0111

90

-4-200
-a-220
311
Z! 2

4.09

#111
-4-220
-a-223
-311

80
70

4.OB

60
50

CL

do

-0

4.07
30

20

4.06

10
4.05

to

a)

30
20
C.D. rrAlcm
sq

40

50

10

b)

20

30

40

50

C.D. irA/cmsq

C)

Figure 49. The relationship betweencurrent density and structural characteristicsas determined
by X-ray diffraction for a conventionallydepositedgold nickel alloy from a Ronoval N electrolyte
in terms of (a) lattice parameter(b) preferred orientation and (c) hardness.

123

4.1
4111
200
220
4.03

-311
-222

4.09

CL

a)
.U4.07
4.06

05
a)

10

15

20

25

30

35

40

C.D. M/cmsq

10

20

30

40

50

C.D. ffAlcmsq

b)

i
leo

le

15 20
25
C.(L Wcmsq

30

35

40

C)

Figure 50. The relationshipbetween current density and structural characteristicsas determined
by X-ray diffraction for a conventionally deposited gold nickel alloy without booster from an
Auronal MRN electrolyte in termsof (a) lattice parameter(b) preferred orientation and (c) hardness.

124

a)

....
1

*111
-o-200
220
-*--311

90

70
60
50
C
.

40"
30
20
10
0
05

b)
10

15

20

C.D.A/cm
sq
Figure 51. The relationship between current density and structural characteristics as determined
by X-ray diffraction for jet deposited gold from an electrolyte containing 60 n-d 1-1booster in terms
(b)
lattice
(a)
preferred orientation.
parameter
of

125

a)

100
90

-+-200
220
-311

80
70
60
50
40
30
20
10
g

b)
10

15

20

C.D.A/cm
sq

Figure 52. The relationship betweencurrent density and structural characteristicsas determined
by X-ray diffraction for jet deposited gold containing 80 ml 1-1booster in terms of (a) lattice
parameter (b) preferred orientation.

126

a)

30rl
20t:

.6

10
0
05

b)
15

10

20

C.D.A/cm
sq

as determined
Figure 53. The relationshipbetweencurrentdensityandstructuralcharacteristics
by X-ray diffraction for jet depositedgold nickel alloy from an electrolytecontaining1.9 g 1-1
(b)
lattice
(a)
booster.
1-1
H
60
preferredorientation.
parameter
nickel and

127

a)

I
CO

80

-s-220

70 :.

60
50
40
30
20' ,
10

b)
0

10

15

20

C.D.A/cm
sq

Figure 54. The relationship between current density and structural characteristicsas determined
by X-ray diffraction for jet depositedgold nickel alloy from an electrolyte containing 3.0 g 1-1
(a)
lattice
(b)
booster.
1-1
60
preferred orientation.
parameter
ml
nickel and

128

The effect of the booster can be clearly establishedunder conventional deposition conditions
by comparing Figures 49 and 50. Figure 50(b) shows that in the caseof the Auronal MRN, a
distinct 111 texture is formed between 10 and 15 mA crrr2, the normal operating range of this
electrolyte. Indeed, below this range, the deposit appearancewas matt. Above this range, the
deposit showed signs of "burning" at the edgesof the sample. Figure 49(b) shows that with the
addition of the booster, the III texture was predominant above 5 mA Cm-2,with the apparent
suppressionof other growth directions. Pure gold, as has been seenearlier, possesseda distinct
3 11texture under conventionaldepositionconditions. It would appear,therefore, that a 111texture
is one of the necessaryconditions for the effective performanceof a nickel hardenedalloy gold.
Hardness measurementsshowed that the depositswith the booster were 15% harder than those
booster
be
density
15
It
the
that
to
reduced the
seen
of
mA
Cm-2.
can
also
a
current
up
without,
in
its
deposits
lattice
to
those
compared
produced
absence.
parameter
effective
The lattice parameter of the conventional depositswithout booster exhibited a mean lattice
%
less
0.27
than that of annealedgold and remainedessentiallyconstantwith current
parameter
density. The valuesfor all the planeswere comparablewithin the overall accuracyof measurement.
The lattice parameter of the conventional deposit containing booster was also lower than that of
being
less
-0.33%
than that of pure gold and showed a small
the
mean
value
annealed gold,
increasinglinear dependenceon current density. However the 220 planeswere significantly larger
and were comparableto those of the electrolyte without booster.
In both cases,the crystallite size of the III planesas determinedby the Scherrer equationwas
for
The
for
the III reflection was -350
the
than
value
other
measured
planes.
calculated
greater
A for depositsproducedat the lower current densities,decreasingto -200 A with increasedcurrent
density. The crystallite sizescalculatedfor the other planesmeasuredwere typically in the region
A.
booster,
from
In
the
the
100
elecirolyte
containing
samples
produced
the
closer
of
case
of
RMS
Averbach
Warren
that
the
a
significant
strain contributed
and
analysis
revealed
analysisusing
to this difference as canbe seenfrom Table 23. In addition, a slight asymmetryof the reconstructed
faulting
but
twin
that
some
was
present
as explained earlier, no accurate
suggested
peaks
be
their
could
magnitude
made.
measurementsof
Figures 51 and 52 show the data calculatedfrom samplesproducedbyjetting from electrolytes
1-1
booster
but
Figures
6(b)
80
7(b)
1-1
60
no
nickel.
n-J
respectively
and
show
and
ml
containing
increasing
be
It
that
can
seen
with
current density, the 111 component
the preferred orientation.
%
220
60
The
the
the
to
component.
expense
of
around
at
contributions
rapidly
of orientation rises
from the 200 and 311 remained fairly constant and close to their values expected in a random
is
This
consistentwith aIII
sample.

texture.

129

Figures 51(a) and 52(a) show the influence of the boosteron the lattice parameter. Thereisa
general trend of a reduction in the lattice parameterfor all planeswith increasingcurrent density.
It will be noted that the 200 plane exhibited a significantly smaller lattice parameterthan the other
planes. This would suggestthat a distortion of the lattice wasbeing createddue to the incorporation
of the booster (or breakdownproduct of it) within the 100 (200) planes.
As was observedin the previous samples,the 111planesexhibited a larger apparentcrystallite
size than the othersas determinedusing the Scherrerequation. For both concentrationsof booster,
A
be
in
found
300
III
to
the region of
the
whilst that of the other measuredplanes was
plane was
in the region of 150 A. This may be attributed to both stacking faults as well as residual strain as
can be seenfrom Table 23.
The presenceof nickel reducedthe lattice parameterof most of the planes examinedto below
A.
A
densities,
increasing
4.07
This latter value was about
low
4.07 at
to slightly above
current
the sameas that for the samplescontaining boosteralone. Examination of Figures 53(a) and 54(a)
increasing
density,
fell
200
lattice
the
the
that
current
similar to
with
parameter
of
plane
revealed
that of the samples with booster alone. With relatively large concentrationsof nickel in the
in
lattice
220
311
the
the
the
parameter, particularly at
and
also
exhibited
reductions
electrolyte,
high current densities.

The crystallitesizeof the 111planesasdeterminedby the Scherrerequationwasin the region

A.
A
in
Again,furtheranalysisrevealed
100
200
whilst thatof theotherplaneswas theregionof
of
that both stackingfaultsandRMS straincontributedto this difference.
To summarise,both the booster and the nickel induced aIII preferred orientation but it was
density
influence
booster
the
the
current
that
a
wide
exhibited
greater
over
range. The
clear
indicated
both
lattice
by
that
the
the
the
of
presence
of
parameter
measurement
evidenceprovided
booster and nickel reducedthesevaluesto below the pure gold value, probably due to incorporation
lattice.
indicated
Indeed,
that certain planes incorporated
the
the
additives
the
evidence
within
of
a larger proportion of thesematerials. The true graft! size for the III plane, after correction for
jetted
faults,
indicated
for
the
that
samples,a small crystallite size
all
residual strain and stacking
A
300
200
in the region of
to
was produced. The nickel had a slight influence in reducing the
However,
deposition
further
under
conventional
conditions.
underjetting
conditions,
crystallite size
it appearedto be the main causeof the reduction of crystallite size.

130

8.2.3 Sampled current pulse voltammetry of the Ronovel N electrolyte.

Polarisation curves were producedfor the Ronovel N electrolyte both with and without nickel
using SCVP. Figure 55 shows the results of this study. In the absenceof nickel, but with 60 ml
1-1booster, a well defined Tafel region was observed,the slopebeing-186mV/decade. Beyond the
Tafel region, a small mixed activation/diffusion controlled region was observedwhich led into a
small but well defined limiting current plateauat a current density of 3.6 A Cm-2.With the addition
of 1.9 g 1-1nickel, the shapechangedconsiderably. At low overpotentials, a much steeperslope
was observedleading to what appearedto be a small plateauxat a current density of 0.078 A Cm-2.
Beyond this, a more well defined Tafel region could be seen, with a slope of
-290 mV/decade.
However, the limiting current plateau seenin the absenceof nickel had disappeared.The initial
plateauthat occurred on this curve is probably the limiting current density for nickel. Theseresults
will be discussedin Chapter 10.

C?
0

C?

-3

-4

001
.

01
.

.II
Appliedcurrent density A/cm sq

10

100

Figure 55. Polarisationcurve of the RonovelN electrolyteboth with and without nickel using
SCPV.
I

131

CHAPTER 9

THE APPLICATIONS OF HIGH SPEED SELECTIVE JET

ELECTRODEPOSITION

There are a number of potential applications for which HSSJE would be suited. These are
mainly in the electronics industry. With a suitable scale-upof the system, it could be adaptedfor
engineeringuse, applying the principles outlined here to other metals. There are also areaswithin
the decorative market that could also be exploited. The following Sectionsoutline some of these
applications in more detail.

9.1 APPLICATIONS WITMN THE ELECTRONICS INDUSTRY.

There are 4 main areasof the electronics industry where such a processmay be utilised.

9.1.1 The direct writing of Microwave Integrated Circuit Substrates (MICS).

MICS are used extensively throughout the Telecommunicationsand Defence industries for
mounting active devices such as amplifiers, delay lines etc. The substratescan be made from
PTFE
by
These
or
composites.
quartz
are
metallised
sputtering a "keying" layer
alumina,
sintered
of chromium, followed by approximately 0.1 jim of gold. Circuit tracks are either defined by
photoresist and gold plated through the defined lines. Alternatively, the whole substrateis plated
with gold and the tracks defined by a print and etch process. Each processhas its disadvantages.
The additive processsuffers from photoresistattack by the gold depositionprocess.This is due to
the production of cyanideat the interfaceasa by-product of the depositionprocess.This effectively
failure
leading
definition
the
to
the
resist
a
complete
of the adhesionof
of
poor
or
edge
undercuts
the resist. There are a number of formulations that are claimed to overcome these problems,
including a tin brightened gold (111)electrolyte that operatesat a pH of 0.60. However, the
is
industry
doubtful
for
the
electrolyte
where very pure deposits
an
microwave
such
of
usefulness
high
definition
The
tracks as the photoresist is
process
can
produce
very
subtractive
are required.
does
into
However,
the
and
the
stage
not
come
contact
with
gold
electrolyte.
at
etching
up
applied
to 80% of the electrodepositedgold is etchedoff, constituting a considerablere-processingcost.
Consequently,thesemethodsare expensive.Apart from the gold, the main cost lies inthe production
form
in
These
However,
an
enlarged
and
are
produced
require
photo-reduction.
masks.
of suitable
by using the direct writing facility provided by HSSJE,the circuits can be written without the need

*Auruna332, suppliedby DegussaGMB.

132

for masking directly from the CAD designs.A sputteredor electrolessplated layer is still required
in order to make the insulator conductive. After the direct writing process,thesethin metallised
layers canthen be removedby etchingwith virtually no attackon the written gold layer. Photograph
38 shows a simple ring oscillator producedby direct writing.

The propagationof microwavesignalsis not asgoodasthat for a conventionaltrack. It will

be necessaryto improvethe selectivityof the processbeforeit may be usedon currentdesign
technology.However,thereis analternativeapproach.Thereasonthatthepropagationis poor is
dueto an impedance
mismatchbetweenthetrack, thesubstrateandthe groundplane.By altering
difference,the gaussianshapemay
the impedence
the thicknessof the substrateto accommodate
fact,
due
losses.
large
In
to the absenceof sharpcomers,lossesmay be improved
cause
not
comparedto conventionaldesigns.Conventionaltrackstendto radiatesomeof their signalfrom
the comersof the track. Alternatively,by usingthe samethicknessof substrate,the track could
be widenedto correctthe problem.In both cases,the newtrack designwould haveto be mathematicallymodelledin order to modify overall designfeatures.This may not be acceptableto
it
be
into
to
to
so
will
necessary
continue
research
methodsof improving
engineers
electronics
many
the selectivity.

9.1.2 The selective plating of reel to reel components.

Large quantitiesof strip or pressedstrip components

suchasconnectorsandleadframesare
jet deposition
currently being producedeitherby controlleddepthimmersionor by submerged
fixed
held
between
With
fixed
being
the
either
or
moveable
rubber
masks.
masksystems,
reel
with
limit
This
tends
to
thespeedof throughput.
as
a
step
and
repeat
operates
process.
plating
selective
Conversely,themovingmasksystemtendsto loseaccurateregistrationwhenrun at high speeds.
The useof resistmaterialsallowsboth high throughputandvery high definitionbut is limited to
flat pressedstrip. Additionalfacilitiesfor applicationof theresist,exposureanddevelopingincrease
the capitalcostof suchplant.
There hasbeena distinct trend over recentyearsto reducethe thicknessof gold appliedto
is
It
find
0.15
thicknesses
to
uncommon
of
about
not
gold
applied.
connectors.
commercial
jum
is notenvisagedin theintended
Suchlow thicknesses
matingof connectors
areusedwhererepeated
in
As
Such
the
used
consumer
are
particularly
goods
market.
a consequence
systems
application.
in
high
deposition
12
be
the
to
thickness,
order
rates,
of
up
very
s-1
can
achieved,
this
14m
reduced
of
leadingto very high stripspeeds.This is possibleasverythin coatingshavenothadtimeto develop
for
features.
However,
the military and aerospace
market, suchthin
any pronouncedstructural
highly
be
2.5
thicknesses
to
with
n-dnimum
unacceptable,
of
14mor above
considered
are
coatings
HSSJE
is
is
The
HSSJE
It
the
being
this
that
to
process
aimed.
systemwill
market
specified.
still

133

be
high
to
at
produced
very
production rates without the need for any
components
such
enable
'
form of masking. The size of the plant required and the volume of electrolyte will be considerably
reduced, thus reducing the capital expenditureand reducingthroughput times. Multiplejetsmay
be used for extra speedor where more than one area requires selectiveplating. The use of such a
small systemwill enablelarger numbersof connectorsto be producedin smaller floor areas.This
should considerably reduce the cost and lead to higher specification products being available at
currently commercial quality product prices.
As well as connectors,the gold plating of lead framesfor the semiconductorindustry is carried
for
Whilst
is
a number of applications, the use
systems.
silver
replacing
gold
on
reel-to-reel
out
of HSSJE could make gold more competitive as well as giving a high reliability product.
9.1.3 Bump plating.
Tape AutomatedBonding is a techniquethat is acquiring importancein the electronicsindustry.
The processconsistsof the production of lead frames on a metallisedplastic strip, similar to a 35
integrated
lead
frames,
film.
In
to
the
to
the
circuits
order
connect
ultrasonic
photographic
mm
bonding of gold or aluminiurn wires is used. To facilitate this, a gold bump is required at the end
for
in
However,
difficulties
lead.
There
technique
this.
a
photoresist
a
number
of
using
are
of each
selectivejetting can overcomemany of theseproblems.

9.1.4 The direct writing of etch resist for printed circuit boards.
The use of electrodepositedmetal etch resistshas beendescribedin Chapter 3. Using HSSJE
it will be possible to directly write the tracks using a metal etch resist. Although such a system
it
in
high
find
today,
techniques
the
use
could
conventional
volume
well
with
compete
not
could
PCB
Prototype
PCB's
in
the
of
prototyping.
are relatively expensiveas they
area
an application
By
direct
board
be
the
etch
using
writing
metal
resists,
of
a
could
photo-tooling.
need one-off
from
directly
design
By
design
(CAD).
the
a
computer
aided
using
as the
rapidly
very
produced
be
in
to
the
system
moved
the
control
will
enable
nozzle
relation to the board
computer
pattern,
be
The
of
such
a
system
would
relatively low in
pattern.
capital
cost
resist
thus writing an etch
Writing
Direct
Laser
PCB
systems
such
as
to
of photoresists.
manufacturing
comparison other rapid
However, it would have the disadvantageof not being able to produce through hole boards. This
there
be
as
are many existing processesthat can provide
a
prototype
with
a
problem
such
not
may
through hole connections,either manually or automatically.

134

There are other applicationsmore suitedto metalsother than gold but thesewill not be discussed
here. The electrochemicaland hydrodynamicconsiderationsthat apply to gold will most likely be
applicable to other metals.

9.2 DEMONSTRATIONS OF THE USE OF HSSJE

A number of test samplesshowing demonstrationsof the potential applications have been
produced. Some of these sampleshave undergone initial trials with regard to their potential
for
for
been
demonstrate
have
Others
the
to
possibilities
use
a particular
produced
application.
application.

9.2.1 Microwave circuit test samples - 50 ohm lines.

If HSSJE is to be used for microwave circuit applications, it should be capableof transmitting
the signal with minimal losses.There are two primary areasof signal loss. The first is radiation
loss, due to sharp edges,comers etc that allow the signal to radiate from the conductor. In other
impedance
is
due
is
The
to
it
behaves
mis-matching.
and
complex
aerial.
second
more
as an
words,
It is not proposedto describein detail this problem but very briefly, there is an impedancemismatch
if the thickness and width of the circuit track does not relate in a specific way to the thickness of
is
If
there
dielectric
the
the
a rnis-match, the signal
side.
ground
plane
on
and
reverse
the
substrate
is projected back to the source,leadingto a loss in signal strengthor evendamageto the transmitter.
There are a number of ways to assesstransmissionlosses,the simplest being the construction
be
from
losses
lengths.
The
lines
then
the
50
can
calculated
signal
transmission
of
varying
ohm
of
640
Four
line.
tracks
circuit
on
single
were
produced
Am thick alumina substrates
responseof each
face
followed
by
The
10
the
substrate
of
was
plated
gold.
opposite
with
chromium
sputtered with
HSSJE
face
The
track
to
track
using
pure
was
plated
with
a
single
gold
a centre-line
gold.
of
pure
itm
depositing
640
After
The
the
track,
track
the
10
total
thin sputtered
width
was
jim.
thicknessof
jim.
layer was removedusing chemicaletchants.The trackswere thentestedfor transmissionproperties.
At the sametime, 4 conventionally producedstrip-lines were tested.The referencefrequency was
10 GHz. It was found that the HSSJEgold exhibited a transmissionloss of 0.06 dB/mm whereas
for
increased
dB/mm.
The
loss
0.01
line
the
transmission
reason
a
of
showed
the conventional
loss was due mainly to the deposit profile. The gaussianshapeled to an overall reduction in the
in
Because
the
the transmission
track.
of
the
reduced
volume
gold
of
total mass of gold within
line, the impedancewas increased.Measurementsof the DC resistancesuggestedthat the reduction
in
to
the
in resistancewas proportional
reduction the cross sectional area. As a consequence,it

135

would be necessaryto improve the selectivity of the deposition process in order to produce
microwave circuitry of an equivalentquality to thosecurrently being produced. Alternatively, the
impedencecharacteristicsof the HSSJEdepositscould be accommodatedby a small redesign of
the circuits basedon the deposit profile and accommodatingan increasedthickness. It would be
before
it
the
to
assess
economics
of
such
a
process
carefully
could be usedfor microwave
necessary
circuitry.

9.2.2 The plating of connectors with alloy gold.

Someinitial trials havebeenconductedon the wear propertiesof HSSJEgold nickel alloy

Wearmeasurements
depositson connectorcomponents.
werecarriedout usingthe GEC Contact
TesterCTIL This is aninstrumentdesigned
to allowthemeasurement
of contactresistance
against
numberof insertionan adjustablecontactforcebothprior to, during andafter a pre-determined
/withdrawalcycles. Actualpairsof contactsarematedratherthanthe pin anddisc configuration
is
is
the
test
thusmuchmorerepresentative
of the actualwear
used;
geometry
commonly
which
jaws,
halves
between
half
individual
The
gold
plated
one
on
each
contact
are
clamped
situation.
of the test stage. Onehalf of the teststagecanbe reciprocated.The otherhalf of the test stage
is providedwith X-Y controlfor alignmentof the contacthalves. The Z adjustmentcontrolsthe
The
instrument
Photograph
39
between
force
the
test
the
stage.
gives a true
shows
pair.
contact
by determiningthevoltagedropacrossthecontactpair when
four point measurement
of resistance
force
The
is
25
through
the
measurement
contacts.
system
passed
mated
milliamps
a current of
load
beam.
loads,
Measurements
55g
bridge
two
were
made
gauged
cell
at
and
strain
a
stiff,
uses
100g. Contactresistance
measurements
weremadeafter the initial set-upandthenafter 50,100
insertion/withdrawal
40
The
A
insertion/withdrawals.
200
was
cycles
per
minute.
number
rate
and
valuespresentedwere
at eachconditionandthecontactresistance
of contactpairsweremeasured
an averagefor eachsetof conditions.
The tests were carried out using male and female connectors plated with both HSSJE and
jetted
The
0.5
1.0
deposits,
thicknesses
samples
were
of
and
prepared
at
a
with
conventional
jum.
1.9
1-1
Ronoval
N
5A
density
electrolyte
containing
g
using
a
nickel whilst the
Crrr2,
of
current
15
The
at
mA
CnO.
plating
conditions
were
plated
conventional
nickel
under
samples prepared
deposits
1-1.
For
1.7
directly
the
this
simplicity,
were
was
g
produced
electrolyte
concentration of
intermediate
layer
Both
female
of
nickel.
no
male
and
with
connectors
onto the copper substrates
found
distribution
It
the
the
that
over
to
of
gold
mating
surfaces.
was
show
micro-sectioned
were
desired
the
area of contact.
deposit
over
constant
thickness
was
the

136

After testing, the wear scarswere examinedusing scanningelectron microscopy with an energy
dispersive X-ray analysisfacility. Copper X-Ray maps were produced of the contact regions to
determine the extent of the penetrationof the gold layer.
The results of contact testing indicated that in the caseof the jetted samples,higher contact
loads gave rise to lower contact resistanceswhereasthe conventional samplesonly showed this
effect with the 1.0 14mdeposit. The overall contactresistancefor both types of deposit was within
generally acceptedlimits, below 8.0 mOhms.
Examination of the wear scarsafter 200 cycles indicated that jetted 0.5 Am deposits showed
little apparentwear with loadsof 55g after 200 cycles, whereasthe equivalentconventionaldeposits
showed significant wear. However, at a thickness of 1.0 Am, the jetted samplesshowed severe
wear with penetration of the coating, apparently abrasivein nature. The equivalent conventional
depositsshowedlesswear althoughsomecoatingpenetrationwas apparent.No wear was observed
for any of the samplesafter 50 cycles.
.
These results are very limited but they do indicate the potential for the use of HSSJE for the
plating of connectorsand further work will be undertakento identify the optimum conditions for
good wear properties.

9.2.3 Thermocompression bonding properties of HSSJE pure gold.

In order to establishthe thermocompressionbonding properties of jetted pure gold, an array
of 20 deposit spots of 3.0 lim thickness were produced at a current density of 5.0 A Crrr2.Gold
industry
bonded
between
by
thermocompression
the
semiconductor
was
adjacent
used
wire as
loop
formed,
by
These
the
to
tensile
test
wire
at
a
a
pulling
gradually
subjected
were
spots.
increasing load until failure occurred. The bond areas were then examined using an optical
%,
failures,
85
fracture,
by
failed
Most
the
the
occurred
wire
remainder
of
within the
microscope.
bond ball. No direct pull-offs were observed.

9.2.4 The direct writing of printed circuit boards.

The ability to move the jet in relation to the substrateallowed the jet to be used to directly
fibre
Topreventan
immersion
circuitboard.
reinforced
onto
a
copper
clad
pattern
resist
writean etch
deposit of gold forn-dngon the copper and to minimise contaminationof the gold, a 0.05 - 0.1 ILm
deposit of gold was plated onto the board prior to processing. The circuit pattern was imported
into the computer that controlled the X-Y table in the form of an HPGL file, a common CAD

137

format. The tracks were written using pure gold at a linear tracking rate of 1.5 mm sec-1and at a
current density of 6.5 A Crn-2.It was found that a slightly higher current density could be used
when tracking the jet without any degradationto the deposit. A deposit thicknessof 3.5 lim was
measured. After completion, the thin background gold layer was chemically removed and the
un-coatedcopper cladding was etchedaway using a 500g 1-1ferric chloride solution at 60-C. Using
0.9
Virtually
jet,
400
track
of
nun
was
produced.
width
no undercutting of the
a
consistent
a
lAm
tracks were observed.

138

CHAPTER 10

ANALYSIS AND DISCUSSION

10.1 GENERAL

71is work has beenthe first comprehensive

studyof depositstructuresproducedusing the
It hasbeenshownthatbothgold andgold
techniqueof High SpeedSelectiveJetElectrodeposition.
alloysof an acceptable
qualitycanbe producedusingthis processat depositionratessignificantly
higherthanhavebeenachievedpreviously.In addition,thesedepositsattaina reproducibledegree
of selectivitywithouttheneedfor masking.Thefactorsthatcontrolthemaximumrateof deposition
aswell asselectivityhavegenerallybeenidentified.Ile morphologyandtopographyof thedeposits
havebeenstudiedandrelatedto the depositionconditions.Ilis Chapterattemptsto correlatethe
of depositionandto relate,wherepossible,
resultsof the investigationinto anoverallmechanism
to previouslyreportedmathematical
this mechanism
modelsof suchsystems.
One of the most important factors when attempting to deposit metals at very high deposition
rates is the processby which deposit deterioration sets in. An understandingof such mechanisms
is essential if the rate is to be increased ftirther. Consequently, the method by which such
deterioration occurs will be discussedin depth as a basisfor any future studiesthat may be carried
out on this technique.

In order for metalsto be electrodeposited

to ensurethat an adequate
at high rates,it is necessary
supplyof metal ions be providedto the substrateto replacethoseconsumedby the deposition
process.Ibis meansthat all factorscontrolling such transportmechanismswill influencethe
maximumrate.Thesefactorsaretheoverallmetalion concentration,the degreeof agitation,the
thediffusioncoefficientandthecurrentdensity.Additionalfactorsmayalsoinfluence
temperature,
the overall rate. Competingelectrochemicalreactionssuch as hydrogenevolutionor oxygen
halt
the metalreductionprocess.Speciesother than thosetaking
or
even
reduce
reductionmay
duringthedepositionreaction
part in thereactionsuchasorganicmolecules,by-productsgenerated
influence
in
the
the maximumdepositionrateby interfering
electrolyte
all
may
or anionspresent
by
diffusion
is
It
the
affecting
surface
of
the
adions.
of
electrocrystallisation
probably
process
with
true to saythatthemostinfluentialfactorcontrollingthemaximumdepositionrate(in theabsence
factors)
is
bulk
factor
detrimental
Ibis
the
of
electrolyte
agitation.
rate
the
controls
aformentioned
of
the rate at which metal ions are re-suppliedto the diffusion layer effectivelybecomingthe rate
determiningstepin any processthat is underdiffusioncontrol. In the caseof HSSJE,very high
deposition
feasible.
The
flow
rates
of
maximum
are
obtained
are
agitation
when
electrolyte
of
rates
Such
influence
flow
thethickness
turbulent
conditions
that
exist.
strongly
conditions
ratesaresuch

139

of the hydrodynamic boundary layer adjacentto the diffusion layer. The maximum possible resupply of metal ions will be achievedwhen this boundary layer is of the samemagnitude as the
diffusion layer. However, limits are set by the way in which the growing electrodepositinteracts
with both the boundary and diffusion layers and this will be discussedin depth later.

It hasalsobeenshownthat it is possibleto depositalloysin a controlledfashion.In the case

of gold alloys,the situationis morecomplexassomeof theco-deposited
metalis incorporatedin
the form of an inorganiccomplex.However,it hasbeenshownthat in termsof the structureand
physicalpropertiesof thedeposit,highspeeddepositsretainanumberof thecharacteristics
observed
in thoseproducedunderconventionalconditions.
During the courseof this study,a noveltechniquehasbeenusedin an attemptto establishthe
masstransfercharacteristics
of the gold depositionsystem.The validity of this techniqueandits
applicabilityto othersystemswill be discussed.
10.2 MASS TRANSFER MEASUREMENTS
Mass transfer was measuredin an attemptto characterisethe gold system. Very little work has
been carried out on the masstransfer characteristicsof metal depositionusing HSSJE. Most of the
models available comefrom experimentscarried out using the reduction of ferricyanide. However,
as explained previously, during metal depositionat high rates, the growth of the deposit interferes
with mass transfer measurement.Therefore, the methodsof SCPV and SVPA were developed.
For pure gold, no limiting current plateaux were observed.The data obtained from the Ronoval
N electrolyte in the absenceof nickel did exhibit a plateauwhilst nonewas observedin the presence
of nickel. In the caseof copper, a limiting current plateau was also seen. The apparentlimiting
currents observed were used to calculatethe Sherwoodnumber in accordancewith equation (3).
Alkire and Chen'08.
This was used to comparewith correlations obtained by Chin and Tsang,105These are shown in Table 26.
and Chin and Hsueh.120.
From these figures it is clear that the limiting current plateaux did not exactly agree with the
three correlations. However, for the laminar flow correlation given by Chin and Tsang, agreement
between
For
flow
18%
turbulent
+20% and +25%
the
+
conditions,
agreement
was
was within
.
for both the Chin and TsangandAlkire and Chin correlations. It is thought that the poor correlation
influence
deposit
but
in
due,
the greatestcontribution is most likely to
to
the
growth
of
part,
was
be due to measurementtaking place before a steady state condition had been achieved. in both
be
density
limiting
higher
expected.
current
would
cases,a

140

in the caseof the pure gold masstransfer experiments,as no limiting current plateaucould be
seen,a graphical methodconsistingof extrapolatingboth the Tafel slopeandthe high overpotential
region was used. Extrapolations were obtainedusing a linear regressionprocessusing the points
that gave the highest correlation coefficient for eachregion. The point of imtersection represents
the limiting current density. Figures 56 to 59 show the extrapolationson the polarisation curves.
It was decidedto adopt the correlation derived by Alkire and Chin to comparethe results for the
gold as theirs was the more recent study. Table 27 shows the experimentally obtained limiting
currents for both SCPV and SVPA methodstogether with the values calculated from the Alkire
& Chin model.
Ibis data showsa very closeagreementwith the correlation of Alkire and Chin. Basedon these
diffusion
layer within
data
it
is
the
to
the
thickness
of
obtain
some
quantitative
on
possible
results
the impingement region.

Analysisof the polarisationcurve of the RonovalN showeda similar agreementwith that

limiting
density.
Figure
59
the
the
the
current
shows
assessment
of
model.
graphical
predictedusing
Table27 showsthisvaluetogetherwith thatpredictedby theAlkire & Chinmodel.It is interesting
to notethatthelimiting currentdensityplateaufrom theelectrolytewithoutthe nickeloccurredat
latter
As
lower
by
the
the
than
the
graphical
method.
method
value
obtained
somewhat
a value
be
it
in
the
reasonableto assumethat the
would
close
agreement
with
model,
providedvalues
be
SCPV
limiting
not
reliedon andthegraphical
should
current
plateaux
obtained
using
apparent
approachusedwherepossible.The use of the graphicalmethodis not possible,however,in
in
is
little
Tafel
the caseof
the
curve,
as
or
no
polarisation
region
apparent
on
where
situations
copper,asno clearextrapolationwaspossible.
Ile resultsof themasstransferstudiesshowthatthetechniques
of both SCPVandSVPAare
for
HSSJE
deposition
limiting
density
metal
where
current
values
obtaining
of
method
a suitable
data.
However,
it
interferes
high
the
such
conventional
of
obtaining
with
means
would
rates
at
in
highly
be
the
of
not
case
reversiblesystemswhereno
the
may
as
accurate
that
method
appear
is
Tafel
observed.
region
clear

141

ET
Ln

E
c
-:::

(
(N

IIIII

1111111

1' 11111111111!

I -A IIIII

Ln

";zv

C4
A-

IIIII

-L-

(N

C
-J

IIII

Ln
6

CD

14ua4odj, 3AO

Figure 56. Graphical evaluation of the limiting current density for jetted pure gold at a Reynolds
SCPV.
'L
data
by
3355
obtained
= 4.41 A cm-2.
using
number of

142

CT
Lfl

(Z)
D
L
C
-J

(N

C)

111

IIIIIIIfIItIIIIIIII.

-1

CN

Lr-)

Ln
CE

0
i

A-

(D

jejquaqodJ@Ao

Figure 57. Graphicalevaluationof the limiting currentdensityfor jettedpure goldat a Reynolds

il,
6.3
data
by
SVPA.
A
67
10
obtained
=
using
cm-2.
of
number

143

AIIIIIIIII

IIIfII
q

llzv

(N

Cr)

uI-)

Ln

ci:)

jejquaqod-J3AO

Figure 58. Graphicalevaluationof the limiting cuffentdensityfor jetted pure gold at a Reynolds
'L
9.97
A
data
SCPV.
by
13545
cm-2.

obtained
using
numberof

144

(-D

ci-

(D

Ln
FE

cr
CA
cr s
Ln U

-J

L(i
LriII
IIE

2
LD
I

00
C: C:

C2r-ql

III

-I

IItIIIIIIIIIIIIIIIIIIIIIIIItIIIIIfIII

IZZI,
a

Ln
m

c10

L-A

m
A-

Lr-) (N

12TquaqodJBAO

Ln
0

Figure 59. Graphicalevaluationof the limiting currentdensityfor jetted gold from a RonovalN
Reynolds
10600
data
by
both
a
number
at
of
using
obtained
and
without
nickel
with
electrolyte
SCPV. Electrolytenickel concentration= 1.9 g/l, limiting current densityvaluesare shownon
the graph.

145

10.3 THE INFLUENCE OF DEPOSITION CONDITIONS

The factors that control the deposit quality have already been mentioned in Section 9.1. To
summarise, these are the current density, temperature, metal ion concentration, flow rate and
electrolyte composition. Additionally it hasbeenshown that the nozzle to work-piece distancecan
influence the quality. Thesewill now be discussedin more detail.

10.3.1. Nozzleto substratedistance.

The effects on the flow characteristics of the un-submerged jet with reference to the
nozzle-to-substratedistancehave beendiscussedin Chapter 6. The experimentscarried out on the
nozzle to substratedistanceshowedtwo effects. The first was that the selectivity was improved at
H/d values of less than 1. This can be explained by the current distribution. When an anode is
placed very close to a cathode, there is a tendency for a reduction in the effects of secondary
current distribution. This will be pronouncedif the IR drop betweenthe anodeand cathodeis less
than the total overpotential at the anode and cathode. Under these conditions, primary current
distribution will predominate, which like Ohms Law, is based on geometrical factors. As a
consequence,an increasedrate of depositionwill occur within the impingementregion. The second
H/d
4,
distance
that
at
values
above
needle
structures
were
observed
at
a
was
of
observed
effect
-d' = 100/irn or d'/d = 0.25. The mechanismof the developmentof thesestructuresis described
in detail in Section 10.6.2.2. but essentially,under certain circumstances,needlesform at the point
jet
low
This
that
the
commences.
would
at
suggest
values of H/d, the wall jet
wall
at which
commencesoutside the impingementregion (d'Id 2: 1) whereasat values of H/d > 4, the wall jet
commencesmuch closer to the jet centre-line. This is in general agreementwith the findings of
the studies on submergedjets (See Section 6.2.1). The exact value of d'/d will depend on the
it
but
be
for
jet
Reynolds
that
may
concluded
un-submerged
electrodeposition, the
number
nozzle
is
H/d
local
between
transfer
the
the
of
characteristics
and
value
mass
similar to that
relationship
of the submergedjet. Consequently,the H/d value must be kept at a value below 4 in order to
avoid local variations in mass transfer, which can lead to undesirable deposit structures being
formed.
10.3.2. Current density.
The current density influenced the depositcharacteristicsin many ways. The most obvious was
the deterioration of the deposit abovea certain current density for any particular set of deposition
The
is
density
This
to
systems.
all
electrodeposition
maximum
common
useful
current
conditions.
for
9.0
for
6.0
A
in
A
be
found
the
pure
gold
and
to
Cm-2
Cnr2
alloy gold, giving
region
of
was
deposition ratesof 3.4 Am/secondand2.8 /,tm/secondrespectively. A discussionof the morphology
density
be
its
later.
have
It
been
deposit
to
the
will
current
given
the
relationship
will
and
noted
of

146

that in the deposition of the samples,a constantnumber of coulombs was passedfor each spot.
However, it was found that the measuredthicknessof the deposit at the jet centre-line increased
with increasingcurrent density. Figure 60 showsa typical exampleof the behaviour of a pure gold
deposit. There are a numberof reasonsfor this. Figure 17showsthe spreadof the depositmeasured
optically. It can be clearly seenthat the diameterof the depositwas high betweena current density
of 0.25 and 3.0 A cm-2although not readily measurableusing the Dektak. In addition, Figure 25
function
density.
If thesetwo effects are taken into
the
the
as
a
of
current
efficiency
current
shows
consideration together, the behaviour observedin Figure 60 would be expected.

20

10

0
01

345
Currentdensity A/cm sq

Figure 60. The relationship betweenthe measuredthicknessat the jet centre-line and the current
density for the 0.17M citrate gold.
A reduced current efficiency in the lower current density region, together with a decreased
density
thickness
the
the
to
over
current
measured
overall
range of
reduce
selectivity combined
0.25 to 3.0 A Cm-2.It can also be seenthat betweena current density of 3.0 and 4.5 A cm-2the
deposit
be
is
This
the
as
and
expected
efficiency
width
may
constant
constant.
thicknesswas almost
4.5
A
increase
in
in
increase
The
thickness
cm-2
coincided
roughly
with
above
an
this
range.
over
increase
in
A
The
in
5.0
density
the
thickness
cm-2.
of
was
current
the current efficiency above a
6.0
4.5
A
However,
density
between
the efficiency and
10%
and
of
Cni-2.
current
a
the region of

147

deposit width remainedconstantover this range. This would indicate that a changein the density
occurred either by micro-void or foreign matter incorporation into the deposit It was not possible
to measurethe density of the deposits,althoughmicrosectionsdid not show any signs of porosity
up to a current density of 7.0 A cm-2.Betweena current density of 5.0 and 7.0, a relative increase
in efficiency of 10% occurred. Over this range, an increasein thicknessof 10% also occurred.
This would explain the increasein thickness with increasing current density above 5.0 A crn-2.
Additionally, abovea current density of 7.0 A cm-2,the depositbecameincreasingly nodular, thus
artificially increasingthe apparentmeasuredthickness.
It is interesting to note that the width of the deposit passedthrough a maximum at a current
density of 0.75 A crrr2and thereafterreduced.The model developedby Alkire and Chin, together
with experimental results using a redox reaction indicates that low currents should lead to high
selectivity. In the case of copper deposition, they found that the opposite was true, with high
currents exhibiting better selectivity. This wassimilar to the depositionof pure gold. They attributed
this behaviour to the difference in the exchangecurrent densities of the copper and ferricyanide
electrolytes. If the Alkire model was correct, then in the caseof pure gold, the value of k (Equation
26) would have to be in the region of 10-1and the systemwould be operating under conditions of
mixed ohmic and charge transfer control. The polarisation data that closely correspondsto the
deposition conditions used to generateFigure 17 can be seenin Figure 36. It can be seenthat for
a Reynolds number of 13545, a current density of - 1.0 A Cm-2signifies the onsetof mixed charge
transfer and masstransfer control. This doesnot agreewith the Alkire/Chin prediction. However,
it should be notedthat the Alkire/Chin modelwasbasedon theoreticalcalculationsandexperimental
conditions over a "nozzle current density" of between0 and 100 mA crn-2.This is at least an order
in
lower
the
than
this work. Additionally, the reactive ion
experimental
values
used
magnitude
of
lower
in
Consequently,
than
this
this part of the
order
of
magnitude
an
work.
was
concentration
for
for
the
the presentstudy. The model and experimental
conditions
used
apply
may
not
model
data did show that at higher reactantconcentrations,the selectivity was increasedat higher currents.
This was becausethe impingement region operated under mass transfer control. Under these
in
improved
deposition
increase
the
the
concentration
an
rate within the impingement
conditions,
jet
led
increase
in
to
the
to
and
wall
a
significant
selectivity. The experimental
compared
region
in
this study agreewith such a prediction and therefore this part of the model was
obtained
results
Significant
improvements
in
to
the
studied.
conditions
selectivity were observed at
applicable
for
in
higher
ion
densities
the
the
control
region
mixed
relatively
metal
concentrationsused
current
in this study. At current densitiesbelow 0.75 A crrr2the selectivity increasedand this agreeswith
low
densities.
higher
The model predicts that a
for
concentrations
at
current
reactant
the model
be
in
increase
in
improvement
selectivity
would
observed
as
an
concentration increases
moderate
the exchange current density reducing the charge transfer resistance compared to the ohmic
be
Tafel
Such
the
the
at
appreciable
commencement
more
of
would
an
effect
region,
resistance.
density
increased.
This,
then, explainsthe shapeof the curve observed
the
was
current
reducing as

148

in Figure 17 with the maxima coinciding with the end of the Tafel region and the start of the mixed
charge transfer and masstransfer controlled region. Further discussionof the effects of current
density on the selectivity will be given later when the deposit interaction with the fluid flow is
discussed.

10.3.3. Electrolyte velocity.

As expected, the electrolyte velocity significantly influenced the deposit quality. The mechanisms by which the quality was altered was dependenton the interaction of the flow with the
deposit as well as the influence of enhancedmetal ion replacementat higher flow rates. These
mechanismswill be discussedin Section 9.6. The Alkire/Chin model suggestedthat an increase
in the velocity at large currents improved the selectivity becausethe impingementregion operated
at a higher fraction of the limiting current density comparedto the rest of the surface. Therefore,
an increasein the flow should favour the impingementregion and improve selectivity. However,
under the experimental conditions used in this study, no significant effect on the selectivity was
in
is
for
This
difficult
deposits
to
those
that
velocity.
explain,
particularly
changes
with
observed
is
behaviour
did
It
that
such
occur, particularly at current densities
possible
quality.
were of good
density.
However,
deposits
difficult
in
limiting
to
terms
to
were
the
current
such
measure
close
before
limiting
deposit
in
deterioration
the
the
current was reached.A
set
well
of
of selectivity as
in
increase
impingement
deposits
towards
the
the
nodulation
edge
an
of
exhibited
region,
of
number
indicating that the stagnationregion was operatingat a lower fraction of the limiting current density
but measurementsof deposit widths were difficult due to the roughnessof such samples.

10.3.4. Temperature.
The temperature influenced the structure of the depositsin two ways. Firstly, an increasein
temperatureincreasedthe diffusion coefficient and enhancedthe rate Of masstransfer. This led to
density
increase
in
limiting
in
increase
the maximum useful current density.
the
current
and
an
an
Secondly, it influenced the flow characteristicsby altering the viscosity. This led to a significant
between
deposit
flow
be
interaction
discussed
in
the
the
this
the
and
electrolyte
and
will
alteration
in Section 9.6. The Alkire/Chin model did not include temperatureeffects and therefore a comdid
influence
The
be
temperature
the selectivity of the
significantly
not
made.
cannot
parison
deposits measured.

149

10.3.5. Electrolyte composition

The effect of the composition of the pure gold electrolyte will be consideredseparatelyfrom
that of the alloy gold. It is clear from the results that an increasein the metal ion concentration
markedly increasedthe maximum current density and deposition rates at which useful deposits
could be produced. However, it was found that above a certain concentrationof metal ion, this
maximum current densitydid not increasefurther. For example,at a gold concentration of 0.17M,
the maximum useful current density was found to be 5.5 A Crn-2with a deposition rate of 2.9
jim/second at a pH of 6.1. However, increasingthe concentrationto 0.28M reducedthe maximum
current density to 5.0 A Cm-2but with the samedepositionrate. It is suggestedthat the reasonfor
this behaviour lies in the stability of surfaceperturbations.As describedin Section5.1.5. instability
is
controlled, in part, by the magnitude of the concentrationgradient at
surface
perturbations
of
the surface. Increasingthe metal ion concentrationallows the growth of smaller perturbations by
increasing the magnitudeof the concentrationgradient for any fixed thicknessof diffusion layer.
Low metal ion concentrationsallow the growth of perturbationsas the condition of a low surface
adion concentration( the condition required for instability) will occur at low current densities(low
ion
higher
densities
iL).
Increasing
be
if
the
to
concentration
current
metal
allows
achieved
values
before the stabilising effect of surfaceconcentrationis lost. There will come a point at which an
increase in the metal ion concentrationwill have a negative influence on stability of the growing
increased.
is
Therefore, the maximum
the
the
concentration
of
gradient
magnitude
surface as
current density will be reduced. The fact that despitea reduction in the maximum useful current
density for the 0-28M citrate gold was observed,the depositionrate was the sameas for the lower
concentration electrolyte would tend to confirm this theory. In both cases,the surface ion coninstability
be
the
the
at
point
was observed.
same
at
which
would
centration

IncreasingthepH of thecitrateelectrolyteincreased
themaximumusefulcurrentdensity.This
would be expectedbasedon the stability theory.The citrateelectrolyteoperatedat a pH of 6.0
hasa lower currentefficiencycomparedto that at a pH of 8.1. This is becausethe hydrogenion
latter
in
deposition
lower
hydrogen
is
is
the
the
case
and
potential
of
morenegative
concentration
than at lower pH values.Therefore,moresurfaceadsorbtionsiteswill be availableat higherpH
andencourages
stability.
values.This effectivelyallowsa greatersurfaceconcentration
The role of the supporting electrolyte is also influential in the maximum deposition rate. The
both
decreased
density
a
maximum
current
exhibited
and deposition rate
electrolyte
phosphate
is
for
further
be
The
this
the
un-clear
and
to
work
reason
will
citrate.
required to establish
compared
differing
ions
degrees, with the phosphateions
to
is
It
the
that
adsorb
supporting
this.
possible
level.
higher
adsorbing at a much

150

The electrolyteconductivityinfluencedthe depositin two ways. Firstly, a reductionin the

conductivityof about50% loweredthe maximumusefulcurrentdensityto 3.75 A crrr2and the
depositionrateto 2.3lindsecond.However,it improvedtheselectivityby about17%.Thereduction
by reducingtheconcentration
in conductivitywasachieved
of supportingelectrolyteto anextremely
low value. The Alkire/Chin modelpredictedthat a reductionin the conductivitywould improve
theselectivityfor low appliedcurrentsbut at highcurrentsno influencewouldbeobserved.It was
foundthat over the currentdensityrange0.25 to 8.0 A cm-2,theselectivitywasconstant,with a
maximumR=2.5. Thebasisof theAlkire/Chin modelwasthatat low currents,the systemwas
dominatedby chargetransferandohmicresistance
effects,with the wall jet regionbeinggreatly
At highercurrentdensities,the systemis controlledby mass
influencedby the ohmicresistance.
transferandconductivityshouldnot influencethesystem.Theresultsdo notagreewith themodel.
by thefollowingmechanism.
In the wall jet, the
It is suggested
thattheimprovedselectivityarises.
is
linear
function
distance,
be
drop
that
there
of
radial
assun-dng
no IR drop in the
a
will
ohmic
astheelectrolytelayerin theradialwalljet is exceedingly
axialdirection.Thisis a validassumption
thin. Because
of this, anysignificantreductionin theconductivitywill increasetheohmicresistance
for anyvalueof currentdensitybeyondtheohmiccontrol
in theradialdirection.As a consequence,
region, a reductionof conductivitywill reducethepotentialat any particularradialpositionthus
lowering the depositionrateat that point. In this way, the spreadof the depositwill be reduced
andthe selectivityimproved.

10.3.6. The influenceof nozzlesize.

It was not possible to obtain data for small nozzle sizes(< 300 i1m) under identical conditions
to those used for the bulk of the experimentsin this study due to pressurelimitations of the pump.
Smaller nozzles required significantly higher pressuresthan could be obtained from the pump in
indicted
Numbers.
However,
Reynolds
the
that the nozzle size
results
to
similar
attain
order
influenced both the selectivity and the maximum useful current density. Using the 400 PLmnozzle
both
increasing
to
the
the maximum useful current
nozzle
size
appeared
reduce
as a reference,
density as well as the selectivity. The reduction in selectivity was presumably due to the overall
increase in the conductanceof the electrolyte in the wall jet. As the nozzle size was increased,so
increased.
increase
in
jet
This
jet
the
thickness
the
apparently
thickness
wall
wall
of
the overall
but
not measured.
observed
was
The reduction in the maximum useful current density is not so easy to explain. There is
insufficient evidencewith which to describethe causeof this phenomenon.The effects of scaling
be
derived.
before
further
may
explanation
a satisfactory
study
need

151

A reduction in the nozzle size led to a reduction in the deposition rate of around 80 % as well
In order to ascertainwhy the deposition rate was
as a reduction in the selectivity to R=4.5.
reduced, it was necessaryto establishthe total massof gold depositedfrom both the 100 pm and
the 400 prn nozzle under similar conditions, exceptfor the Reynoldsnumber for reasonsdescribed
above. Deposit half profiles, similar to the selectivity plots except using thickness vs d' were
obtained from samplesproducedat a current density of 6.0 A Crn-2and a time of 5.7 secondsfrom
both nozzles. It was assumedthat there were no voids or inclusions that would reducethe deposit
density. A polynomial regressioncurve fitting routine was applied to each profile to obtain the
best fitting formula for eachcurve. The following data was obtained;
3_5.90SX4+
17.39
6.316
32.21
22.
OOSx
O.S67x3
+
yxX2 +

(30)

for the 400 pm nozzle and

y-3.3

+ 0.107x

0.942
X2+ 0.264 X3_ 0.021 X4
-

(31)

for the 100 pm nozzle.

Thesewere integratedin two axial directionsin order to find the volumeof eachdeposit.If
depositionconditionswere identicalfor eachdeposit,the ratio of the volumeto the numberof
be
very similar. It wasfoundthat for thedepositproducedfrom the400
should
coulombspassed
0.00156
However,
0.00108
obtained.
was
of
a
ratio
of
was obtainedfor the
a
ratio
nozzle,
pm
depositfrom the smallernozzle,30% lower than the larger nozzle.This is not as high as the
depositionratereductionof around80%wouldsuggest.Themassof thedepositswerecalculated,
The
19.3
deposit
density
theoretical
g
cm-3.
each
of
mass
of
was calculatedfrom
a
assuming
Faraday'sLaw. The cathodecurrent efficiencycouldbe calculatedfrom this data.It was found
that for the largernozzle,an efficiencyof 76% wasobtained.This comparesvery well with the
density
for
this
current
of 74% (Figure25). The efficiencycalculatedfor the
measuredefficiency
%.
for
There
53
in
two
the
are
possible
reasons
reduction
was
efficiency.The first
nozzle
smaller
lower for thesmallernozzleandasthemasstransport
is that the Reynoldsnumberis considerably
be
likely
ions
is
to
reducedas a resultof this, thenthe efficiencywill be reduced.The
of gold
interpretation
density.
Throughout
involves
the
the
theproject,thecurrent
of
current
reason
second
densityhas beengiven in termsof the nozzlediameter.This is not strictly valid as deposition
In
impingement
is
the
the
the
the
case
of
region.
smaller
nozzle,
selectivity
worse
outside
occurs
the true currentdensitywould probablybe lower
than with the largernozzle.As a consequence,
density
for
for
is
is
100
Evidence
this
the
the
useftil
current
maximum
taken.
nozzle
that
than
an

152

highef than for the larger nozzle, being 10.0 A crn-2,despiteoperating at a much lower Reynolds
it
is
is
likely
It
that
a combination of both possibilities that leads to the reduction in the
number.
deposition rate from small nozzles.
10.3.7. The effects of pulsed current.

The applicationof pulsedcurrentdid not improvethe maximumcurrentdensityasmayhave

beenexpected.Undertheconditionsof depositionstudied,therewasa reductionin themaximum
useful depositionrate for the equivalentdepositquality producedunder DC conditions.The
morphologicaldiagramsshownin Figures32 and33 showthattherewasa narrowregionof duty
cycle and on-timefrom which smoothdepositscouldbe produced.However,for the equivalent
density
deposition
the
the
maximum
useful
at
which
electrolyte
produced
rate,
current
average
6.0 A Cm-2,the "smooth"depositswereactuallyslightly porous.The structuresin the diagrams
can be interpretedin termsof the peakcurrentdensitiesapplied.At low duty cycles,and short
is
density
high.
For
duty
5%,
a
cycle
the
very
example,
at
of
an on-time
current
peak
on-times,
density
6.0
density
Acrn-2,
the
0.1
of
peak
current
an
average
current
was 120A
msecs.and
of
Cm-2.High peakcurrentdensitygaveriseto fractaltypestructures.This wasnot too surprisingas
individual
lead
due
high
to
the
to the
of
nuclei
will
rapid
growth
potentials
momentary
such
high
Additionally,
distribution
the
at
overpotentials.
current
experienced
primary
of
predon-driance
leading
instability.
instantaneous
in
to
concentration
an
reduction
surface
experience
will
surface
Thesetwo factorswill lead to the rapid growth of perturbationsin the directionof the electric
field. At higherdutycycles,thepeakcurrentdensitywaslower. This reducedtheprimarycurrent
distributionbut wouldhavemaintaineda high rateof nucleation.However,it is knownthatAuCN
inhibit
This
during
takes
the
the
and
probably
off-time.
adsorption
can
place
surface
adsorbson
the lateral growth of nuclei leadingto growth by meansof 3-dimensionalnucleation.As a
do
lateral
form
therefore
the
and
growth,
nuclei
not
merge
a
growing
of
reduced
consequence
structure.
psuedo-nodular

10.4 SOME PHYSICAL AND STRUCTURAL PROPERTIES OF PURE GOLD HSSJE

DEPOSITS

Someof the moreimportantphysicalandstructuralpropertiesof puregold depositsproduced

during
These'properties
been
have
the
this
HSSJE
course
of
experimental
work.
examined
using
havebeencomparedto depositsproducedundermore conventionaldepositionconditions.Con0.2
(after
from
deposits
exhibit
a
grain
size
of
around
electrolyte
a
citrate
gm
ventionalpuregold
have
hardness
kg
for
III
100
faulting)
for
the
and
planes
values
of
around
and
strain
accounting
Such
been
has
311
deposits
texture
These
orientation.
a
preferred
observed
a
strong
exhibit
mm-2.
by other workers as describedin Section2.2.3. It was not possibleto obtain data on the 311

153

crystallitcs as higher orders of reflection could not be obtained with this experimental method.
However, examinationof the lattice parameterswould suggestthat no stackingfaults were present
as they are all the samesize. These samplesexhibited the lowest RMS strain for the 111 planes
of all the samplesexaminedover the currentdensityrangeanalysed.The morphology of the deposits
produced may be describedas angular and crystalline.
When deposits are produced from the sameelectrolyte using HSSJE, both the structure and
morphology are significantly altered. This is due both to intrinsic changesin the deposit structure
due to the deposition conditions as well as the interaction with the electrolyte flow. The latter will
be discussedin the following Sections.The intrinsic changes-result from the very high rates of
deposition. The grain size is considerably reducedto a value in the region of 200 A, a tenfold
reduction. Such a reduction is the most likely causeof the increasein the deposit hardnessup to
featureless,
kg
The
200
and
mm-2.
surface
appearance
was
smooth
gradually
around
of
a value
developing smooth rounded mounds with increasingcurrent density. This rounded mound morphology is similar to that developedin the caseof alloyed golds. The mechanismof the growth of
these structures is discussedin a subsequentSection.
A (220) preferred orientation develops which, as has been suggestedby Lin et a137may be
is
in
be
lattice
A
the
observed,
which
slight
reduction
parameter
may
species.
caused adsorbed
due to the incorporations of small quantities of foreign species.This would not be surprising at
bury
deposition
high
the
takes
place
can
easily
surface
as
speed
at
growth
which
of
rates
such
is
important
both
jetted
deposit.
It
the
to
that
the
conventional
note
and
within
adsorbed species
This
lattice
deposits,
the
the
self
consistent.
parameter
of
of
measured
planes
was
each
gold
pure
faults
fairly
No
detected,
deposit
the
that
structure
was
ordered.
structural
were
well
would suggest
low
densities.
This
D,
low
for
true
that
the
at
current
means
and
probability
=D
very
a
except
ff
23.
in
Table
is
as
crystallite size
Some pure gold depositswere produced for trials of thermocompressionbonding properties.
The results of thesetrials indicate that despitethe relatively high hardnessof the gold, good bonds
frequent
failure
breakage
Such
the
as
most
mechanism.
results would
wire
with
were achieved
ductility
despite
that
the
adequate
was
maintained
pure
and
an
relatively
the
was
that
gold
suggest
hardness. These results indicate that pure gold HSSJE deposits would not be suitable for wear
being
despite
hardness
the
the
of
connectors
same order as alloy
as
such
applications
resistant
deposits. Failure would inevitably occur due to cold welding. However, this would allow pure
deposition
lead
frames
for
be
the
deposits
selective
of
such
as
where good
to
applications
used
gold
bondability is required.

154

10.5 SOME PHYSICAL AND STRUCTURAL PROPERTIES OF GOLD ALLOY HSSJE

DEPOSITS
In the caseof the alloy gold, conventionaldepositsproduced from the Ronovel N electrolyte
exhibited RMS strains higher than the equivalent pure gold samples. However, no evidence of
stacking faults was seenfrom studiesof relative peak shifts. There was a slight asymmetry of the
peaks. Unfortunately, the twin fault probability cannotbe calculatedfrom the III peak. Therefore,
whilst it is known that twin faults existed within the deposit, their contribution could not be
measured. It is therefore most likely that in this caseD, ff < D. It is possible that a significant
hasstudiedtransition metalhardened
contribution to broadeningis dueto twin faulting. Nakahara77.
gold depositsproducedunder conventionaldepositionconditions, using the TransmissionElectron
Microscope (TEM) and observedsimilar topographic features as in this study, with the deposit
surface exhibiting "rounded mounds" or small nodules. It was found that the rounded mounds
A.
111
between
200
300
It
orientation with a crystallite size of
and
observed exhibited a strong
formed
inhibition
that
such
a
structure
as
of lateral growth by adsorbed
a
result
of
concluded
was
species, presumably transition metal complexes.The sameinhibiting molecules adsorbedon the
top surface of the growing planesand causedcontinuousnucleationleading to the small crystallite
high
hardness.
A
high
number of twins were observedwithin the structure. It is evident
size and
that gold nickel alloy depositsproducedconventionally shareda number of morphological features
deposits
but somesignificant differenceswere observedin the
jetted
both
and
alloy
gold
pure
with
micro-structure.
In the case of the jetted samples, similar values of D, ff were observed for the conventional
Ronovel N and jetted depositscontaining only booster. The presenceof nickel however led to a
There
%
in
-25
this
value.
appearedto be no direct dependenceof D, ff on current
reduction of
density. It is generally acceptedthat increasing the current density in simple electrolyte systems
leadsto a reduction in crystallite size.Theseresultswould suggestthat in the caseof the conventional
deposits, an inhibition processas envisagedby Nakahara.was operative. The fact that a similar
jetting
under
conditions suggeststhat inhibition processeswere also
observed
crystallite size was
influence
increased
for
the
crystallite
size
and
not
an
of
small
current density. The
responsible
is
difficult
identify
to
and
this
un-clear
as there are a number of possible
process
of
exact nature
inhibiting species.These include AuCN, CN-, booster and transition metal cyanide complexes. It
is most likely that there is an equilibrium betweenthe adsorbateswhich alters depending on the
deposition
The
conditions.
and
structural properties are therefore altered,
concentration
prevailing
depending on the nature of the inhibiting speciesinfluencing the growth of the deposit.

One of the most significantdifferencesin physicalpropertiesbetweenthe conventionally

by
jetting
influence
is
deposits
the
those
produced
of nickel additions.
and
alloy
producedgold
Conventionallyproducedpuregolddepositsexhibita hardnessin theregionof 100kgMnr2,whilst

155

jetted pure gold depositsmanifest a hardnessof between 160 kg mrn-2atlow current densities and
200 kg Mm-2at high current densities. Deposits produced from electrolytes containing booster
exhibited a consistenthardnessof around 200 kg 1=2 over the current density range examined.
When nickel was added to a conventional electrolyte as in the case of the Auronal MRN, the
hardnessincreasedfrom 100 kg Mrrr2 to between 150 and 200 kg mm-2.Similar hardnessvalues
were observed when nickel was addedto the Ronovel N electrolyte containing only booster. In
the caseof the electrolyte containing only nickel, there was a tendencyfor an increasing deposit
hardness with increasing current density. In the case of the electrolyte containing booster and
nickel, the oppositetrend was seen.The hardnessof the nickel containing depositproduced using
HSSJE, is reduced proportional to the quantity of nickel added to the electrolyte, from 200 kg
Mm-2 down to as low as 110kg mm-2.There is no direct evidenceto explain this behaviour as the
jetted samplescontainingboosterboth with and without nickel exhibited similar structuresin terms
of RMS strain and stacking faults. The main difference was the reduction in the crystallite size in
the caseof the nickel containing sample. This alone was insufficient to account for the changein
hardnessas no current density dependencewas seenin terms of the crystallite size. However, a
linearly increasing current density dependencewas observedin the lattice parameters.The nickel
in the deposit reduceswith increasingcurrent density and there is an empirical linear relationship
for alloys whose individual componentstructuresare similar betweenthe lattice parameterand the
atomic percent of an alloy constituent (Vegards Law) This would imply that some of the nickel
lattice
in
incorporated
being
the
the form of metal atoms.It is known that when transition
within
was
metals are addedto a gold electrolyte, conventionally produceddepositsincorporate the majority
in
form
A
in
in
the
the
transition
of
a
cyanothe
complex.
change
metal
way
which the transition
of
is
deposit
interacts
the most likely explanationof the reduction in hardnessobserved.
the
with
metal
It is clear from Figures 39 and 43 that the changein the hardnessis a function of the nickel in the
in
deposit.
This tendsto confirm the inhibition mechanismas the main
the
that
not
electrolyte and
influence on the hardnesschangesobserved.
The wear properties of gold alloy depositsproducedby jetting have already been describedin
Chapter 9. It is further suggestedthat the changein the inhibition process is responsible for the
difference in the wear characteristicsobservedbetween conventional and jetted deposits. It was
found that jetted depositsshowedsome reduction in the wear resistanceparticularly with thicker
coatings. There was also evidencethat the wear mechanismwas abrasivein nature. Such abrasive
deposits
from
in
is
alloy
produced
properly controlled electrolytes under
gold
observed
not
wear
DeDoncker
Vanhumbeek32have
deposition
conditions.
and
suggestedthat in the
conventional
behaviour
is
the
strongly relatedto the proportion of cobalt present
wear
alloys,
cobalt
caseof gold
ion
high
latter
being
the
complex,
with
to
that
as
a
cobalt
values
of
present
required for
as metal
in
If
high,
incorporation
the
the
too
the
electrolyte
cobalt
concentration
was
resistance.
wear
good
leading
high
deposit
to
too
the
suppressed
was
a value of metallic cobalt in
the
within
complex
of
the deposit. Such depositsexhibit abrasivewear behaviour. In addition, Antler31-has found that

156

in order to obtain good wear resistance,the deposit must have a low ductility as well as a high
hardness. Sucha combinationwould not be expectedfrom a depositin which the alloying constituent
has suggestedthat it is the inhibition due to
was presentpurely in the metallic phase.Nakahara77.
the nickel complex and its incorporation into the depositthat is responsiblefor the crystallographic
structure observedin gold nickel alloys. It would seemto follow, therefore, that due to the high
rates of deposition achieved in HSSJE, the inhibition processis changed, with much less of the
incorporated
into
deposit
but
being
the
asmetal within the gold lattice. This would
complex
nickel
explain the reduction in the wear resistanceobservedby Bocking and Cameron.

10.6 FLUID FLOW AND ITS INTERACTION WITH THE DEPOSIT

In order to discussthe way in which the flow and the deposit interact, it is necessaryto outline
the establishedmechanismsby which the fluidjet interactswith an impingedsurface. Let us consider
the overall flow mechanismsoperating during HSSJE. In the case of a non-submergedjet, the
identical
from
flow
to that experiencedwithin the
the
nozzle
a
profile
with
emerges
electrolyte
nozzle tube. Providing the nozzle tube length is an order of magnitude greater than the nozzle
diameter, then this flow regime will effectively be that existing within a tube. However, if H/d is
is
in
leading
flow
by
flow
1,
to
the
the
the
then
air,
a
than
affected
surrounding
reduction
greater
interaction
leads
break
high
H/d
At
to
turbulent
this
ratio's,
eventually
and
a
the
edges. very
at
in
influence
deposition
be
has
The
flow
the experiments
that
this
can
seen
the
on
structure.
up of
distances.
during
Most
large
the
to
this study
carried
out
substrate
of
work
nozzle
conductedwith
did not include such a regime and will only be consideredwhere necessary.As the emerging free
jet approachesthe substrate,interactionwith the later reducesthe axial flow rate, with a consequent
diversion of flow in the radial direction. This region is the stagnationzone, the size of which will
dependon the flow rate of the free jet. Within this zone, a hydrodynan-dcboundary layer of almost
both
The
flow
develops.
to
the submerged
this
properties
are
common
thickness
of
region
constant
jets.
Towards
flow
is
into
the
the
the
the
edge
of
stagnation
zone,
redirected
and non-submerged
decelerates
flow
flow
This
flow
has
Axial
direction.
the characteristics
as
radial
accelerates.
radial
is
jet
behaviour
However,
jet
termed
jet
the
the
the
the
wall
region.
of
wall
region
and
of a wall
dependson whether it is submergedor not. In the caseof the submergedsystem, interaction occurs
influences
its
behaviour.
We
discussion
fluid
thus
to the
will
restrict
and
our
the
surrounding
with
jet
At
boundary
layer
for
jet
the
the
the
stagnation
edge
of
zone,
a
wall
region.
non-submerged
boundary
Beyond
layer,
is
Blasius
flow
having
the
type
profile.
uniform.
plate
a
to
starts grow,
With increasing radial distance, the thicknessof the boundary layer increasesuntil the fluid layer
becomesa completeboundary layer, subjectto viscousdrag from the substrate.This is the transition
high,
hydraulic
jump
drag
becomes
then
the
When
sufficiently
occurs.
the
viscous
region.

157

10.6.1 Interaction of the flow below the maximum useful current density
Most of the models for the impinging jet have been basedon fluid thickness and limiting
limiting
The
current methodmakesuseof a ferricyanide/ferrocyanideredox
measurements.
current
system. Sucha systemprovides a very good meansof establishingthe masstransfer characteristics
of thejet as it doesnot producea solid product that would interfere with measurements.However,
in electrodeposition, the product is a growing layer of metal. Figure 61 shows how a pure gold
depositgrew with increasingtime. The conditionsof depositionweresuchthat a smooth, featureless
deposit was produced. The growth rate at the centre of the deposit showed a linear growth rate
with time.

0.28Mcitrate gold
Temp.= 40 C
Re. 10458
C.D. 3.0 A/cm sq
Depositiontime, secs.

Cl)
cn
W

1.0
2.0
0
+
C]
X

4.0
8.0
15.0
20.0

2
R dimensionless
distance

Figure6 1. The effectof increasingdepositiontime on the selectivity.Thedatafor T=0.5 is not

shown.
This would indicatethat masstransferwasconstantin the stagnationregion.Also, at R=0.5,
This
in
its
linear
time.
with
positioncorresponds
relationship
approximately
also
was
thegrowthrate
impingement
However,
this
the
relationship
was
not
valid
outside
the
zone.
to theedgeof stagnation
jet
the
thickness
the
62
the
Figure
at
of
centre-lineto variousvalues
of
ratio
a
plot
shows
region.
be
for
deposition
It
ie
8
impingement
that
times
seen
R
can
the
seconds
region.
above
of outside

158

has
fully
developed,
"dome"
the
the ratios are virtually constant.
shape
characteristic
when
However, during the initial stagesof growth, there is an accelerationin the rate of growth of the
stagnationzone comparedto the wall jet region, particularly at high values of R. It is proposed
that there is a suddenincreasein the rate of deposition in the stagnationzone due to an increase
in the local current density at this point. This is becausethe distancebetweenthe deposit and the
substratehas been reducedand becauseof the highly non-uniform current distribution within the
jet, the electric field is enhanced.The depositgrows at an enhancedrate within the stagnationzone
with respectto the wall jet region. This can be seenby the significant increasein the ratio at low
deposition times.

24

0.28MCitrate gold
Temp.= 40 C Rez 10458

20
nnti",
I
ZA
r
Ratio

of R=0

to R=1.0
0 Ratioof R=0 to R =1.5
v Ratioof R=0 to R=2.0

16
co

10

20

30

Time
Figure 62. The effectof increasingtime on the ratio of centre-linethicknessto variousvaluesof
R.
Additionally, due to this increasein current density, the walljet operatesat a lower current density
deposit
happen.
is
lower.
As
First,
two
things
the
the position at
grows,
the
efficiency
at which
from
is
be
flow
longer
jet
forms
the
the
away
stagnation
region
shifted
as
no
will
the
wall
which
becomes
larger.
into
Secondly,
flow
In
the
the
region
stagnation
effect,
the
substrate.
normal to
This
increase
in
to
the
becomes
aerofoil.
jet
of
an
effects
acceleration
similar
accelerated,
wall
boundary
layer,
in
the
the
thickness
have
turn would reduce
of
the
which
of
reducing
effect
would

159

the thicknessof the diffusion layer comparedwith a flat surface.Consequently,an enhancedcurrent

density over and abovethat previously experiencedwould prevail in the transition region between
the impingementregion and the displacedwall jet region. As a consequence,the efficiency would
for
improve.
The
this lies in the sudden reduction of the ratio as observed in the
evidence
also
deposit
deposition
As
in
increasing
to
time.
the
the
the
continues
grow,
growth
rate
with
graph
in
impingement
is
jet
to
that
the
there
although
ratio
region,
a
a
comparable
attains
region
wall
be
deposit
becomes
increasingly
in
This
the
these
as
expected
would
values.
slope
upward
noticeable
"domed", further displacing the wall jet away from the stagnationregion and increasingthe local
be
in
for
Figure
63.
The
jet.
Additional
in
this
the
mechanism
can
seen
wall
evidence
acceleration
data for this was taken from the study of the effect of nozzle to substratedistance. It can be seen
that when the nozzle is very closeto the substrate,a greaterdifferential thicknessoccurredbetween
the impingement region and the wall jet. This is becausea narrow gap would emphasisethe
difference in current distribution between the two regions. Further evidenceof the mechanisms
local
hemispherical
detailed
flow
transfer
and
mass
on
a
study
rates
of
require
operating would
beyond
dimensions
This
the scopeof this work.
the
the
was
as
nozzle.
same
substratesof

Graph

30
0 Ratioof R=0
L Ratioof R=0
17 Ratioof R=0
Ratioof R=0

0.28Mcitrate gold
Re. 10458
C.D. 3.0 A/cm sq
Temp.= 40 C0

to R=0.5
to R=1.0
to R=1.5
to R=2.0

20
0

10

0
01

H/d
Figure 63. The effect of the nozzleto substratedistanceon the ratio of the centre-linethickness
R.
of
to variousvalues

160

10.6.2 Interaction of the flow above the maidmum useful current density.
As hasbeenshownearlier, thedepositslosetheir featurelessappearanceunder certainconditions
of current density, flow or temperature.The depositsthentakeon a nodular, needle-likeor dendritic
character. The morphology diagramsshow suchtransitions. There are many factors that influence
these transitions and it is certain that the interaction of the flow with the deposit will dependon
such factors as the interplay betweentemperature,current density, flow rate, nozzle to substrate
distance and chemical composition of the electrolyte. Such complex interactions are difficult to
evaluatebut each individual growth structure will be discussedseparately.It should be noted that
in the case of the alloy golds, no structures other than nodular types were observed under the
be
limited
discussion
As
to that of pure gold.
the
consequence,
a
will
examined.
conditions

10.6.2.1NoduIar deposits.
As the current density exceedsthe maximum useful current density, the deposit growth habit
changes from a relatively smooth surface, exhibiting small rounded mounds, to a true nodular
is
just
it
fact,
In
that
the
a coarserversion of the rounded
appear
structure
would
nodular
structure.
is
fixed
dimensions
for
There
transition
to
the
simply
grow
greater
point,
mounds
no
mound.
density.
formation
different
for
The
creates
current
of
nodules
a
applied
surface
of
greater values
the impinging electrolyte. Surfaceimperfections reach length scalesof the diffusion and boundary
layers and local interaction with these become likely. If the magnitude of the nodules does not
diffusion
layer,
layer
boundary
the
then nodular growth will
the
thickness
the
of
either
or
exceed
interaction
As
direct
fluid
flow
this
type
the
of
growth,
with
with
no
occurs,
unhindered.
proceed
this subject will be discussedin greater depth later.

10.6.2.2 Needle-type deposits

At low temperatures, an increase in current density leads, in most instances, from nodular
deposits to the formation of needle-like forms. Thesestructures form very rapidly under suitable
densities,
from
jet
but
higher
low
At
they
the
grow
centre-line
at
current
current
conditions.
densities, they commencefrom a certain distancefrom it. The exact position at which they grow
is a function of the current density but would appearto be associatedwith the edgeof the stagnation
density,
diameter
for
free
is
for
the
the
the
Evidence
that
this
current
same
of
needle
region
zone.
in
fashion
from
diameter
flow
They
increasing
this
to
a
radial
extend
region
a
rate.
with
reduces
formation
deposition
The
irrespective
600
the
conditions.
and number
of
prevailing
Izin
of about
flow
function
Higher
be
the
temperature.
the
temperatures
tends
to
rate
and
of
a
produced
of needles

161

lower
formed.
Examinationof depositsexhibiting needles
low
flow
the
number
of
rates
needles
with
in the processof formation has indicated that the tip radii are very small (<0.1 Am). However,
have
tips
that
reachedtheir "maximum" length of around 225 Am show radii in
examination of
the region of 1-2,um. This suggestsa mechanismby which the needlesgrow and what limits their
length. It is proposedthat the needlesgrow by a mechanismof sphericaldiffusion. With low metal
ion concentrations,increasingthe current density rapidly leadsto a nodular deposit formation due
to ion depletion. Once the nodule size exceedsthe thicknessof the local boundary layer, needle
structures form by creating a wake in the direction of the flow. This wake causesturbulent eddies
that disturb the boundary layer leading to enhancedlocal agitation that allows a preferred growth
in the direction of the flow within the wake. Once the growth tip attains the critical radius for
in
direction
flow
behind
diffusion
the
the
then
of
growth
proceeds
via
spherical
growth,
needle
eddy. Higher current densitiespromote the onsetof needlegrowth by generatinglarge nodulesat
increaseddistancesfrom the centre-line. Additionally, an increasein the current density promotes
the rapid growth of thesenodules, leading to a greater number of needlesto be formed.
The type of needle structure strongly dependson the prevailing temperatureas described in
Section 8.1.2.2. At low temperatures,flow rates and current densities, the needlesare varied in
flow
have
high
larger
At
there
they
of
needles
and
a more
rates,
are
a
number
size and shape.
in
both
leads
Increasing
the radial and axial
the
temperature
to
needles
growing
size.
regular
direction. At low flow ratesunder theseconditions the needlesgrow mainly in the axial direction
form
The
from
jet
form
the
the
stagnation
region.
usually
emanating
within
structures,
core
and
layer.
interaction
boundary
It
is
dependent
highly
is
their
the
suggestedthat
on
take
with
needles
the variance in size and shapeof the needlesseenat low flow rates and temperaturesis due to the
increasedviscosity of the electrolyte when comparedto higher temperatures. Due to the viscous
form
damped
dependent
local
highly
This
flow,
that
the
the
are
on
conditions.
and
eddies
of
nature
low
high
flow
in
At
lead
the
temperatures,
the
and
size
rates
and
to
shape
of
needle.
a
variation
will
due
increased
to
the
size,
shear stresseswithin the flowing
consistent
a
more
the needlesare of
liquid. This leadsto a less dampededdy formation beyond the protruding nodulesand therefore a
High
habit.
due
temperatures
to
the
to
also
proceed
allow
eddies
undamped
growth
regular
more
High
flow
increase
the number of needlesbecauseof
lower
the
electrolyte.
rates
of
the
viscosity
boundary
layer.
As
between
interaction
the
thinner
the
and
nodules
well as radial growth,
a greater
is
leads
limit
It
this
that
to
the
they
of radial growth. As the
grow.
process
thicken
as
the needles
needlesthicken, they effectively shield the growing tips and rob a greaterproportion of the current.
This shielding effectively reducesthe overpotentialat the growing tip and the critical overpotential
for needle growth is reduced. In addition, it is likely that the metal ion concentrationavailable to
local
limiting
density.
lowering
it
has
been
Indeed,
the
is
thus
current
reduced
the tip
seriously
ion
low
concentrations,considerablenodule growth occurs on the needles
that
metal
at
observed
Henceforth,
is
but
to
the
tip
impingement
tip.
the
this
close
seen
needle
not
no
the
region
within

162

longer grows in a radial direction. However, althoughno further increasein length occurs, some
growth in the diameter of the needlesmay still take place. This would explain why fully formed
needleshave comparitively large tip diameters.

10.6.2.3Field orientedjet core structures.

Someof the more unusualand beautiful growth patterns are observedat high current densities
and medium to high temperatures.Theseare field orientedjet core structures. Photographs9 and
12 show examplesof such forms. It can be seenthat they are varied in shape,and indeed, they
are a small number of the variations on the generaltheme. However, there are two basic types of
jet core growth. These are central growths, that extend into the central region of the free jet and
edge growths. The latter grow along the outer edge of the free jet. The variations that occur to
these basic shapesis largely due to local turbulencesand electric field variations, each of which
becomemarkedly modified asthe depositgrows. There is no clear distinction betweenthesegrowths
however as exampleshave been observedthat obviously begin their growth as needlesbut then,
after attaining a certain axial size, start to grow within the free jet. Other examples commence
but
is
diverted
direction
free
jet
in
then
the
the
the
along
radial
edge
of
either
or along the
growth
centre-line. Thesestructuresare not true dendrites, as they possesno crystalline regularity. Some
do have a regular growth front, resemblingDBM structures. They tend to grow along the free jet
forms,
from
but
flattening
branching
form
fern-like
to
growing
a
single
and
point
a
edge as
cylindrical configuration. Multiple layers of thesebranchesmay be observed,resemblingthe petals
just
layer
Others
flowers.
a
single
show
and resemblea crown.
of
One thing is common to this type of growth. In all cases,they appearto start at the edge of
the stagnation zone. Those that grow along the jet centre-line do so from a point or points away
from it. Photograph 12 shows the way in which a centre-line core structure forms. Initially, a
from
distance
forms.
Then,
deposit
the centre-line, a nodule
one
or
more
at
points
at
some
nodular
layer
jet
boundary
forms
The
likely
and
the
a
wall
radial
needle.
most
point at which
penetrates
this would occur is at the edgeof the stagnationzone. At this point, the wall jet commencesand
the boundary layer is at its thinnest. This would account for the regular radial position of the
high
density
12(c).
Because
in
Photograph
the
current
of
associatedwith these
needlesobserved
by
head
to
the
the
tails
compared
experiences
enhanced
growth
the
needle
of
virtue of
structures,
flowing
in
It
direction.
Here,
influences.
the
the
and
rapidly
meets
electrolyte
grows
axial
ohmic
it is subject to both a high electric field and a high flow rate and growth accelerateseven further.
It can be seenthat in addition to growth towards the nozzle, secondarygrowths may be observed
in
direction
flow.
form
The
for
formation
the
the
from
the
of
the
mechanisms
as
needles
nozzle
away
described
to
those
previously.
of these are similar

163

The mechanismof growth of the ferri-like forms that grow along the edge of the free jet are
not so clear. Examination of all the depositswould indicate that centre line forms tend to grow at
lower values of Reynoldsnumber, lower current densitiesand lower temperaturescomparedwith
the former. It is thought that the crown-like structures developas a result of additional turbulence
in the edgesof the free jet due to the greater velocities but the exact mechanismwould require
further investigation.

Oneof the featuresof the depositsformedat high currentdensitiesis their lack of crystalline
regularity. Many of the fern-like or crown-likeforms resemblefractal structureswhilst others
resembledensebranchedmorphology(DBM) types.Generally,therewouldappearto bea regular
growth front like that observedwith DBM structures.However,closerexaminationrevealsa
significant numberof irregular growthswithin them. Becauseof the highly non-equilibrium
conditionsof deposition,it is not surprisingthat a mixtureof both maybe present.The presence
of a regularlygrowthfront wouldsuggestthattheseareDBM typeforms.The methodof growth
in
5.1.5),
by
Barkey
(Section
whicha thick boundarylayer existsat the growingtips,
suggested
during growth. Tip splitting is certainlya
is unlikely underthe high ratesof flow experienced
featurebut it is morelikely that this occursdueto nucleationandgrowth on or closeto the tips
leadingto secondary
andmultiplearmsforming.Thisprocessis repeated
creatinga multi-branched
front
induced
be
by
Stability
the
growth
may
of
meansof theconstancyof the impinging
growth.
flow togetherwith the effectsof the electricfield, which would alsobe constantacrossthejet.
However,therearemanyexamplesin whichcertainbranches
growattheexpense
of othersleading
to a non-uniformgrowth front. The most likely explanationis that all the structuresare fractal
(DLA) and that in somecases,regularityis produceddue to the
diffusion limited aggregates
flow
interaction
the
of
andtheelectricfield. Indeed,undertheseconditionsof growth, the
overall
depositionis truly diffusioncontrolled.

10.7 THE GROVrM

OF NODULAR DEiOSITS.

Whilst the fractal structuresproducedat very high current densitiesare an interesting field of
limitation
deposits
do
to
the
that possess
they
a
major
of
smooth
constitute
production
not
study,
lower
densities
All
by the formation
the
above
phenomenon
are
at
current
preceded
useful properties.
deposits
have
been
be
Smooth
deposits.
to
shown
produced at rates as high as 3.4
of nodular
density
is
increased,
if
deposit
becomes
increasingly
However,
then
the
the
current
,um/second.
It
has
been
for
therefore,
applications,
useless.
shown that smooth deposits of
most
nodular and
both gold and gold/nickel alloy, exhibit rounded mounds. Microsections have shown that these
With
increasing
densities,
to
the
to
the
substrate.
a
close
region
current
extend
mounds
rounded
height.
At
in
both
density,
depending
and
some
radial
size
current
grow
mounds
on the
rounded

164

prevailing conditions, the mounds becomenodules, that is they no longer exhibit integrity with
their neighbours.This is thetrue limiting condition to high speedjetdepositsof gold. Thernechanism
by which thesestructuresform will now be discussed.

10.7.1. Inhibition versusdiffusion mechanisms

Nodular depositsare produced when diffusion controls the rate of reaction.- They occur as a
ions)
(partially
low
adion
electronated
concentration,low ratesof surface
of
surface
consequence
diffusion and are generally associatedwith 3-dimensionalnucleation. In Chapter 5, the various
factor
irregularities
discussed.
The
that controlled
of
were
main
amplification
of
surface
mechanisms
it
be
depended
being stabilised by means of
on
amplified
or
not
would
whether a perturbation
surface tension. The surface tension is controlled by the surface concentrationof adions. At low
is
influence
lost
the
the
of
surface
concentration
stabilising
and the perconcentrations,
adion
turbation will grow, forming a nodule. In the caseof gold, rounded mounds (the early stagesof
hardened
deposits.
depositing
Nakahara
formation)
thick
alloy
gold
often
observed
when
are
nodule
for
The
formation
these
such a growth was suggested
the
mounds.
mechanism
of
rounded
studied
to be due to inhibition of lateral growth due to adsorbedspecies.However, as such growths are
deposition
be
deposition
in
diffusion
this
the
systems,
may
controlled
other
not
under
often seen
described
by
deposition
Eisenmann,
21.
If
the
as
of
gold
mechanisms
consider
of
we
only mechanism.
from
high
is
At
AuCN
CNthis
reaction.
species
and
produced
an
adsorbed
growth proceedsvia
deposition rates, significant quantitiesof CN- will be producedinfluencing the surfaceequilibrium.
As adsorbtion is a relatively slow step, it is likely that only a low surfaceconcentrationof adsorbed
AuCN can exist on the surface under theseconditions and growth will thus proceed with a low
higher
density,
lower
The
Stability
the
the
the
current
adion
concentration.
concentration.
adion
is
increasingly
lowered,
the
the
growth
that
surface
concentration
of
smaller
as
theory suggests
increases,
the
tension
the
surface
surface
concentration
controls
of the growing
as
perturbations
is
becomes
lost
When
the
small,
stability
concentration
exceedingly
and smaller
surface
crystallites.
larger
The
increasingly
form
deposits
to
nodulation.
extensive
nodular
grow
will
perturbations
from pure HSSJEgold show evidenceof 3-dimensionalnucleation. This occurs when little surface
diffusion occurs under conditions of high applied overpotentials. It is suggestedthat particularly
in the caseof pure gold, nodular depositsresult when the AuCN is reducedas soon as it reaches
high
diffusion.
forces
for
Consequently,
little
the
the
time
overpotential
surface
the surface with
immediate nucleation with near neighboursleading to a small perturbation. As the surface coninstability
from
benefits
due
diffusion.
is
low,
to
the
and
grows
enhanced
perturbation
centration
This creates a situation where further growth occurs on the perturbation at the expenseof the
from a single nuclei, or small group of nuclei,
Consequently,
the
grows
perturbation
surroundings.
field.
diffusion
the
direction
in
the
and
electric
gradient
the
of
rapidly

165

The typical inverted conesectionalprofile of the noduleresultsbecausethe radiusof the growing

perturbation is not small enoughto benefit from spherical diffusion as a dendrite would. This is
because3-dimensionalnucleation producesa cluster formation which is significantly larger than
the growth of a spiral dislocation that leads to a dendrite. The cluster of crystallites will benefit
from some diffusion in a lateral direction, leading to an increasein the diameter of the nodule as
it grows. Additionally, as the nodule robs the diffusion layer of ions as it grows, it effectively
inhibits the region surrounding it from further growth. This ultimately createsa growth that is not
integratedwith and proud of its immediatesurroundings.The degreeto which the noduleprotrudes
above its surroundings is dependenton all the factors that control its growth and is therefore
predominant at high current densities. At lower current densities, more ions are available in the
diffusion layer and thus can reach the regions adjacentto the nodule allowing them to grow as
well. Consequently, at lower current densities, nodules may be incorporated within the deposit
with only the tops showing. Such a situation would account for the rounded mound structure. It
is clear from microsectionsthat where roundedmoundsare observed,they emanatefrom a single
point on or close to the substrateand grow as individual entities but due to surrounding growth,
are integrated within the deposit.
Whilst such a mechanismmay operatein the absenceof surfaceinhibition, it doesnot preclude
the influence of inhibition on nodule growth. Indeed, inhibition of literal growth could also lead
to nodule formation by a slightly different route. In Nakahara'sstudy of cobalt hardenedgold, he
found that the rounded mounds were evenly distributed with diametersof the same order as the
thickness. Such regularity would not be expectedbasedon the randomnessof diffusion processes
exclusively and indeed, nodular deposits of pure gold exhibit a wide range of sizes. Nakahara
suggestedthat the reasonfor thesemoundswas the inhibition of lateral diffusion by non-metallic
species. As a consequence,small perturbations were amplified in the axial direction. He also
inhibiting
due
the
to
that
adsorption
of
molecules on the top surface of the mound,
suggested
continuous nucleation occurred, in effect, 3-dimensionalnucleation. This was responsiblefor the
small grain size observed.
Both mechanismsare equally feasible in the formation of nodules. In the caseof alloy golds,
it is clear that even under conventional deposition conditions, a relatively small grain size is
inhibition
3-dimensional
is
This
a
result
surface
as
of
and
usually
nucleation, which is
produced.
the way most brighteners work. In the caseof pure gold depositedconventionally, the grain size
is not unusually small, indicating that little or no inhibition is in operation. Under conditions of
high speeddeposition, the grain size is reducedto similar valuesas the alloy golds. It is well known
that increasingthe current density leadsto a smaller grain sizebut in this caseit is uncertain whether
factor
is
due
to
this
alone.The cyanidegeneratedduring depositioncan readily
purely
the reduction

166

adsorb on a surface such as gold particularly as it is formed on the surface. Further studies are
required to establishthe actualmechanismof noduleformation, particularly with regardsadsorption
phenomenon.

10.8. SUMMARY OF FACTORS CONTROLLING THE NLkXIMUM DEPOSITION RATE.

It is clearfrom theprecedingresultsanddiscussionthat the factorsthat controlthemaximum

depositionrateduringHSSJEarecomplexandhighly interactive.Underconventionaldeposition
conditions,the acceptedwaysof increasingthe depositionrate suchas increasingthe metal ion
concentration,increasingtherateof agitation,increasingthetemperature
andtheuseof additives
are practicaland valid. Underconditionsof high speeddeposition,suchfactorsbecometotally
dependenton eachother.It is to be expectedthat whena systemis pushedto its operatinglimit,
small changesin the operatingconditionscanhavea profoundeffecton the performanceof that
system.This hasbeenshownto be the casefor HSSJE.Jettingan electrolytethroughan air gap
hasbeenshownto be capableof increasingthe maximumdepositionratesof gold by up to 3 fold
for thick deposits(> 10tLm).Additionally,themethodproducesdepositsselectivelywithout the
it
has
However,
been
for
for
that
theconditionsandelectrolytestested,this
shown
masking.
need
increasein depositionrateswould appearto be the maximumachievablewithout a resultant
degradationof depositquality. Increasingthe flow rateleadsto an increasein depositionratesas
boundarylayerthicknesses
thediffusionlayerandhydrodynamic
arereduced.However,increasing
theflow rateleadsto sucha reductionin boththataninteractionwith thegrowingsurfaceinevitably
is
interaction
high
densities
This
predominant
at
current
very
where a large diffusion
occurs.
ion
instability
in
low
This
leads
to
theelectrocrystallisation
concentration
exist.
surface
and
gradient
diffusion
layer
is
be
As
to
the
surface
perturbations
small
amplified.
sub-micron,
allowing
process
into
grows
and
penetrates
andbeyondthe boundary
rapidly
outwards
and
a small amplification
layer and into the region of uninterruptedflow. Acceleratedgrowth is then experiencedin the
direction of the flow leadingto manybeautifulbut technologicallyworthlessgrowths.Oncethe
is
deposit
destroyed.
Despite
fact
becomes
the
the
that, in thecaseof
effectively
unstable,
surface
density
is
0.7
limiting current
the
current
useful
of theelectrochemical
around
maximum
puregold,
density, it would not seempossiblethat a further increasecouldbe achievedwithout the useof
is
However,
increase
inhibiting
the
often
use
of
associated
such
materials
additives.
with
an
growth
in polarisationand in the caseof gold, a reductionof currentefficiencywould be probable.In
incorporated
become
into
deposit,
is
likely
its
the
to
which
often
materials
affect
such
addition,
functionalperformance.
The use of pulse plating has been examinedas it can often improve depositquality and
ftirther
increase
in
deposition
However,
the
no
examined,
under
conditions
ratescould
smoothness.
be obtained.It is likely that the conditionsat the interfacedid not allow the evenestablishment

167

of a pulsating diffusion layer that followed the micro-profile of the surface. As a consequence,
tertiary current distribution wasaffected.A further factor wasthat eventhoughequitabledeposition
rates to DC could be achieved, the depositswere more porous due to gaps between the mound
structures. Thesealmost certainly result from inhibition of the lateral facesduring the off-time by
speciessuchas AuCN or CN. It is worth exploring other pulse regimesbut there are theseintrinsic
problems to be overcome.

In the caseof alloy golds,muchhighercurrentdensitiescanbe achievedbut at theexpenseof

influence
due
lower
to
the
of theadditivesonthepolarisation.Manyapplications
current
efficiency
a
tobeapplied,asin thecommercial
goldsnowrequirevanishinglysmallthicknesses
of alloyhardened
connectormanufacturingindustry.For this industry,it may well be possibleto apply suchthin
in
However,
for
this
than
themajority
shown
study.
of
magnitude
greater
an
order
at
rates
coatings
be
hard
thicker
to obtain without the
that
would
coatings,
such
rates
require
of applications
degradationof the deposit.On the basisof the evidenceand the mechanisms
proposedin this
Thesis,it would seemthat we haveindeedreachedthelimit.

168

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173

Photograph 1. The X-Y table (in the fume cupboard) with the control computer and ancillary
equipment.

174

Photograph 2. SEM micrograph of a pure gold deposit produced using H/d = 4.375.0.27M phosphate gold electrolyte.

Photograph 3. SEM micrograph of a pure gold deposit produced at a current density of 0.75 A
is
The
deposit.
"dull"
topography
to
that
similar
of
a
conventional
appearance.
typical
a
of
CM-2,
0.17M Citrate gold, 55oC
175

Photograph4. Optical micrograph of a pure gold deposit produced at a current density of 4.75 A
"rounded
0.17M
typical
mound"
a
appearance.
citrate gold, 55-C.
showing
CM-2

Photograph 5. Optical micrograph of a pure gold deposit produced at a current density of 7.0 A
55-C
0.17M
gold,
2
citrate
structure.
CM showing a nodular

176

Photograph 6. SEM micrograph of a typical radial needlestructure.

Photograph 7. SEM micrograph of a typical non-directional organic type of growth, classified as

"severe needle" type.

177

Photograph 8. SEM micrograph of a structure growing into the edgeof the jet.

178

Photograph 9. SEM micrograph of a jet core structure. The colour has been addedby computer
enhancement.

179

oex
$sun

211(U 410NO

382X
laeum -

P--69497.

25KU 110: 19MM

$losses

P'Sesis

leoum-

51u wo i9mm

SA0800

25KU WD:14NM

S: 00909 PIS0029

321X
leou"

".,

.-

'-

..;

I-- I-

--

b,

Vw . 4w .-,
W. 4.,
--olk
.,.

job
_44
ter

-.

-, *

-IV

P-80014

325X
MUM

25KU WD:13MM

szooese

V09821

- s .--,
jz,.

;iz e C.- .-W 562 ,

-,

F'

Zw
low

%v

r"'.

lit

: A'

IM

74(-V.

0.17M
increasing
time.
deposit
with
the
growth
of
the
Photograph 10. SEM micrographs showing Re. 3335. (a) 0.8 secs. (b) 1.5 secs. (c) 2.5 secs. (d)
==
A
7.0
density
CM-2.
Current
=
gold.
citrate
6.0
(f)
secs.
5.0
(e)
3.5 secs.
secs.
180

1,27KX
20um-

25KV WD 18MM

s 00000 P: 08812

0 UM_

25KU WD JeMm

s 00000 p 00011

higher
but
10
deposits
in
Photograph
at
the
shown
Photograph 11. SEM micrographs of some of
denCurrent
deposition
0.17M
increasing
times.
gold.
citrate
magnification showing the effects of
3.5
(d)
2.5
1.5
(c)
(b)
secs.
0.8
(a)
secs.
3335.
secs.
Re.
secs.
A
7.0
=
cm-1.
sity =
181

L- SE1

cm
tv
W, 10.10

mia

Tm
,

mwlaamo

Photograph 12. SEM micrographs showing the growth of the deposit with increasing time at a cur0.17M
Current
density
jet
density
produced.
are
citrate
gold.
structures
core
rent
at which
= 10.0
A CM-2.Re. = 12078. (a) 0.6 secs.(b) 2.0 secs. (c) 2.0 secs. (d) 3.5 secs. (e) 6.0 secs. (f) 8.0 secs.
182

Photograph 13. SEM micrograph of a pure gold deposit produced at the maximum useful deposition
rate of 3.4 jAm/secondat a current density of 6.0 ACM-2. Deposit thickness = 18.0 Arn.

Photograph 14. SEM micrograph of a conventionaldeposit produced at a current density of 5.0 rnA
18.0,
Deposit
thickness
=
um.
cm-1.

183

Photograph 15. Microsection of a pure gold deposit produced from the optimised citrate gold electrolyte. Current density = 2.0 A CM-2.Re. = 12078. Temperature = 55oC. X 2000

Photograph 16. Microsection of a deposit produced from the optimised citrate gold electrolyte. CurTemperature
Re.
55oC.
A
12078.
X 2000
4.0
density
CM-2.
=
=
rent
=

184

Photograph 17. Microsection of a deposit produced from the optimised citrate gold electrolyte. Current density = 6.0 A CM-2.Re. = 12078. Temperature = 55oC. X 2000

Photograph 18. Microsection of a deposit produced from the optimised citrate gold electrolyte. CurTemperature
55oC.
X
2000
Re.
12078.
7.0
A
density
=
cm-1.
=
rent
=

185

304X
LI 0,100ti

25f...U WD: 41titi

00

Photograph 19. The effects of electrolyte velocity. 0.28M citrate electrolyte. Current density
4.75 A CM-2.Temp. = 55oC. Re. = 1044.

Photograph 20. The effects of electrolyte velocity. 0.28M citrate electrolyte. Current density
4.75 A CM-2.Temp. = 55oC. Re. = 5220.

186

Photograph 21. The effects of electrolyte velocity. 0.28M citrate electrolyte. Current density
4.75 A Crn-2.Temp. = 55oC. Re. = 9396.

density
5.0
Current
ACrn-2.
0.17M
influence
The
22.
citrate
gold.
=
Photograph
pH.
of electrolyte
Temp. = 55 -C. Re. = 12078. pH = 5.3.

187

Photograph 23. The influence of electrolyte pH. 0.17M citrate gold. Current density = 5.0 A rM-2.
Temp. = 55 oC. Re. = 12078. pH = 6.1.

Photograph 24. The influence of electrolyte pH. 0.17M citrate gold. Current density = 5.0 A CM-2.
Temp. = 55 oC. Re. = 12078. pH = 8.1.

188

ENT-9.80 KY Wo 20
200
v
UNYJETPLATEINGSAu
L- SE1

Photograph 25. A typical exampleof a "rose" type morphology produced using pulsed current in
conjunction with HSSJE.

Photograph 26. A typical exampleof a "crown" type morphology produced using pulsed current in
HSSJE.
with
conjunction

189

Photograph 27. A typical exampleof a "field oriented random" type morphology produced using
HSSJE.
in
with
pulsed current conjunction

L- ', EI

EHT- 10.0 KV
10. Ommi1

Wu- 15

PHOTO- 11

mm

1TI1;
i]

-kA'

--cal.

1,LE4

k"m

';

in
using
pulsed
current
"smooth"
type
produced
morphology
Photograph 28. A typical exampleof a
HSSJE.
conjunction with

190

in
"nodular"
type
produced
current
A
using
pulsed
29.
morphology
typical exampleof a
Photograph
HSSJE.
with
conjunction

from
deposit
Ronoval
N
17.2
gold
produced
a
eleca
prn
of
An
Photograph 30.
optical micrograph
X
A
Re.
10800.
8.0
density
Current
but
CM-2.
"booster"
1-1
=
=
no nickel.
trolyte containing 60 ml
2000
191

Photograph 31. A microsection of a gold deposit producedfrom a Ronoval N electrolyte containing

60 ml 1-1"booster" but no nickel. Current density = 9.0 ACM-2. Re. = 10800. X2000

from
Ronoval
N
deposit
produced
a
A
electrolyte containing
32.
gold
Photograph
microsection of a
60 ml 1-1"booster" and 3.0 g 1-1nickel. Current density = 6.0 A cm-1.Re. = 10800. X2000

192

Photograph 33. An optical micrograph of a 17.6 pLmgold/nickel alloy deposit produced from a
Ronoval N electrolyte containing 60 ml 1-1booster and 0.7 g 1-1nickel. Current density = 8.0 A
CM-2.Re. = 10800. X 1000

Photograph 34. An optical micrograph of a 17.9 fzrn gold/nickel alloy deposit produced from a
Ronoval N electrolyte containing 60 ml 1-1booster and 2.2 g 1-1nickel. Current density = 8.0 A
1000
X
Re.
10800.
CM-2=

193

Photograph 35. SEM micrograph of a 2.5

deposit produced from a Ronoval
gold/nickeI
alloy
jum
electrolyte containing 60 ml 1-1and 1.9 g 1-1nickel. Current density = 10.0 A CM-2.Re. = 10800.

3, OSKX
leum

26KV W0115MM

S: 00000 P: 0189I

Photograph 36. SEM micrograph of a 2.5 jAmgold/nickel alloy deposit produced from a Ronoval
Current
1-1
density
ACM-2.
1-1
1.9
12.0
Re. = 10800.
60
nickel.
g
and
n-d
=
electrolyte containing

194

26K UWD 14 MMS:

018000 P: 00004

deposit produced from a Ronoval N

Photograph 37. SEM micrograph of a 2.5
gold/nickel
alloy
jam
electrolyte using conventional deposition conditions. Current density = 10 mACM-2. Temperature
= 350C.

Photograph 38. An example of a directly written ring oscillator produced by HSSJE with both a 400
layer.
"seed"
the
1001im
metallised
of
nozzle after removal
Itm and a
195

Photograph 39. The connector wear test configuration as used by the GEC Contact Tester showing
an actual contact pair under test.

196

DATA TABLES
Thesetables list the most relevant data obtainedduring this study.

197

0.041M CURATE GOLD ELECTROLYTE

G?ld (aspotassiumgoldcyanide)
Diammoaiumhydrogencitrate
Citric acid
Potassiumhydroxide

8.2 g 1-1
45.0 g 1-1
15.0g 1-1
to pH 6.0

Kinematicviscosity

25-C
40oC
55-C

0.0100203cm%w,
0.0073904cm%wI
0.0058590CM2SeC-1

Conductivity

25-C
55-C

49.6 mScnrl
83.12mScnrl

0.28M CURATE GOLD ELECTROLYTE

Cold (aspotassiumgoldcyanide)
Diammoniurnhydrogencitrate
Citric acid
Potassiumhydroxide

54.0 g 1-1
45.0 g 1-1
15.0g 1-1
to pH 6.0

Kinematicviscosity

25-C
40-C
55-C

0.012284cm2se%-,
'
0.009221cm,2sec-I
0.0076567cm2sec-I

Conductivity

25-C
55-C

55.3 mScar'
97.6 mScnrl

0.17M CURATE GOLD ELECTROLYTE

Cold (aspotassiumgold cyanide)
Diammoniurnhydrogencitrate
Citric acid
Potassiumhydroxide

33.5 g 1-1
45.0 g 1-1
15.0g 1-1
to pH 6.0

Kinematicviscosity

25-C

0.005906cm2swI

Conductivity

55-C

92.3 mScra-I

0.28M LOW CONDUCTIMY CURATE

Cold (aspotassiumgold cyanide)
hydrogencitrate
Diammonium.
Citric acid
Potassiumhydroxide

54.0 g 1-1
1.0 g 1-1
1.0 g 1-1
to pH 6.0

Kinematicviscosity

55-C

0.04232cm2sw,

Conductivity
0.27M PHOSPHATEGOLD ELECTROLYTE

55-C

48.8 mScnrl

Gold (aspotassiumgoldcyanide)
hydrogenphosphate
Di-potassium.
Potassiumdi-hydrogenphosphate
Potassiumhydroxide

53.1 g 1-1
40.0 g 1-1
10.0g 1-1
to pH 7.1

Kinematicviscosity

25oC
40oC
55-C

0.009164cm2sec-I
0.006891cm2sec-I
0.005426cm2sec-I

Conductivity

25-C
55-C

52.44mScnrl
90.02mScurl

TABLE 1. Composition and someproperties of the pure gold electrolytes used in this study.

198

SAMPLE NO.

Awl

To".

PH .

ELECTROLYTE
l

25 C

Nozzle

al

0.041M Citrals

tywas

:02

Nozzle size ern

Total-coulo,

ribe

05

54

)0041

rate uissic

1
0oposit quality

0 Obe

SAMPLE NO.

so

lie

0 ISO 0.381

- 4

Terro. .
PH .

Total couiornbe
Thick, @" um
Plating rote U/2*C

0 675

0 942

ELECTROLYTE

25 C

Nozzle size cin

1
025
031
123

2
4
05
075
11
003
094
1 26
625 41 45 31 25

Omas
0
0

am, 1, offla
So
46
0 074 0 207

o
106
0 339

PH -

I$

7
a
1 225
15
1 75 12
1 68 220 f 251 1 283
208 1782 11583 1388

125
-1 57
249

ome. 2 m"
M, 9
T-77
1288
161i
is
0
0 774 0 970

502
7*8
am's

amp,

I)MV6

I
:, 49010W"

Is
a
7.54
52

Is

17

am's

ReynoldsNo.

;9- 31 235

10
it
121
13
14
25
275 13
3 14 345 1 377 1 5.02
125 11 35 1042
78

em, p Ums

WIS

190

ww

offloo

0041,
kle

a"

on*

14
5
625
025

is
a
754
52

is

17

I
is

00a0111 offl314 cm, $

am*

one

arm

0.041M Cluraft

Nozzle velocity Was,

Nozzle area cm eq

101

Nozzle size efn

al

14
5
028
825

'Ascosity C" sailsoc.

10

ELECTROLYTE

25 C

To".

coasis emai,

13
4

Nozzle area cm aq

00,11

Aull

to
1,
12
25
275 13
314
345 1 377
125 11.35 io 42

am'?

-:

15

D*pc)ot quality

SAMPLE NO.

0.041M C41rals

Nozzle velocity Was

Ol

Reynolds No. 798.4

an*

13
Spot nurnber
Curnsmidensity Alcm eq
Current applied mill,
Tornesacs

lee

Au2

9
225
283
1388

a am'?

lea

::

7
0
15
1.75 12
1 88 220
251
208 1782 1563

00"GaP *",

1
00010"02

Viscosity ern qq/sec.

1a

1 25
1 57
249

603ser 0.3011, small

Thickness um
Plating

2
3
4
025 1 05
075
1
031 1 003
094
1.20
123 625 4145 31.25

Nozzle area ern sq

04

15
Spot number
Current density A/cm eq
Cufront applied mA
Tirm sees

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

Reynolds No. 3992

'Ascomily ern tiqlase.

00.4

0-10110

1
Spot number
Cu"nt density AJcr, sq
Current applied rriA
Tornipsocis
Total coulornbt
Thickness Urn
plating rate u1soc
IDepolat Quality
I

ELECTROLYTE

an

naion n*/sn
I

cm Iq

raw W

one

004

0 001INS

25
0 04

63

106

83
0 256

0 152

0 426
I
i

is

one
1

11
0 520

136
0 793

140
0 963
t

156
1 126

ow

185
132
4

Z/sn
n

on

s- wnooth & brighl d- smoolh & dull

ob - s". b4ight n- sloght nodulatkbn
on - severe nodulation no - slight noodie growth
one - severe noodle growth ic - lot com dendfile
er - cracks nd -" vioble, do at

PE
1 no
I

Reynolds No. 5068

T
is00,

Viscosity cm eqtsee.

21
3
4
51
a
7
1
9
10
il
12
05 1 075
1 1 25
115 1.75
2 225
025
25
275
31
--1 26 1 57 188
220
0"
251
063
293
3.14 345
377
V 31
123 625 4145 31 25 249 208 1782 1503 1388
125 11 35 1042
emoi, omini omas 0-as smair @"to essIty amirs om, r aa0-oe
0
0

anis

171

Is

I1

1-

somesurnent
only

sne

Nozzle or" em eq

15

Nozzle sz* cm

qualffi,

DEPOSIT QUAUTY KEY

14
13
15
5
L
4
-502
628
754
78
625
52
0"It
OM?a 00.1.

0.041111,11
Chraw

Nozzle

@I

am

PH

7hicknissioum

vi"

d1

Wd

25 C
is

=-P.

Awill

Temp.

-Plating

9
I

SAMPLE NO.

Spot nurnber
Current density
Cu"nt applied
T.rns, soice
Total coulombs

a
7
a
4
a1
9
10
It
12
1 1 25
15
1175
2 225
25
275
3
_075
094
2SI
1 26 1 57 1188 220
263
314
345
377
208 1782 IS63 1388
4145 31 25 240
125 11.35 1042
a50,30,11
eMall am's 00MIF 0mol am'? a00Irs
99
so
120. 144
154
ISO
T 126
0 let 0317 0357 0"
084)8 7"s

2
1
025
OS
083
031
123 82S
0-al
0
33
0 0053
rid

one

13
14
is
5
4
6
502
626
754
78
025
52
am"
aam"

17

P4
one

TABLE

199

is

11

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

ELECTROLYTE

Am$

SAMPLE NO.
Tonw. -

25 C

pH .

61

0.041M Civals

Nozzle imelocity"Wift

18

Nozzle size em

C,04

rate u1sec
I

qual Ty

0.00126

Viscosity cm sq/ooc

001002

0035

0118

0256

0414
0 41 4 0591

10

no

Tomp. -

40 C

pH .

61

07199

dl

AwS

1 162

1017

De

rid

SAMPLE

no

end
no

Nozzle area em oq

40 C

pH

@I

We

Reynolds No. 1082

: 00120

Mocosity, crn sq/vec.

0027
4

to

74

44
0106

104
0 418

0 237

d, s

103

Nozzle velocity

14
0 786

0 40
an

0"

91
10
11
12
is
14
15
is
25
225
215
3
4
5
a
a
263 3 14 345
377
502
628
754 1005
78
1358 12 5 11 35 10 42
025
52
39
oowr 6
0
coniars od"19 00,tirm om's 0-9

157
1 004

an

ELECTROLYTE

Tornp.

Au7

NO.

Is

17

0.04 1m Chre's

--

Nozzle are cm

0
42
0 0067

urn
Pis:Mting
f tw*o u0

15
14
is
5
a
a
028
754 1005
025
52
30
0001900119 don't

1 352
junt"I

13
4
502
78

ELECTROLYTE
Nozzle Velocity RV;

9
10
11
12
225
25
275
3
28.3 314
345
3 77
13 88 12 5 It 35 10 42
oml? down 001*20 ottiddi,
i6o
is I

2
4
5
7
1
6
a1
05
075
21
025
1 1 25
15
1 75
064
2 51_
063
1 26 157 1 as 220
031
208 1782 1563
I Z3 62 5 41 45 31 25 249
a00=
60
oo:vsoe0"10 omly 00-

Thickmess

7185

13
Spot "Uniber
Curretif doriory Iklem so
Current aDpl-ed mA
Tirne socs
Total coulonnom

ReynoldsNo.

1a

SAMPLE NO.

Nozzle area crn aq

2
3
4
5
0
7
1
05
075
025
1 1 25
15
1 75 1
2
094
15
157
1 be 220
251
031
083
128
123 825 4145 31 25 2499 20 6 17 82 15 63
G
Do10"i"if . 41m od'Sof
a o"If
oGd.? . 0m,f
0
2.2
a 103
10 3 123
137
49
ISO

Spot mumbor
Curreml density Aicm sq
Curremtappied mA
Time mcs
Total coulorrtos
Thlekn*64 Urn
Plabrig
i0opost

an

223
1 784

174
1M
9m

21 1
1 859

20
1 919

am

on

1 on

11

18

207
26538
In,

0.04 1M Citrade

Nozzle ares cm eq

rrvm

Reynolds

I.

No.

2706

Is
a

17

Nozzle size er"

Viscosity
0,51
crn
sq/90c.
1

Spot

Toialcoulo,
Thmkiiegl

4
1
1 20

1 25
157

15
1 88

62 5 41 45 31 25

249

20 8 17 82 15 63 1386

05 1 075
004
0 63

025
031

123

Time socs

urn
Platilmo rate U,

d/s

0. 117

225
263

11
275
34S

12

3
3 77

13
4
502

14
5
628

is
a
7S4

12 5 It 35 10 42

76

a 25

52

149

d/9

40 C

Nozzle velocity

at

Nozzle size crit

Cox,?
174

is a

do
Is 7

tn1

an
I

ELECTROLYTE

AuG

pH

ed

2
251

10
1 25
314

0 154 0 262 0 418 0 S63 0 &M 1 062 1 255 1 496 1 656 1 Till

Q-Al, ty

To".

1 75
220

0 006

F-

SAMPLE NO.

01

104

! D"wt

71

oiqws e. 64
82

00-1

nbs-

21

numbs,
r,
mj otmety !, cm sq
Current Opp', #a n, ,

"Vee

#=

90W, 0 *. is 8
179

o"If

Idid.

an 1 on 1 en I

cunsm Opp,,*a mok

Tinto ovc$
Total coulo-be

Thlelintes urn
plat'r, o rote ul
FD*poot

queWy

I DEPOSIT OUAUTY KEY

VIS"I as"Barnomt
only

00-P

in

to

Nozzle woe crn eq

Viscosity

Reynolds No. 5412

er" eq/80C

0om

otittdii
ootddil
71
71

00

"

24
0
0 0036

Co...

0.041M Career

5
227
0 121 00227
0 22

5
1 25
1 57

a
15
1 ba

249

208

39

004

4
3
11
1
1
0 25 1_2ES 075
1
i 031
0"
1 26
26
31 1 063
123
123 1 GE S 41 45 3

1005

k125
Spot MUMb9f
_
current oonwty Aicm so

71
9
a1
1 7S
2 225
220
251
283
1782

IS63

1388

oolido* 0-19

o"'?

of-, f

-,?

05
94
0382 0452

128
143
0718 0915

142
1025

10
25
3 14
125

11
275
345

13
14
Is
Is
17
11
a
4 1 5M1a
0055 000
1005
502
6 201 17 54 to

12
3
377

11.35

75

1042

COWN 101010 0

Is
161
1 26 1410

don't

Is
1.777

151
19015

on

an

825
oo

TO
39

52
0-

0-

182 1
2592

9 f:

8
1

-1 .

on
1

In
1

an

on
1

1-

on
an I. on

"a
no

it - wnooth A bnght d- wmath & dull

ob - men%-bnghtn- slight mdulabcm
an - severe nodulabon no - slight needle growth
*no - severe needle growth )c - 191core dendnt*
er - cracks md- no visible deposit

TABLE

200

Is
057
o0ddid*

AR

I
nd

Is

11

SAMPLE NO.

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER

ELECTROLYTE

AuD

Tamp*

40 C

Nozzle

15

sty md"

16
4

Spot number

075
05
1 1 25
025
031 ES3_ 094
1 20 1 5Z.
123 .62 5 41 45 31 25 249
omal, OM,011omaa omlPf om, *
72
0
47
93
11
0 0018 0 113 0 23 0 373
Z
Z
Z

Dopoestquality

004

13

Cument density A/cm aq

Current soptiod mA
Time epcii
Total couiombo
Thickne" um
[ lah. g &to U,

0.041M C411rale

Nozzle size cm

11111

PH

we

15
1 88
20 8
-1,
TOM
03
0 49S
E

1 75
220
17 82
am"
- Tr1 -2
0 029
Z

Awl 0

T".:

40 C

as

VOco:

ty Cm Sq/98C

Diiistoot Qua"

11

13

12

2 225
275
25
251
283 3 14 345
15 63 13 as 125 11 35
ot-, a om" aI129
14 7 148
176
0 825 1 061 1 168 1551
E

0 11
d

is

17

0.041M Cities*

fly in/@*

Nozzle art em

"d

16

Nozzle ve

01 0 021

Is

14

3
5
4
a
a
3 77
502
754 1005
628
52
1042 78
025
39
am, 11 amiss 00W,G 00"'. am"
184
lea
164
1574 21538 2624

Is

004

Nozzle area Cris84

0001"

Viscouslyem lics/96c.

as

0 ODrM

0 21_4_ 0357
a

0 457
8

0 564
Wall

0 774

1 025

1 232

1 4Z?

R yno4do No. $742

3
2
4
5
1
1
a
9
10
"
12
05
075
025
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175
2 225
25
275 13
063
094 -11 26 157
031
1"
220
251
283 3 14 345
3 77
20 8
82 1503 13 58 12 5 11 35 10 42
123 82 5 41 45 31 25 249
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aa.
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46
67
80
0
13
95 -0mly
104 -0-s,
121
142
154
162
163

platimg rose ulvoc

8110

17
Spot numbes,
Current devty A,/cm 9q
Cumitnt applied mA
Time sects
Total Coulombs
h,cks,v*** um

FleynoldisNo.

ion

ELECTROLYTE

61

pH

area ern aq

10

SAMPLE NO.

Nozzl

19

ia

all

Mal

DATA

13
4
is
is
4
5
a
a
502
628
754 1005
7a
625
52
39
amill 00"24 omill 00"19
182
148
2 0769

1W

am

17

2 366

an

am

1
--

SAMPLE

ELECTROLYTE

Aull

NO.

Tornp.

55 C

Nozzle velocity m/
Nozzle

1111

PH

Spot number
Cumiint density Alcm so
Cumism app,, *a mA
Time space
Total couiombe

11
025
031
123

21
O.L
063
625
A

0-

Th, cksivssswm
Plasma so

01 0 01a

u,

Doposist quai. ty

SAMPLE

nd

NO.

Tamp. .
PH .01

3
0 75
094
4145
a mm
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0145

0.041M

; "

72

Nozzle or"

-".

1.20 cm

Cilrose

Viscosity

51

4
1
1 26
31 25

1 25
157
249

, -ft74

omt*

0237

0381

15
1 88
208

175
220
1? 82

00-6
100
051

1-11
123
069

d_

ob

Aul 2

ELECTROLYTE

55 C

Nozzle velocity miss*

Nozzle szo cm

a1

91
2 R 225
751
283
ll

-.
cm all

CM SQ196C.

10
25

iS 63

1388
418

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125

10

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01.1?
21
1 51S
151S

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to
1 52

14
0898
e,.,

11
275
345
11 35

Current

appiped mA

Time sisace
Total Coulombs
Th,clinsi,se u,, s
Piatimic;rate uisoc
IDepositausil, ty =
I

DEPOSIT QUAUTY KEY

Visual assessirrien1l
only

No.

1363

is
a
754
5 2

16
a

17

- -J

12
3
777
-

13
4
502
76

1042

14
5
628
825

1005
39

on
M

am

0 04 1M Chrove

Nozzle area cm aq

as

11.49

Reynolds

21
3
4
51
a
71
1
a1
1 1 25
15
05 1 075
1 75 1
025
2
1 20
57 188
220
003
094
251
031
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200 17 82 15 63
123 025 4145 31 25 249
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74
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13
0 171 0237 0381 0495 0857 0832
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d
d
d
so
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9
10
11
225
25
275
283
314
345
13 56 12 5 11 35
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1 19

n
a. A

3414

12
1
3
1 3 77
110 42

1
13
14
15
5
4
a
a
502
020
7S4 1005
76
625
52
30
_
0 10 00"
00"19 L=11,

o
n

on
I

am
I

to- ornooth & bnghl d- ornoolh & dull

ob - sami-longht n- slight nodulation
n* - slight needle growth
on - severe nodsilabom
one-severeneedlogowd
le-letCaredendrile
cr - cracks nd - no visible detiosil

TABLE

201

No.

Viscously CM eq/
1

Spot number
Cument clonstv kc,,, 90

Reynolds

17,

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

55 C

Tomw. :

Nozzle velocity m/.

Norr 0 air* er"

al

pH

0.041M Chrele

ELECTROLYTE

Kul 3

SAMPLE NO.

Nozzl area cm aq

:
04
"101

Total Coulomb$

ea

Thickness um
Plating rate u see

0
05
0 0008
no

Quahly

am,?

as
42
0101 0,188 0301

83
0399

94
0539

0?

61
6

53 C

Temp.:

004

Nozzle size cm

Total Couiornbs

0-

. -

55 C

Torrip.

pH

00.11

is

185
183
162
2 84 3 $to 4 IS4

a-

I
,

Reynolds

No.

10241

w
1M

N
13
4
5 02
78

14
5.
6 26
0 25
001"

619

15
IS
a
a
a
7 54 10 05
52
39
00"'9

17

18
I

00-9

76
18 7 17 1
17
2 1923 2 816 3 596 4 385
85

125
13 137
1 1 145 1 315

--

0.041M Citrals

Nozzle velocity riVas

Nozzle are cm

00mi

01
go
117
109
too
03419 0556 0697 0844

ELECTROLYTE

Aul 5

SAMPLE NO.

011

Qq

71
53
0 17 0285
1
I
al

Pal

00"

17

em, q

51
7
a
a1
91
12
10
it
31
1 75
2 225 1 25 275
1 25 1 15
2Si K 263
314
345
377
157
1 88 220
20 8 17 82 15 63 1388
249
13 SO 12 5 11 35 10 42

a-ti

't-i

32
03
0
0 01
0005
005
05 0077

Thickness urn
plat'no at* u1swc
soc

2
4
1
05 1 075
0"
063
126
625 All 45 31 25

1
025
031
123

00-

167
2141

V'scosity cm altsee

13
Spot number
Current density A)Cm
Cm so
Cu", t apphed MA
Time soce

0-

0amit

is
16
6
a
754 1005
52
30

Nozzle area cm eq

15

Nozzle velocity mdsa

at

PH

0.041M Citrate

ELECTROLYTE

14
5
628
625

i - - FPI
=
bn
P
P
E
- . -

ObIA
I

Aul 4

'time

oes-

.......

SAMPLE NO.

13
4
502
78

12
3
377
1042

US
13.3 156
107
0 71 0 772 1008 1 172 1 497
01
071

asso-a

10
"
25
275
3U
345
125 1135

it 1
It

al

so

tion's

kitpowt

Reynolds No. 6827

tiainte

00toes 0

a-

00

%Awo: ty cm sqlaw.

7
51
a
a
a9
2 225
125 1 15
1 75
2 51 293
157
le$
249
20 8 17 82 15
6 " 13 86
633
1563

3
4
21
1
05 1 075
004
083
1 26
02 5 41 45 31 25

1
025
031
IZ3

Spot numbw
Current density A/cm oq
Current appl, *d mA
Time socs

Is

Nozzle area cm eq

1104

Viscosity

a
15
1 88

7
175
_220

61
91
10
2 225
25
251
203 3 14

20 8

17 82

15 63

-,

00m.; oowr

em Weec.

1
:0*-

122M

ON"

_:

lileynoide No.

Spot murnber
Cu"t density A,c- so
Current applied MA
T, ffw socs

Total coulombs

1
- O25
031

05
063

3
075
094

23
123
1

62 5

41 4S

31 25

00mil 10-10 0on't

Ir"

It-,

24 9

54
7173

24

04
0
0
0
0 OB7

Thmkqls
um
platiria rate Ufsec

5
4
11 1 25
1 26 1 57

058

71
0285

84
10
0_404_ 0561

L
I
I

D"wt

nd

It 0
124
0 850 0 992
-9

Aul 6

To

25 C

ELECTROLYTE
Nozzle

fly rrdw

Nozzleare ef"

pH

Spotnumber

C;urr, nt density Alem aq

Current sopowd
T, rne we*
Totefcoulombs

mA

1 26
31 25

251
15 03

10 42

0ams
Dopos

00-41

Plating

60-,

un
?at* u1swe

visual

Assess"W"t
only

Th, cknes*

DEPOSIT OUAUTY KEY

51

075
025
-F3 - 1 - W-94
123 4 45
00:iiot
100

Deposit quality
I

rid

I
I

ZZ

625.

52

39

a. -

133
1 172

14
1 344

168
2 1538

178
2 848

154
2 962

too
4250

am

an

on

am

an
I

is

Nozzleareacm sq
Viscositycm sq/0@c

.2
004

6
325

35

408
Go

440
so

00:019 =WI

11

10

3 75

ReynoldsNo. 651.3

12

1
13
a

425

45

4 711_ 502
83
78.

534
74

565

597

828

so

057

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475

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4
I14
Is
55 16

025

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568

754
521

0 tims

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to

17

as

a is
401

879

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446

E-n.
Z

me
.
I

78

377

10 42

17

14
is
Is
5 a
a
628
7 54 1005

0.29M Carsup

11 35

19
21

13
4
502

ww

-I

SAMPLE NO.

12
-- 3
377

L-

.i

11
0704

12 5

13 8a

Ill
275
345

-a .
en

swic
I

d- ormoth & dwil

s- ornooth & bright
n- sioght nodulabon
ob - sobnqht
ne - slight needle growth
on - severe nodulation
m*odle growth ic - lot Cora dentinte
tine . "vqrs
er - cracks no - no "*, bl* deoes-11

TABLE

202

is
1

Aul I

SAMPLE NO.
Temp. :

0.25M Citrate

ELECTROLYTE

25 C

Nozzle Velocity Was

@I

PH

Nozzle at?@cm

Spot number
Current density A/cm aq
Current applied mA

1
025
031

2
075
004

123

41 45

Const

Depowl

quality

SAMPLE

NO.

31 25

oonol 00"WI
75
024
0

0
4

3.
1
1 26

V'scoory

15 83

o0n`?C 00"I'M
97
156
0 621 1 467

Cm "/vive.

Total Coulomb$
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Nozzle velocity

aI

Nozzle size ern

025
0.31
123

075
094
;1 as

1
1 26
31 25

oo
54

oo57

p &I'Mit rate u

13

0 182
to

11

425
534

45
4
5
855
565
So
69

78

00,
2`1 7
2614

0-19
2173
.

74
0-

00""'
00-

121
13
14
475
55
507 -5 625 -691

15
a
754

is
17
65
7
a is
Is41 879

657

521

48I
481

I. nrN

o'nol
0
'nilt,

on*/

on i
arel

625

onoo

558

Conn

no

one

010
04

Reynolds

0001

%necooty cm actlese.

25 C

1a

2 13
2 51 13 77
15 63

3 25
35
4 06 440
96
so
10 42

Conn
117
0 749

00"
141
1 353

are

00",

going
ZI

no

91

375

otin't

10

4
502
78

4 71
63
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12

13

4 75
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028

14
15
55 1
a1
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a 25

568

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Conn

45
555
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025
031

075
094

lZj

4`145
IInC6
54

C0".
83

h. ckness u
Plating rate u/sac
Deposit

0 13

0266

00"

I'M.

Temp.

pH

so

Total Coulombs
Tfilckreal
uill

40 C

01"
14 7
094

i0tima felt

N rz

al

5
3
3771
1042

a
7
325
_35
408
440
98
so

C-

-1CM11

Wo

We

an.

1
7.1
0

we

375
4 71
83

eynoldsNe.

Depowt

quality

DEPOSIT QUAUTY KEY

visual assess"Wnt
only

nd

oonl? '

0171

Conn
- 98
0314

Sul

1
101

4 1 425
S02 1 534
78 174

11

12

45
585
69

13

14
55

5
828
825

475
Sol
057

Conn

Conn

one

riliss

size Cm

004

DO. "
172
11

Conn
as
1 $04

Can'.
204
2 125

35
440
so
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2 326

4 Ala

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568

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is

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a
754

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879

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461

446

is

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0.26M Citraie

5
21
3
4
1
31 325
2
075 1
1
025
377
408
1 26 251
031
094
90
123 4145 31 25 1563 1042

u1sec

879

1w*11c l

hl: zz: velocity

o0w,

Is

01229

It

a
375
4 71
8L

Nozzle or*& Cm Sol

: 00121

NAscowly Cm sti/sec

009"

Spot number
Current dqAW!X
Current acipi,ed
Time sacs

00m,

17
7

4
*1
orle
-a
-1
1

004

ELECTROLYTE

Au2O

NO.

a is
4 at

521

Nozzle area cm eq

nVas

31

- 7n e

quahty

SAMPLE

Is
85

i -0 i -0
0.25M Citraw

4
2
11
1 20 1 251
31 25 is 83

-1

3258

N zz: velocity
Nozz

90

No.

"a

1
Current do's-WAICMI
current app"ed
fA
Tim@ secs
Total Co. iombs

446

35

Nozzle area cm eq

ELECTROLYTE

pH

Spot number

is

0.211M Citrow

mise

ObIns

Aul 9

Temp.

83

10

1N

1
9

Qualfty

SAMPLE NO.

00"C's 1-11
182
18,
1 677 2 045

1_O

1=

! Depolut

oo-

a@

ELECTROLYTE

15
Spot number
Current demo? y Adem 9q
Current sop,, ed mA
Time sacs

9
a
3.75 1 4
02
5.02
471

'I
35
440

an.

25 C

PH

"

10 42

Reynolds No. 1625

a/n*

Aull

Temp.

5
a
3 325
377
408

4
2
251

I
00012"
'"

Nozzle area cm aq

Ime sect
Well Coulomb$
hrckness um
Plating rate U/sm

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

Reynolds

k
9
1
4
4
502
50 2
7a
7a

10
4 25
534
74

oonin 0-9
C. M..
21 8
245
225
2 627 3 141 3 041
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1
nj
nine
n

11
45
585
69

K
12
475
475
So
597?
5
85
857
as

13
14
5 55
ON- 691
$68
625

"... 0 'o249
2277
3"
3455

Conn
255

Is
6
a
754
51
52
521

Coft.

am

Is
as
816
4 at

00"
Conn

00.21

00"',

PC

IC

t
on

snln*

Ic

6- wnoolh & bright d- Smooth & dull

Sir - som-brighl n- slight nodulation
on -severe nodulabOn fie - elightne"14o growth
she . severe needle growth jc - lei core dendmie
er - cracks nd - no visible, dooosit

TABLE

203

17
7
879
440

408
I

No. 887.6

18

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

SAMPLE NO.

ELECTROLYTE

Au21

0.20M Citrate
1

Temp. :
pH

40 C

Nozzle velocity m/se

Nozzle *z* cm

$I

0,

area

VOco:

ty em

10
Spot number
Current density A/cm so
Cumerlt sophed mA
Time set: s
Total Coulomb*
Thickness urn

2
075
0 04

1
025
031
123

3
1
1 26
31 25

41 45

flow?

oonas
a1

00"A
83

5
4
2 K
3
2 51 377
15 03

a
325
4 08

42
1042
10

ao"
155

10"IN
jonn
Is
II 1
1
Is

8
-9
00"Vil
18 7

7
35
4 40

a
375
4 71

so

Nozzl

cm

IC3190C

!Deooo.t quai ty

SAMPLE NO.

Ik

4
5 02

10
425
S 34

11
45
5 65

83

78

74

so

0010TI 0T 89
183 - -AQ

con's
194

all-

10nM

Temp.
pH

40 C

Nozzle velocity

61

12
475
5 97

13
5
6 28

is
is
55
5
6 911 7 54

057

825

568

521

481

446

30

con2l)

oonn

CoM4

oo"M

Dom,

0 om,
00m,

Ion's

on/nd

---

Current constry A/cm so

Current aor-d -A
Time secs
f6talcoulombs
Thickness un,
imsting
Pi I, raTo
rate us sec,

no

004

Tomp.
%)H

Spot numoor
C,,ri,enj oon$.ty A C- So
-,, ent soooeo MA
T"to
Total coulombs
Th-'ess
.,, 11
plalino rate u1sec

to C

Viscosity

Nozzto size cm

181
0 04

Temp.

55 C

DH

61

Nozzl: area cm sa

Vaco lycmea/soc

14
55
691
Sao

is
is
15
Is
6
15 as
5
a Is
7 54
521
51
481
on"
11.11
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17
is
7
a
8 70 IC 05 1
39 1,
4 46

0-1.

11-1

E F -

snime

no

sn*

Reynolds No. 7308

124

10
11
12
13
14
is
4 25
45
4-, 5
5
55
9
S34
565
7 54
S97 r
528
Sol
74 -6 i- -6-S-7-r- a 25 5 8-8 5 21
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10 CS 1

2 149
It

One

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one

sie

ants

sne

Will

11,1

0 28M Caraie

Nozzle velocity m, "

Nozzle a.: * cm

4W

it'"s

14011,01,

ELECTROLYTE

Reynolds No

00072

-no

2
3
41
5
7
6
11
a
91
1
075
3 25
1
35
375
025
4
0 9A 1 26 25,
377 4 08 A 40
031
4 71 502
9a
89
83
78
123 41 45 31 25 1563 11042
! - --I
- . I -. In . -I
t--V
It14
-- 41
as
157
155
155
161
154
0 896 11 507 1015 1742
0 0099 0
104 2 103

Au24

I.

::

0.28M Carate

09powfous"

SAMPLE NO.

on.,
an*,

cm @a/sec

-; -fne

so"
som

NozZio velocity miss

at

0,911c,

M
7
a
aI
111 10
11
12
13
13
35
3 75
3 25
41 425
5
45
4754 1
47
71_ 502
534
440
4 71
565
408
59 7
597
628
7a
go
89
83
74
69
a 57
057
625
0 11"'1
Vnn
....
- In. in
onn 00"19 oenooo o1noo C.
I_ 162
167 is?
17 175
Is I
2012 2 170 236S 2333
1 687 1 $76 2012

ELECTROLYTE

Au23

SAMPLE NO.

one

Nozzle area cm oq

10

Nozzle are Cm

0.25MCitram

/me

2
3
5
4
-1
075
025
1 Z 2
3
031
094
1 26 2511 377
5563 1042
123 4145 31 25 1563
irW2
0 030 0""
-InN
Inn ....
73
49
14 7 159
094
520
0
520
0 0 118 0234
94 111526
04

17
is
7
a
$792 1005

20

Spot numb*f

IS
05
6

ELECTROLYTE

Au22

tiorn

737 1W
0 0 147 0 266 0 992 1
2 054 2 777 i 48-7 T703
1737
!= :

no
*D
"
am
on
sm an
I
f
II
f

Wing 810 wc

Reynolds No. 2160

: -ze

oq

2
0 04

Nozzl area cm so

Reynolds No

1045

is
is
a
as
7 54 5 is
521
2 1 481
i1o"M
onn oo"P,
on.

17
7
11
8 79 110CS I
4 46 139

V,Oco: tv cm sa'soc
#

Spot mumber
A,cm on
Current con"
Current aDDItedmA
Tirne sees
Total coulomt's
Th ck, ess urn
jPlating rate u sec
Gus,-tv

71
2
3
5
a
a
1
a
1 0 2 10 75
2
3 3 25
35
3 7L
1
3 77 408
4 40 4 71
094
1 20 251
031
e9
98
! 3_
4145
145 31 25 1563 1042
123 45
_
C1.11, 'Inn
InIS io"r
76
203
14 2 189
19 7 206
49
0 Ila
0"
118 0 243 0909 1814 2052 2 15 2446

DEPOSIT QUAUTY KEY

v, susi assessment
omly

Is
is

9
10
11
12
4 425
45
4 75
502
534
565
So
7a
74
9 657
io"It
oon44 DnII I In"
214
206
202
27 44 2764
28
_
On

wonsi sr%,
n*
c
Ic
1
1

13
s

It
55
691
Go
5 25 55,
515
581
I Inn or"'.
on,

sn'sne
snoen.
1

c
1

a- smooth & bright d- wrooth & civil

so - gernt-bngnt n- wight nociviscon
on - Severe nodulation me- slight "*@CIOgroWth
growtM IC - ?at core Conant*
Ong. evere
et . cracol md - me vivoie cooosit

TABLE

204

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER

Au2 5

SAMPLE NO.

ELECTROLYTII

55 C

Temp. .
pH .aI

Spot mumber
cu"ent de8. noA cm oq
Cu"M

opphod

Tn'*

MA

c,

Total coulombs
Th. ckeas um
plotong rate U'soc

00.

nd

55 C

Nozzle velocity

pH .

61

Nozzle size cm

2
075

T V

29
007

um

rate womic

Depostt cuaittv

i"A

-0

w748 1

12

13

0
4

10 4511 4 75

4 25
534

502
78

on't

's

74

00"19

10

.011

DM#

OM.

o"m

wMe

on

000121

000788 1

12

13
5
628
625

area crn eq

375

440

471

Ton,

I? "

10 45II

4 75

565

597

425
534

502

74

go 89 63 78

2 -"It

17

5*,,

OMP

: T. I.

IC je

10.10

Imo

18

so

7
17 7
12269 2527 2609

is

657
o

,192

-0194

2922

3 104

RoynoldsNo

14

0"12

IC

5.224

L-IL is

55
591 LL54
521

sea

,:.

SI,

9.

17 la

es
a4
81

8 79
446

loos
39

9-0

le

Je

0.26M Carsto

Nazzie votocity Pnim

is

Nortie

004

iwze cm

15

Is
18
5
55
a
es
a
754
628
679
691
a
16 446 1005
481
825
568
521
39

on

viecoi. ty cm le/c

I
35

408

ELECTROLYTE

55 CI

14

em w

Noule

004

a
3 25

1042
fl

567
657

Reynoids No. 2612

00012S

0.28M Citrate
.

3 77

t-

es

so w

Au27

Tomo -

4 71

17 1
158
173
ss
108 516 781 iz_,
933 1084
176
0 05911 1 1

nd

SAMPLE NO.

O..

5
3

-4s-

t . -)

Viwoe, ty cm sa,

a
375

440

5
83
98 so
so
I223 0
00- 0 00"" 0 ,
168
la1 [L3jgL
1872595
19 2739
ISO2007
191 3195
75 2506
12
1
I'll,

mtso

04
26 251
031
31 25 IS83
123 ILI

Total couiomos

408

Nozzle area crn sq

Temp. .

A cm so

I
35

a
325

ELECTROLYTE

I
025

004

ob

Au2d

C. rwt
appimA
T,, ',
ecs

Plating

cm

038 10o
4 0
154
53
11
478
092 0202 0729
0
1

number

Th, ckess

SAMPLE NO.

Spot
Current o9miury

Nozzte gre

D*povt 0.61'ry

.5

4
2
02,
075
3
004
26 251
377
031
123 41 45 13125 1563 1042

0 25M Citrato

Nozzle velocity miss,

ll

DATA

Nome

aroa crn sq

VISCOWTVem go, we

Roynolds No

000126

; 404

"

.0w?

III113
4

mubo,
-d,
A emi "stv
,cu-"qm ODO1,00 A

Spot

so

F--"c

9
Totai coulomos

10
10

25 10 75
31 10 94 11 26
123 14, AS 131 25
... "A
1 61
48
039 10 154

.. -,!

-"I

rT-h,
emmegs um

0 10

plotima rate u sec

Id

DeDowt Q. S"N

1a

11

T*mo DH -

251
1563

a
3 25

3 77
1042

T-

fl

14 9
43

10
0653

4 08

4 71

4 25
534
74

502
7a

45

ses
69
I
0-3
17
,
168

12
4 75
S97

$57

227

2507

17 0

2725

Nazz

14 1

13

orlp cml

is

5 55 754
1
6 691
15
568
21

25
625
" nfl

-1.1

118 81

153

'a '? 110 is

es [--879-[10
a 7i
085
05 i
8le

- ..

18 2
le 3
3 31 13 493 13 805

2928
tm

i
i
i
S"
S,
-i"

0 27M Phosphaw

NoZz: velocity mise

71

9
4

9a a9T783
TI- 17 4 176
la ISO2096 2 256
667
1 1899

ELECTROLYTE

25 C

440

3 75

I"

so

Au2I

SAMPLE NO.

7
5

2
.

: 00124:
i
coolill

Nozzle area cm go

00

Viscolviv

cl" 90'wc

Reynolds 140 1732

I
N
Spot muber
A cm so
Curntni cerivy
Curnp,? spol, ed mA
Tmw secs
Total co. lovs
Th, cKmess wM
Plating rate U'vec

1
025
0 31
123
oW2
No mic

075
094

1 25
41 45 131 25

3
3 77

251
1563

1042

325

3S

406
06

440
89

11"

3 75
4 71
93
-9

4
502
78
ton'*

10

- 425

534
74
I o1w

II

12

- 45 , 4 75
565
69
. 0-

5 97
0 57
to""

13

14

is
a
a

5
55 .
6 28 , so,
754
a 25
568
5 21
0"

is

17

as

04
4 at

5 79
4 48

o..

i
Depost

cual-tv

DEPOSIT QUALITY KEY

no

9 so

s- smooth

& bnght

sb - wrr4-bnght

visual seseswriont
oniv

sn*

d- w"ooth

?II

IC

lit

& dull

n- slight noculaton

an - severe nodulation no - Slight nfealf growth

She . Savors miggictsgrowth Ic - !WlCore concinto
offies'l
Cf - Cracks no - .0 111010

TABLE

205

Is
ai
1005
39

1
1

11

SAMPLE NO.

Au29

Temp. al

25 C

pH

71

Total Coulombs

Nozzle

-3

51

is

Nozzle area cm eq
Viscowry cm sq/

size cm

Reynolds No. 2183

0-

16
7
35
440
so

325
408
go

."

. 0-9

a1
9
3 75
4
4 71 502
87
7-8

0-

- =!.

10
425
534
74

06"it

It

12

13

14

15

is

17

eolllliti

No th,c

no

quality_

SAMPLE

0.27M Phosphate

Nozzle velocity mise

so-?

Thickness um
Wing rat uioac
Deposit

ELECTROLYTE

9
1
2
3
4
2
025
05
1
3
063
031
1 26 251
377
123 4145 31 25 1563 1042

Spot number
Current bill
Aicm so
Current sopised mA
Time sacs

PURE GOLD DEPOSITED SPOTS. PLATING PARAMET

NO.

aII I anIw/cr
l
-W=I.
ELECTROLYTE

Au3O

25 C

Temp..

Nozzle w1ocity

71

PH

Nozzle

13

miss

are cm

Current clerialry A/cm sq

025

Curremi appited
Time sece

031

mA

Total coulombs
h, ckness um
Plaiing rate w9ec

10

Nozzle area cm aq

OlDtfs

.0

04

Viscosity

00,181

cm go Igoe

1
5

05 11

12

71

91

3 25 1 351 3 75

0 e3 f1 26 1 261
41 45 131 25 11563
1"..

123

141

Spot number

0.27M Phosphate

377

4 08
96

1042
Otis"

V-lr

onlef

S. 17

4 40
89

1
11

12

1-

502

$34

78

74

No.

4350

I
is

13

is

is

is

41 4 25

4 71
e3

ew-v

10

Reynolds

I'M$

No th. c
#a

DeDowl

:=

'a

quailtv

silsn,
cr
SAMPLE

NO.

ELECTROLYTE

Au3I

25 C

Temp.

Nozzle velocity

71

pH -

0 Z? M phosprists,

m/se

is

Nozzle size em

Nozzle area cm aq

004

Viscosity

19
number
Currant oertsin,
Cur, e, t ii
Time WCS
Total couiomos
Thickness um

Spot

Plating

025
031

A cm 90
-A

123

3 1A

21

OS 1
1
063 1 1 26
41 as 131 25

2SI
IS63

Reynolds

: 001":

cm sq'see

No

7S56

11

R*yno, d$No.

'101

1
to
4 25
534
74

4
502
78

.2

I1
45
565

is

14

is

No m, c

rate u sec
E

7e-0,
cost

51
a
18
3
3 25 -7 35
3 75
T -7-7 - 7 -08 - 7
40
4 71
1042 - 9 6 - eq
8-3

11

OU

vH

Spot number
Cumem aeriviv A cm so
Current sow, eo mA
Time sect
Total coulombs
Th, ckmess um

JPl8l.r,Q late u, wc

I-

o
66

Nazz

air* cm

-0.01
`10 2

we

!=

ic

0.27M Phosphate

NCzZ:: velocity m/lit,

1119

2
3
075
025
1
-03 - 1 I rg -4 - T -26 - 2 5 1 - T -77
7745
31 25 1563
1042
123

We

ELECTROLYTE

40 C

Temp. x,

Au32

SAMPLE NO.

no

11tv

0 1".
186

n -"

21
004

Viscosity cm so, wee

71

325

35
4 OF 74 - 0
go ' - 8 9
i0itill

Nozzle area cm so

10

it

12

3 75
4 71

4 25
SS4
74

as
565

4 75
597
657

63

C. "

00

I-

502
78
5",

so

, 03s"o 0 Q-ti

C-

13
1
a 25
- t-

14

Is

6 5
691

6
7 54

566

5 21

1
i

! "A

0 0 159 0 326 1 1 19

D#=Coos-l
Quality

so"

me

We

C
I

DEPOSIT QUALITY KEY

Visual osesrneni
onlv

s. 9mooth&bnghI
sb - wnw. bnght

id-wTooth&dYll
n- might noduisticin

in. veremodulabon
no-aiighinciegrowin
en@ - vort
mcie gromm Je - let core Clenerite
er - elecks d - "0 es, elt cleoost

TABLE

206

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DAT

SAMPLE NO.

ELECTROLYTE

AuU

Temp. -

40 C

pH .

7.1

0.27M Phoshate

Nozzle velocity miss

51

Nozzle size em

Nozzleareacm

00,

Reynolds No. 2002

Mwos,

13
Spot number
Current density A/cm so
Current applied mA
Time socc
Total coulombs
Thickness um
Plating

5
71
2
4
a
a1
9
1
10
11
2
3 325
025
075
1
351 375
4 425
45
31 094
3 77 408
440 4 71 702 - 534
1 26 251
585
_O 1123 41 45 31 25 1563 1042
06
89
83
78
74
60
00u001,00
Dii"OUPil 0"19 . -1
06
cGlOll 00M0 00le0l
5
84
164
20

rate Wairc

Dirposit quality

0 269

pH .

'a ine

Is

17

Como

n/n*

snin*

is

Nozzle or* cm

Nozzle or"

004

viscowly cm so 2"

Reynolds No.

:, '"I

cm eq

Ooom

13
Spot number
Current density
Current applied
Time sacs
Total coulombs

Alcm so
mA

025
031
123
eami

Thickness

um
rate u/sec

Plating

075

11
094 11 26
41 45 131 25
00,rioeii1"..
77
46
0 111
a

no

SAMPLE NO.

0 246

40 C

Total couiomtev
Thick, @" um
Plating rare u/saic

N
N

3
--377

3 25
_408

10 42

98

cemit . 0-9
174
Is
1 a7
1 024
e
LMOMS
sirim

*v aloe"ty

21
3
0 75 1
1
094 1 1 26

1
0 25
031
00-a

Ozzie or*

123

ELECTROLYTE

pH .7

A/cm eq
IM-52%ty
Currant applied mA
Time sacs

Au33

Tomp.

4
251
15 63

41 45 131 25
100mil
00
3
431
0 104 0234

cm

1
a1

-? 35

37S

4
502
71

4 71
83

440
89
otui, "

snino

91

00-

'

wine

0-0

Vin-e

10

11

12

13

425
534

45
565

4 75
597

5
628

74

so

657

625

..

00, roe .. we

14

Is

17

is

-1

us,.

SAMPLE

mlaa

iS 63

042
10
42 1

cow,
151
10 11

, 0766
17

T-77

1 569
1669

1 813

Is

091
568

0 0

0-em.

:=F
,ne
w-,.

Nozzle
area
cm
qq

004

V'scilely

Reynolds
No.IOWA

Closer

cm gal

1
71
6
35 1 375
440
4 ?1

96

so

9
4
502

10
425
534

I'l
45
565

78

74

at

83 *

"""

'*

"""'

12
4 75
597

13
5
628

14
55
Sol

is
17
is
is
7
a 1 65
1
754
a is , 879 1-0

$57

625

568

521

481

440

39

elm.

00ml!

10.21

2em,

on-tl

"me

Temp. .
pH .

55 C

N zzle velocity

71

Nozzle size cm

onsier

W*, c, iw*ecfl

wir

eno

tlno

$no

, ; 7*

one

0.27M Phosphate

21

"v"

Nozzle it, "

004

v1scosayernia;

Reynolds

000543

cm aq

No.

1474

see

191
Spot number
Current density A/cm ;7
Current applied mill,
Time secs

3
4
5
2
2
3
1
0 25 0 75
377
094
1 25 251
031
123 Ali 4S 31 25 1563 1042

Total coulombs
Thickness um

P =a
109posit

ae
52

0 3

rate weac
Quality

I DEPOSIT OUAUTY KEY

Vtsu&l assessment
only

no

coml
81

0 259

149
0 03
So

a
325
; 08
96

'Qm11 00W.
20
205
1 919 2 135
n

1
I

ELECTROLYTE

AU36

NO.

0.27M Phosphate

51
4
a
2 1
31 325
251
3 771 408

Is

55

f
no

Is

0.27M Phosphate

Nozzle ireloocity"Viss
71

15

ZZI I I

ELECTROLYTE

Temp. -0C

14

E EI
l

Au34

13

1 919

1040

- 9

no

SAMPLE NO.

0 121

12
475
597
SS7

7
35
440
89

a
375 14
4 71 502
78
om, f .03
aeaq

an

10
4 25
534
74
00

7/n;

11
45
565
so
0.

+qnin*

12
475
597

13
5
628

_057
0 0"M

jqnwlc

14
55
091
568

15

Is

_625
004iir?
'I 00m.

1
sneepc

PC

9- smooth III,bnght d- ovicath & dull

ob - *env-bnghl n- slight nodulaticm
no - slight noodle growth
on - severe nodulation
one - severe noodle growth 1c - lot core dandme
cr - cracks md - no visible deposit

TABLE

207

10

17

is

SAMPLE NO.

A07

70".

55 C

PH .

71

Nozzle

I-Ity"Ves

0-

31
OW5
id

rate uoties:
i

Deposit quality

SAMPLE NO.

PH .

124

Is 8

16 4

0 202

0 703

1 812

1 017

hickritses um
Rating fam u1see
Deposit

om's

111
12
45
475
505
507
69
057

is

2 301 ' 748-2

2 Oil

n1

0.27M Phosphate
10

as

17

15

251
Is 63

34

58

0082

0166

3
377

12
0768

1a
1 375
4 71
83

10 42

325.
408
of

440
"

00"
150
1 497

""If
Is$
1 729

-11,
179
2 Oil

. M?

2_182
193

wn

'0=

omit

nq

...

"
is
2 -308

10

Reynolds No. 7372

:, sts'.
005.0

10

isis

10

11

41 425
502 1 534
761
74

QsMe

161
17
is
71
65
8
a is
870 11005
39
481
448

0M.

1
91

35

one

%siscosity,
cm sqfwc.

a
2

15
6
754
621

Nozzle area ent eq

004

14
55
Sol
568

2 649

n
I

13
5
025
025

oix,,m,

Is r , 719-2 19 8

110

ELECTROLYTE

11
11 26
41 45 31 25

a. -

10
4 25
S34
74

502
78

14

075
094

123

1 Qss

02S
031

a
375
47,
L3

Nozzle size cm

*",

Be

13
Current dentistry A/cm so
Current appt, od mA
Time sects
Total coulombs

0"19

Nozzle trelocity m/se

71

Spot number

ii

7
35
440
89

a
325
408
96

63

Id
I

MC

cm 9qf*ke

15

ss

Au3I

T"..

vlwo"

04

Reynolds No. 3686

OOD543

"d
I

Nozzle area cm aq

:5

Nozzle size cm

h,ckn*ss um
Plating

1
3
2
025
075
2
3
1
031 094
1 20 251
377
123 4145 3125 1563 1042

Total coulombs

0.27M Phossilphate

ELECTROLYTE

14
Spot numbw
Current density AJcm 9q
Current applied mA
Timessece

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

45
56S
80
0-

12
475
597
657
0-

13
5

14
1 55

is

85
a1
754 1 a Is
521 1 481

i 01
Sea

628
625
0

15

00303"1 iiiin"

0 "J"

17
7
879-

I
is
6

446

1005
39

00m,

10"It

quai, ry

no

19

Ea

"

an*

Ic

sea ss
aissis
s
si ssessi

SAMPLE NO.

ELECTROLYTE

Au3fi

Tamp. -

55 C

Nozzle "

styIwee

0.27M Phosphate
.

Nozzle area cm aq

is

Nozzle size cm

pH sis

Reynolds No.

1,019cosity
cm sq/

13me

000543

I
SM

"u
Alcm

025
031
123

Current so ited mA
Torne sece
Total cou, ombs

075
094
41 45

51

2
3
1
251
77
1 28
31 25 1563 _3
1042

0
325
408
96

OW's 10 A OWW" 00
01.11
17
44
It 3
is
is I
0041
0141
0723
1 4a- 1677

Thickness um
Plating rate u1sec
Deposit

21

00"',
00
Is 1
185
2034
2229

--

Temp.
PH

Spot number
Current

density

AJcm so

Current applied mA
Time secs

40

Nozzle ve

7.1.1

Norzfe sire ern

1
025
031

DEPOSIT OUAUTY KEY

ameasernent
only

0I-P

4
025
031

123

123

02-2
iss, ". -1
-

25
_M

60

9
-

a 0"',
1170
2205
VII

51

00183
2473

45
565
as
-

13

4 75
597

5
6 2a
025

its?

18 2
2638

I Q
187
2 846_

I. -lleg
3024

wn

It

14
SS
091
56S
0-1.

q?

Is

7
a Is , $79
481
446

a
1005
39

Is

is

6
7 54
5 21

65

M
11-1

em'.
I

"/00

n.

we

Sample to *value%* the srifluence

of dissolved

Oxygen

a1

as

.1-01.

Reynolds

No.

7372

Is

Is

i?

Issiscosity em, eq/0$c

91

10

11

12

13

14

00-2

55

d- w7ooth & dull

0- ornooth & bnghl
n- vilight nodulation
ob - serni-bnght
no -slight needle growth
on. severe modulsbon
SMO- severe "@Odle growth IC - PI Core dendnts
Cr - CT&CkS rid - no visible dtitioul

TABLE

208

10m,

Nozzle area crn aq

-

425
534
74

12

1-

010
04

---

11

10

wn

0.27M Phosphate

sty fill"

21
3
025 1 025
031
03
0311
123

123

sailcouicimbe
h.ckneas urn
plating rate u1sec,
6-M
urge time mine
Quallty

lAwal

ELECTROLYTE

Aw 40

NO.

91

375 1
4
4 ?1
502
83
78

3S
440
so

SAMPLE

a1

no

quality

11

Is

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

SAMPLE NO.

Aw4l

Tomp. -

40

PH .

7.1

ELECTROLYTE
1

Velocity nVolic

Total coulombs

60-s?

Thickness um
Plating rate uivok:

0mall

0
d

lot Qu

SAMPLE NO.

Temp.

55

Velocity

an

Cuff"t
C
had ,A
mA
LaIaapplied
; .1
c
Im*
IL
'a INICS
Total coulombs
Thickne se u
m
um

00

Do-

Plat'n
P1

35
440
89

375
471
83

0=11

00"

to

4
502
78
*=I'

0,

161

45
565
69

OM60

0aaaa

QsX*0

=a

no

IS
15
13
Is
14
5
55
020 Sol 00. DO 000
025 568

325
408
96

000

000

an.

nitrogen 40 mine
Reynolds No. 13259

0.00i"

cm sq)

81
$1
10
375
41 425
4711 502 1 534
83
78 1 74
0031WO00.10

Is

=I

1
7
35
440
- 89

17

-1

Semple do-swaraledvft

Viscosity

00,01H, am, $ a*"'#

Reynolds No. 5805

00(wai) atia"a"

Nozzie are@ cm sq

004

121
475
597
057

425
534
74

0
no

it

14

a-

role u
Usarc
U,see
ac
sling role

.1

1
2
5
4
025
075
2
1
3
377
031
094
1 20 251
123 4145 3125 1583 1042

A/cm sq
A/c?

.0

0.27M Phosphate

West:

13

Spot
S
r I number
density
C
Current
Z nt d*mw

linscositycitisq/voc.

in

Nozzle size cm

04

ELECTROLYTE

7.1

PH is

0
an

Au42

tool"

00"000 O-MPq am, *

19

025 075 11
2
3 1 325
031 094 1.26 251 3.77 408
123 41 45 31.25 1563 1042 as

CumontdensityA/cm sq
CurrentappliedmA
Timeask:9

Do

Nozzle W" cm aq

1a

'4

Semple dol4worsiledwith nitrogen 40 nine

10

:S

Nozzle size cm
13

Spot number

0-27M Phosphate

omilo

11
45
565
69
a-

1
121
475
597
857

a. -

13
5
026
625

Is
15
a1 05
754 1 610
Is
IS
521
at
481

14
55
Sol
568

Co..

*a-.

a.a-?
-?

10

Olin'.

11-1

wine

*me

17
is
7
a
879 1005
39
446

#
d

Deposit qual-tv

an

Aw43

SAMPLE NO.
Temp..

40

ELECTROLYTE
I

pH

0.27M Phosphate

Sample do-owraled with nitrogen 40 none

Velocity Wdowic

181

Nozzle or"

Nozzle size cm

04

Mocovity

Reynolds No. 104"

em aq

cm sq/mc

Spot Muni

09MINty Aicm 94
applied MA
Time soce
Current
Current

Thickness
st'no

fate

025

075

031
123

094
41 45

1
1 20
31 25

1563

IM"S

. 07M

a. "

90AW4

Total coulombs

4
2
251

3
377
1042

7
35

3S
408
98

a-

8
375
4 71

440
89

9
4
S02
78

"

0-11

om

0-19

10
425
534
74
ImsO

It

12
45 , 4 75
SOS
597
, 657
.
"
003sat)

u1sec

Deposit lZu i1tv

Temp.

me

me

me

Nozzle

PH

00,1WHI

0MV4

one

ans,

is
is
a 1 65
754
a is

17
7
$79

521

481

446

01.21

00.21

emIrl

t /Cm liq

.
mA
app,, ea

T.rne wee
Total coulombs
Thickness um
rate wome

21
075 1J

3
4
2
1
094 1 1M
1 26
031
26 251
IZ3 41451 3125 I563
00
00301400"M ..
74
0
02
151
03
0 0024 0 179 0
0 2914
20,4 0 964
1
025

0 04

51
6
3 325

Viscosity

7
35 1 375

1-10

onsic snoll: sne, ic sne'll:

-aam
--

cm aq

Reynolds No. 5605

cm sq/90C

11

13
11
12
13
t
5
45
475 15
408
440 1 471
534
565
597
62 a
628
565
0
25
go
89
1042
83
so
19
11, ' 057
025
otaiiiil
*
..., # em, fl easke 0"'s
omea 0moti 0
eiriviqi
1
19
1 823
0
01
0
0
0
0
0
0
0
0

10
425

1
4
14
is
5
55
a
Sol k 75 4
568
568
52,
521
0
0""
00

am"
a"
0

0
0

is
So

quality
-.

I DEPOSIT OUAUTY KEY

visual assessment
only

70 - `71 =-'c'
1

-#In.

n".
win*

"n.
anins

no0,
n

w
nw

ale

8 79 110 05

481
cam,

39
448
otoqri, am, *

no,
"a,

1
.

A dull
d- mooth
9- wnooth A beqhl
ob - serri. bnght n- lilight nodulation

on - severe nodulabom no - slight needle growth

one - 9*v*ro noodle growth )c - lot core Clendrils
cr, - crocks md - no viable docioat

TABLE

209

17
is
7 1a

0
1

--

line

1
9
4
502
50 2
78
7

!
Depolpt

is
a
1005
39

Semple,dor-asiread with nitrogen 40 mins

1
Spot number
Current don E

$no

w,*

Nozzle or"

101

2.2s, cm

1-

0.27M Phosphate

Velocity Rveac

40

0
1

ELECTROLYTE

Au44e

SAMPLE NO.

plating

14
55
691
568

um

1i

Current

OMM,

13
5
628
625

12

0
21

AU44b

SAMPLE NO.

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

TeW.

ELECTROLYTE
ViRkpovyWave

10
71

pH

0.27M Phosphels,

Nozzle area em aq

101
0 04

Nozzle lure em

Sample sereled for 40 mms

: -0OM
'"

Reynolds No. 5805

Viscosity cm sqlasc

Spot numbeir
Current density A/cm sq
Current applied mA
Time sacs
Totalcoulombe
'Thickness um

1
025
031

2
075
094

3
1
1 26

123

41 45
414
4145

31 25

ca'sa?
-

5
3
377

0
325
408

7
35
440

10 42

go

89

00"Pall
lisReas00"'I'V5 "Cul0a etrlaaf
52
a1
15S
179

1"19

4
2
251
15 83

0.125
0
125 0259 0092
F = =T

plabrog rate

Temp.
pH Is

WRIR .

ELECTROLYTE

40

Vl.,

71

Nozzle are cm

am"

T =

10
425
534

11
45
585

74

09

0. VM Phosphate

Y N.

Is

[an
-I..

Viscosity

025 1= 05
05 1
1 1.25
0625
25 3 125
1 25

Temp.

40

pH

71

T
225
5 S625 , - 7 5

0.27M Phosphate

3
377
05

Current denetv A/Cm 90

Gmil. tappi, edmA
Time Race
Total coulombs

am. "

Thickness um

08

wma

-2

Velocity missic

IS

Nozzle are em

004

521

481

44e

36

cow?

etrier.

0IMe'll
lua, q

15 1 33

4
3
377
4
n ....

as

a
3
3 77

3
3 77
a

....

1`-,

127
I

rate ulooc

$Mai
on
Wei

SiReFigureld
Reynolds No. 10448

!
81

13

15 1

a
3
377

9
3
377

20

30

1
-5

14

is

17

is

SeeFigurs6i
I

:, -

liflaccaty, cm siqlasic

3
377
6

193

tl

121

Nozzle area em siq

112

00M.

Reynolds No. 10448

Dom
1

31
3
3 77 1 377
2
11
ON3,1 11aam.

'

568

Effectolincressinglims

1
Spot num

625

I NaL disteme mm

ELECTROLYTE

057

15

em sq/9ve

3
2
41
a
a
0
1
o1
aI
3
3
3
3
3
3
3
31
31
3
377
377
377
77 3 77 377
377
3 77 3M
378
go _396
of
go
go _ 96
96
96
96
so
a. 'r
00.21 Do-, 011 a*.,? as"" as%'? am'? 00"'i, am'?
IS2
148
149
145
146
146
138
137
174
152

Au,117

---a
754

17
a
16
aI
65
005
065
a Is _7
a 79 E10

"W"Ic fil

71

SAMPLE NO.

14
55
Sol

Effewoffoozzledistance

Spot number
Current density A/cm sq_
Current applied MA
Time since
Total coulombs
Thickness urn

I H/d

13
5
625

Nozzle orse em eq

004

1.5 1 75 2
3 75 4 37S

121
475 1
507

QWaW 0a,waa

nne emine 1en/ns

I
1

78

83

4 e

ne

Aw"

SAMPLE NO.

a
9
3 75
4
471 502

it

10

12

13

14

Is

Is

17

Is

0 0f
Orion ait
a! *-

224

308

1 493

1 S4

6powl
quality

ELECTROLYTE

Aw4l

SAMPLE NO.
Temp. -

40

pH 1

I
!: %tV
Ajcm sq_
C!
,,!
Current applied MA
Time sees
Total coulombs
Thickness um
plating
at* uivac,

0.27M Phosphate

Effect of Increasing bms

Velocity rivesc

IS

Nozzle area CM aq

is

Norris size cm

04

linscouty cm salsisc

is

Reynolds No. 10448

*0:-

I
1
25
3 14

05
0.111,
O.
's,
07
07
14

2
25
314
1
a. ".
14
14

3
25
3 14
2

4
25
3 14
4

5
25
3 14
a

6
25
3 14
12

a-. .
a_
28II

-O'M
a
1 25

M, l
96
12

00".
15 3
1 275

13

7
25
314
Is
..

"a
191
1 273

314
20
..
204
1 32

9
25
3 14
30

10

11

IL

13

14

Is

a-.
408 1 38

r). pb. t quai, ty

DEPOSIT OUAUTY KEY

Visual assissernent
only

Is

a- ornooth & bright d- oftooth A dull

ob - own-bright n- slight ncpduisoon
he - slight needle growth
an - severe Modulation
ane - severe needle growth ic - jai Core denonte
doocat
er - erecks nd - no "oble

TABLE

210

13

11

Is

IF-P-UREGOLD

SAMPLE NO.

DEPOSITED SPOTS. PLATING PARAMETER DATA

Aw49

ELECTROLYTE

Temp. -

55

Velocity M/SK

PH .

53

Norzi* aze cm

Total Coulomb*

018
04
16

2
1
4
5
025
075
2
3
1
031
094
3 77
1 26 251
:25 15*63 1042
123 41 45 314
0-r

00
-

Th,citness um
st'ng rate ul"c,
k

'0
'0
-

-=
-

DoDo_

a
0

ol'-"

v1scowly cm siqlftc

Day"

Reynolds No. 9399

IF
a
35
375
440
4 71
89
a3

60"19

-1

- 4
Is 7 - 17
1 74 1 V's

I
01
10
4 425
502
534
78
74

00-

. 0wo

00

=8

MT7a

if
45
585
69

12
475
597
057

13
5
628
625

oow, ci 0

"..

18 a 165
Igo
2 12 2 321 2 541 2 881 2 983

an

14
55
891
568
-'.

104
3104

an

AuSO

ELECTROLYTE

Temp. ar

55

Velocity in/me

pH

Nozzle Sze cm

0.25M Citrate

Is
Is
81 as
754
BIG
5V
481
'0""

0"2'

IC
- -

SAMPLE NO.

Nozzle area cm aq

325
408
96

9 162
14
411
16 2
0 0034 0 131 0576 1
555
1555

epowt quailty

The affect of PH

13
Spot number
Current denwtv A/cm so
Current sopiied mA
T,"w sect

0.25M Citrate

1-it

'0M,

is
17
7
a
879 1005
39
446

IC
-. --

The efhw-l of PH
Nozzle area cm so

18
004

Oco"

-V',

Reynolds No. 9399

: =261
00706

cm sofsec,

15
Spot number

4
2

41 45

1
1 26
31 25

Current denstv A, cm so
Current soo,. ea mA
Time sacs

Totalcowo-os

075
094

025
031
123

cow;

ThICKMOSSUM --

vetlm c";.
36

0 115

0 0024

Plat, no rate u, sc
DeDosil oublory

SAMPLE

a
3
777

325

35

4
502
78

4 71 _
83

08
10 42 -4- go

'0..

'oMit

01119 0.12 -'

11 8
0 75S

ISO
1 526

164
1 708

ELECTROLYTE

V*Iccrty

55

3 75

440
80
a5
1 854

Nozzle

*q*

0 04

cm

- 45

_12
4 75

565
so

So?
657

14

__13 a
628
625

ialqm . 0"M

- 55

_156

as

Sol
S68

754

a is
4al

: 031A

18

5 21

"x

is

17
7

---a 0
to
39
4 46
879

1t"?'

0f

In.

"'.

Sri

In

on "c

Ic

?c

Reynoics

No

Effect of pH

Nozzle

IS

:_

425
534
74

IGO
173
2 let
2338
Fn
1=

0 17M Carsta

rn'sec

11

10

Otto's 0-

16 8
2 024

Aw5l

Temp

251
15 63

NO.

ow

V'qcostv

cm
em

so

so

ra

avc

: 00126

9399
I

Go

3
1 26 1 2 2 11 3 71
3
41 45 131 '25 11 6
,6 12

3 25
4 08
96

3S 13 75
4 40 14 71
a9
83

I L2

Spot riumoor
A Cm w
Current cc""V
Curr"t
sopiiaanA
T, ma sitcs

41
21

075
094

02S
031
123

Torsi cowo-tis
Th, cxnass um

0 0046 0 15 0 659 11 97 - 1 375

plaung 819

Depowt

10

4
S02
7a

4 25
5 34
74

13
5

12

11

4 75
5 67
a 57

45
505
Go

14 2

07 17 '59 1 974 2 105212348 2 49d

628
825

a 911
a9
5 68a
56

.61

a
Is 6
IS
23923
2
9 23
2

2 576

Temp

5:

mloac

Is

:-

Nozzie size cm

cH

Current

A Cm .0
Current sops-od n, A
T, mv secs
Totat couiombs
0.1.11

Qua, 'nr

DEPOSIT OUALITY KEY

Vioust assemorneml
only

075

025
031

004

'23

41 45

13
0 0031

Th.ctqess um
plat'no rate U1110tC
I1
IC)OPowt

no

1
126
31 25

2
251

325

35

10 42

408
go

4401
a01

377

7
1 375
471
83

72- 4 12
- 8 TTSF T3 0
of
44
0 141 0 614 = to 1 333 1 $51 1167S
=
-1
1
1
a

19

: 0012

area cm so

V'scowtv

1a

15 63

Nonis

04

Spot nutrimf

Is
a
7 5544 a 'a
Is
5
a'
4 at

4 48 136

17 3

17 5

1!
, 1

71
! 79 J10 C5 11

le

3 763 3 024 IA 70S I

3 32,

0 17M Ciliate

I
Velocity

1
1144
5
55

ELECTROLYTE

Au52

SAMPLE NO.

1a

II

A*vnoics

1
It

4 14 25
502
534
78
74

4L
565

12

13
4 75
5
597 - -5 628
a 28
657
a
a 25
25

69

4
14
1
55
5
41litl
Ga
Oil
568

is

Is

a
as
754
816
5 21 -78-1

.7
7 191
879 1,0051
7-31
1
4-4-6

-20

140
14 3
15 154
1
1 91 1 032 2--174 2 344
a

is
256
a

165
2905

Ili 1 *7 9 1 is 21
ISO
3 244 3 555 4 013 146,37
: 7:

r,

d- smooth & dull

lt . wnooth & bnght
ob . mMM-bnght M- Slight "OdU10110M
no - slight milloole growth
on - severe inoculation
one - ssioro "irsidie growth IC - lot Coro Gonarito
c, - c-acks "d - mo V,vbIQ deves-I

TABLE

211

. 24]

.:

cm atl, see

10

No

14

,n

SAMPLE NO.

PURE GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

AuU

Temv. :

ELECTROLYTE

56

vow"

So

PH

"Vesc

13

Current dor M
cur, rwril go

cm GQ
A
4

Time sece
Total coulomos
Thickness unl
Plating rate weec
h
epowl quality

1 075

025

Temp.:
pH

Vold"

al

Nozzle size ern

025

2
075

325

a
375

35

006"

10

11

425

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ELECTROLYTE

Aw54b

SAMPLE NO.
Ternpi. :
pH

55

vellocily, misec

all

Nozzle size ern

071
345

,iA

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Thickness um

3
11

2
10

1
9

Spot number
Ctirrwnl0,,, __
Iv A/c, eq

Plating

IL
a

am
F' .
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3I 7 242
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0534
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18

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3
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-M

::

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55

123

Total coulor, lbs

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lifiscosify cm sq/9sc

an

14

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597
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088
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14

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6
14

13

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as

is

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at

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t

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901

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,
rate u "a"

21
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1
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1 72 i 2 29
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71 45 31 25
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DEPOSIT OUAUTY KEY

Visual sesessiniont
only

51

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TABLE

212

71

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TABLE 17

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TABLEISA
215

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0
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TABLE18B

LO-1

216

Ueposition

C. D.

Sample

mA cm

Ni Dep.
-2

Ni Scin

gI

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jor A-hay UlTraction zampies

conamons

Hard.

Boom.

N At

-2
kg mm

ml I

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--

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um

RNC 3
ANC 7

3
7

031
0.270

1.7
1.7

2015
204

103
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RNCiO

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0.266

1.7

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13.7

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1.7

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0.77
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40

1.7

131

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00

147

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MRN 7

3
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0.35

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1547

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0

13
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0.28

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MRN20
MRN40

15
20
40

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1.5
15

1553
2007
210

08
09
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0
0
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XAUP 3

1
3

0
0

0
0

949
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0
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0
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XAUP 7

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10
20

0
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0
0
0

952
836
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0
0
0

0
0

0175

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ConvenbonaJ

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las

0
0

Acm
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0.259

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RNXS

0.21

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FINX8

3
3

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RNXIO

5
7

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149

0
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0
0

154
1595

0
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so

142
134

00

Is

2001

60

ISO

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0

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80

17.6

80

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SO

179

60

17.3

RNXII
RNX12
RNX13

19

MNX14

13

Is

Jet plated samples

Jet plated samples

Jet plated samples

RNXIO

5
7

2052
2036

RNX17

2128

RNXIS

Is

RNXI9

024

19

127

0801

RNX20

0158

1.9

132

0.520

so

187

RNX21

013

19

150

0435

60

17.6_

RNX22

o. iI

19

170

0368

600
0

149

ANX23

is

0079

19

0265

60

181

RNX24

143 3

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23

RNX25

1639

ca

RNX26

RNX27
RN

1 982
93 ',
5

ANX15

AN X 28

2
0
0

2
0

167

Jet plated

samples

Jet

samples

plated

75

130

10

TABLE 19
217

=
SPOTS.
DEPOSITED
PLATING
PARAMETER DATA
ALLOY GOLD

11

RNI &2

SAMPLE NO.
Temp.
pH .

55

Velocity nVook:

46

Nozzle size cm

1
025
031
246

Spot number
Current density A/cm, so
Current applied MA
Time *act

Ronoval N

ELECTROLYTE

20

BOOSTERm1A .

Nozzle or"

Reynolds No. 10624

cm sq

7
61
91
10
1`1
12
5
6
a
9
10
628 754
879 1005 1130 1258
125 1042 892
78
69
624

00M.

00"

Thick. *** urn

lating rate urn

05
0002

20
28
138
17.3 172
174
L8 182 178
IGO 163
0 031 0 042 0 441 0 835 1 154 1 456 1 589 1 039 2 205 2 435 2 612

011M

OOM3 oomv

conse

00m,

do-$

O. Mill

80

0WIM21
dr

Total coulombs

00,0.0

is

%Avcowry cm sq/ooc.

004

51
0
3
4
3
1
3
4
377 502
1 25 377
625 31 26 2084 156

2
075
094
829

NICKEL IN ELECTROLYTE911

17
is
13
14
Is
Is
11
13
14
15
is
12
1382 1507 1833 1758 11164 2010
30
568
521
40,
4 4a 410

con, do 00,10,

001

00-2

7MIT
do, 042 DOM,
_ T4_

ao

0
3 821

is 1 167
2 8345 3 205 3 202

it %
2

205 2

12001
II

J
_.

SAMPLE NO.

RN3

Temp. pH .

I
_

_I

Ronoval N

ELECTROLYTE

12126

203 6

NICKEL IN ELECTROLYTE94 -

55

Velocity misoc

2D

Nozzle arms cm aq

46

Nozzle size c, "

04

%floca" c, " 94120c.

BOOSTERmin -

0.5
I
OW?
Or'S3'

50

Reynolds No. 10624

1
2
11
075
025
031
094
246 B29

Spot number
Current density A/cm eq
Current applted mA
Time 99ce
Total Coulomb$
Th, ckness urn

00,12.

piatina rate umigec

rNickol
in deposit %1
artiness ka, mm2

3
51
0
4
4
1 3
1 26 377 _3377 502
625 31 28 20 84 150
. mj

eorVIO, d0-0

10075
1

004 1
11623 11

Temp. -

Velocity

55

1
02S
031
240

101W
,w

--",

Temp.

SE2t number
:M go
Current appi. od rnA
Time sacs
Total coulomb$
Thickness urn
Plating role um
.
wnlrii.

katmm2

2
1
025 1 075
031 1 0 94.
246 1 a29
00,11.

low$

atim

19

1
12

13

14

is

Is

10
1256
624

11

12
1507
521

13

14
17 58
446

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0088

0059

Z)

1a

oomi

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OOM3

0 129
1374

_
-00,.?

0 114
148

1864
4 Is

20 10

0.72

gA

BOOSTER

Reynolds
A.

Im

mlA -

me

90

No. 10824

1
11
12
10
a
9
to1005 11.30 1256
78
so
0 24

is
17
13
15
'a
14
0
14
is
11
13
12
1362 1507 1833 1758 1884 =.
39 1
568
521
4a
481
446

00-7

00M.,

'a-

10082
1

Q-,

00-9

Dom.

. 0-,

don't

1
0 055

11734

TABLE20
218

000753

cm vQ190c,

1
013

is

19

7
17
5 16
625
7S4
879
892
125 1042
oo

1633
481

is

dO3
I'm ' '

NICKEL IN ELECTROLYTE

Viscosity

1382
558

17

F
:

I. 1

Nozzle area cm aq

004

1a

0047

jeo a I

Ronoval

No. 10624

Reynolds

11

ooni"

I 51

10

oa?"!

3
4
14
3 13
I1
377 1 502
1 26 377
62 5 31 26 20 84 ISO
iW? t

Tycrnsq/60C

00,101,
on, , ! ""1
0

15

I
I_

visco

oml

Nozzle size cm
N

: 00124

1005
78

Velocity milask;

PH

9
11 30
69

ELECTROLYTE

55

aroa cm aq

508

ANS

NO.

so

0.72 BOOSTERml/I -

Nozzl:

6 17
7S4 18 79
692
1042

oom3y

NICKEL IN ELECTROLYTE9A is

Ronoval N

3
5
4 N
3 77 1 5 02
0 28
2084
5O
158
125

latima rate Urn/

Ni. kol In d. 0091t %1
witness xtilmm2

SAMPLE

oeigno

832

020
04

oom,,

is
17
Is
13
15
14
Is
14
15
il
13
12
1382 1507 10 33 17 58 1864 2010
446
568
521 481
1@ 39
-4
oofto
oom?
con'r
I~
DOM3
corew

0025

misec:

3
0 75 1
1
377
094
1 26
G
829
25 31 20
0rli, f

loniat

I-,

164 2

Nozzle size cm

1
Zbe a
CM
did, " A, cm so
Current 8000ird rnA
Time secs
Total coulombs
Thickness urn

draso

0 033

ELECTROLYTE

AN4

SAMPLE NO.

00MI,

7
a1
91
io
11
12
5
1
a
8
9
10
6 28 754
879 1005 11 30 1255
75
125 1042 892
69
824

'em"

ALLOY GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

SAMPLE NO.

RNS

T".

55

voCcity"vc

20

pH .

46

Norzie ipze cm

004

Spot number
Current

domimj_m

Cuffent appited mA
Ti sees
ITotai coulombs

4
075
3
094
26 377
820 Le25 31 26 2064

I
025

1
011
246
0""

55

Velocity rNsec

pH .

40

Norzle are cm

I
025

Currtnt

031
246

094
829

secs

Total Coulomb$
Theknese um

00M.00of
0007

Platina raie umisec

Velocity misec

pH .

461

Nozzle size cm

mA

I
025

0
094

031

246 1 829
Im.

um

-i

pH

Spot number
Current

demwty A/cm $0
appited

mA

T,nw socs
Total couioos
Th, ckten
Pisting

um
role um/mc

FNTc-k*lin deposit %
Fvaesv ko-2

9
3
1

00-1

i IA

S02

7
5
628
125

1159

1 011
248
00,12.

2D

829
oo

004

3
3
377
26 377
625 31 20 2084

11

Olft,

0032

I'M

1042

Ranov&IN

Nozzle size cm

094

9
7

12

879
892
. . -F

101 11
a 3-0
9 1256
10
1005
,1eg 024
78
. . -I

oo

00.11

181

13

a
4
502
156

1362

ro-1---"l
r, 7-5-r
1505
NICKEL IN ELECTROLYTEg/l .

2.2

Nozzle are& cm aq

000124

m9covirer"

0 007W

9 L-1
II
a
9
N
30
679 1005
892

7a

1'
0

0.

CO-)

I.

1063

123 8

M.

I
194
176 oom"
192
11a 0845 244 1536
0377
1031
044

11

is
le

Is

01.1,10-1
155
oei

BOOSTERPnIA-

60

Reynolds No. 10024

12

I?
15

1 15
Is
14
13

Is
16
1
1010
1
39

10 1382
II
1633 1758 1864
II's
150,
4 16
$24
521 F 4-8-1 446
1- 558
0169 r76
11-1
omdI16 3 -M,
114
21
3 102
12788 29754 r3-72-9-13368 3855 13822
119 11
154
O. Mll

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I. Ml

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0092

60

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000124

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plyeineq/c

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692

Is

14

13

12

NICKEL IN ELECTAOLYTE9/1 .

9
7
879

17
15
14
13
1884
2010
33 FT
446
4 ie
461
39

. e-

0079

12

Reynolds No. 10024

13

14

is
10L-11
le
17
Is
14
io
9
12
13
a i1 30 1256
10 1382
iL 1507 1633 1758 ISS4'S 20 10
1005
24
le
481
4 46
39 1
521
SOS
so 00.11
8
1'em,
a17 1 00m]oom.
enn',
164
158 71
17 0 10_5
Tr
-15
97
168
Is?
-3
T-4-077
r4
12
3 75
2692
30106
320S
341
3543
258
7-5 4 0777F7
2692
30106
320S
3543
2256
ro-o
10 147
8-7
0131
0 176
178 1
74

. ?

NICKEL IN ELECTROLYTE9/1 -3

BOOSTER M0 -

Nozzi area cm Pq

I
GODUS

%necowlycm 9Q/s*c

.a

007W

12

13

60

Reynolds No. 10624

14

is
9 10 II
17
Is
Is
14
12
13
7
a 11300 12 56
10 1382
II
is 20 Is
879
33
10
1005
1758
18
24
1042
al
446
4 Is
39
a
568 1507
521 16
LIG-1
so 6
I 0OrM
oo-,I0107 0em'?177 017S
on)? a01
0
17
19
181
r4 ISO
0-77-1
2993
823 2096 2321 2585 2804
1241
FO
I 2-op
176
0 143 2 0 1607
0158

a
5
a
G 28 7 54
125

14
12

II
7077
521 14
sea
0 00-1
I
Ise I
1-2-95-777

sq'sec

60

Reynoide No. 10524

. -?

178
173
2 321 2551 2772

V* loc, ty M", 2

025

oowm 1

ISO
193 00192 -1.1
186 I182
237 1 538
1 237
804 12204
04
538
1 1 10174
1 1
0238
0174
lUal
1
11335
11495
1495
1335

ELECTROLYTE

2
075

a
7540

-11

031 ,0

46

V,wowly

OM)

004

a
4

377

176
11
9
le 00381
0
028
381 0645
845
0028

Tomp.

1042

20

117
1

"I 2e 2084
625

AN9

SAMPLE NO.

6
7546

Ronoval N
.

4
3

26

owl

piat.,,
piat.,, G
rate umlsec
umlsec
G rate
FN-ickel
Nickel In
In depooll
depoml %1
lHardneso
kol-2
srcness koi-2

[Curr*nt

2
75

621
125
lo

ELECTROLYTE

55

T, vcs
Total coulo,, os
Th. cknete

0034

lom?

7
5

0001"

oomt
omil 175
-11"
194
131 0
192 a
183 0179
las
188
0419
B88
244
804 2052 2295 2536
536
0 0167
1 1 1128
019 136 1
0098
148
1686

Temp. -

Spot numbor
[Cvrrent comsity A,cm sq
itopited

21

004

502
156

OM3

-M,

RNO

SAMPLE NO.

1042

2D

a
4

1255

caqw,,2

Current

5
4
3
3
377
26 377
625 F31-26 2084

0308

IM deposit

e
754

Ronaval N

Temp. -

soptsed mA

628
125

ELECTROLYTE

2
075

Nickel

502

BOOSTERmIA -

1.5

Nozzl* area cm aq
m sq/c

0. -1

RN?

Spot number
Current density Alcm so

7
5

6
4

NICKEL IN ELECTROLYTE9/1 .

ISO
oil 770
, DM,00-1le137
19
0438 1
52
1 01351
025 1
0168
1406
1289

oo

Plat'. 9 rom umtooc

Nickel In deposit
Jardn*ss qim2

SAMPLE NO.

I'll

oo

Thickness um

Ti

Rcmaval N

ELECTROLYTE

54

Dy

ao

cow.

. l

ion"

TABLE21
219

Omll

11

SAMPLE NO.
Ternp.

ALLOY GOLD DEPOSITED SPOTS. PLATING PARAMETER DATA

ELECTROLYTE

ANIO
63

Velocity nvwc

48

Nozzle size cm

Ronov&IN
20

NICKEL IN ELECTROLYTE9/1

BOOSTERrrg/l -

80

- ;7zzis
Reynolds No. 10624

ar" crn sq

004

viscowly em qq1q*c
V1

07iVI
N

Spot number
Cumont 43*nwty A/cm aq
C. Iftnt opphed mA
Time sece
Tollif coulombs

21
025
031
246

075
094
829

001?71 ll

Thickness um
lating row u/sec:
r l ckel In el*eosl t%1
'mm i
a rdne;;

1
3
377
1 20
62 5 31 20

come

5.3

0 'so -85

0
1

377
20 84

0111'ro coml

13

1144

1
1528

4,
502

5
8
628 - 754

7
a 79

156

125

1042

892

lama

lam?

aof

comly

138

142

37 716
-- 5 601
1

T-91- 7104
1

134

132

-1 48

2=6

1148 3

1 1154

10

11

12

13

a
9
10 OS 11 30
78
at

10
12 50
024

11
13 82
568

low,

00,11,C) Dow?

135

127

125

1 079

1 957

2 035

2 2007

h595

IS
Is

12
13
14
15 07 . 16 33 1758
17 58
5 211 4 111 446
44 6
_
am)_ oo
1-7
lie
122
121

oo'

131

Is

14

2 342
I

2 516
I

17

is 1
16
is 84 120 10
39
4 '16
0MI,

2O 46
.

TABLE22

220

la

114
2 74

left),

It 5
75-5

S&NIPLE

C. D.

Do A

D,, )L

(111)

(111)

D,, A
(222)

<e3>
(111)

a
(111)

2 ". 3

Ni

Booster Hardness
CM3

CIM-3

kg MM-1

Pure u Conv.

3.0 nLAJcmz

2332

744

540

0.000035

n/d

101

Pure Au Conv.

7.0 mA/crn2

2321

860

551

0.000035

n/d

01

102.4

Pure Au Jetted

2.0 A/cm2

324

326

198

0.00011

0.007

163.9

Pure Au Jetted

4.0 A/rn.'

350

349

206

0.00015

n/d

198.9

Pure Au Jetted

6.0 A/cm2

335

327

215

0.000115

n/d

203.5

Pure Au Jetted

8.0 AIcm2

328

304

205

0.000133

n/d

204.1

Ronoval N Con

10.0 mA/cn-s2

261

104

128

0.00015

n/d

1.7

60

198

RonovalN Conv.

40.0 mA/cmP

254

107

128

0.000135

n/d

1.7

60

130

Jetted

3.0 A/crn2

324

340

209

0.000115

0.021

60

Ronoval N Jetted

9.0 A/cm2

289

307

189

0.00013

0.022

60

Ronoval N Jetted

3.0 AIcm2

191

182

104

0.00017

poorpeak

1.9

60

127

1.9

60

170

Ronoval

resolution
Ronoval N Jetted

9.0 A/cm2

200

201

128

0.

TABLE 23. Crystallite size, RMS strain and stacking fault probabilities for some samplesfor the (I 11)
planes only. Note n/d = not detectable.

221

ELECTROLYTE

NIAX.USEFUL
C.D.

MAX. DEP. RATE

0.041M citrate gold

3.0 A Cm-2

1.7,um sec-I

0.17M citrate gold pH 6.0

5.5 A cm-2

2.9 Am sec-I

0.17M citrate gold pH S.1

6.0 A CIIr2

3.4 Am sec-I

0.28M citrate gold pH 6.0

5.0 A cm-2

2.9jum sec-I

0.27M phosphategold pH 7.1

3.75 A cm-2

2.2, um sec-I

TABLE 24. The maximumuseful current densitiesanddepositionratesfor the pure gold electrolytesstudied.

ELECTROLYTE

MAX. PLATING RATE

Ronovel CNI

1.6, um sec-1.

5.0 A =2

Ronovel N

2.0 jim sec-1.

6.7 A czw2

Auruna 7000

2.3 /im sec-1.

10.0 A crrr2

MAX. C. D.

TABLE 25. The maximum useful current densitiesand deposition rates obtainedduring the initial study of
the alloy gold electrolytes.

222

Reynolds nurnber
Limiting C. D.

1893

5252

7538

0.367

0.47

0.591

953

1220

1535

618

976

1148

461

768

923

956

1145

Sherwoodnumber
Alkire, & Chin
Chin & Hsueh
Chin & Tsang

Sh = 21.03ReO-"
Sh
Sh

0.9ReJSc.33(Hld)-0.09
1.51Re-5Sc. 33(H/d)-0-0-14

774

(Laminar flow)
Sh

33(H/d)-0.057

1.12Re-ISC.

(Turbulent flow)
Diffusion coefficient
Viscosity 0.014M Cu

5.7 xlO,3 cm2sec-I

0.010879 cm-sec-I

TABLE 26. Limiting current density and Sherwoodnumber data obtained using the 0.041M copper electrolyte, together with calculatedvalues using modelsderived by other authors.

Reynolds No.

3355

iL(SCPV) A cm-2(pure)
'L(SVPA) A cm-2(pure)
i, (SCPV) A cm3 (R.N. no ni)

4.41(-8%)

6710

13545
9.97(+10%)

6.3(-3%)

5.1(+B%)

'L(SCPV) A cm 2 (R. N. + r)

'L(Correlated)

10600

5.03(+6%)

Sh - 21.03RO

4.78

6.52

8.94

4.71

TABLE 27. Limiting current density data for the 0.17M citrate gold and the Ronoval N, together with
Percentage
&
Chin
deviation
from
based
Alkire
the
the
the
model.
values
on
represent
values
calculated
model.

223

ADDENDUM

Published papers related to this work

224

TEXT

BOUND

THE SPINE

INTO

High Speed Selective Jet

Electrodeposition
C Bocking
GEC-Marconi,
Hirst Research Centre,
East Lane, Wembley,
Middlesex, HA9 7PP

SUMMA RY- High speedselective jet electrodeposition is a process whereby electrodeposits may
be produced in a selective manner without the needfor masking. The principle is that a nonsubmersed, free standing electrolyte jet impinges onto a substrate and deposition occurs within the
impingement region, with little or no deposition occuring in the surrounding areas. The deposition
of copper from an acid sulphaie electrolyte has been examined and deposit structure and quality
has been related to the prevailing hydrodynamic conditions of deposition. The selectivity or
resolution of the process has been examined. Further work has been carried out using an acid
citrate gold electrolyte and some initial results are presented, and also relating deposit structure
and quality with the hydrodynamic conditions of deposition. Examples of applications are
discussed.

INTRODUCTION
High Speed Selective Jet Electrodeposition
(HSSJE) is a process whereby electrodeposits may be produced in a selective
manner without the need for masking. The
principle is that a non-submersed, free
standing electrolyte jet impinges at a high
velocity onto a substrate and with the application of an electric current, deposition
occurs within the impingement region and
the immediately surrounding region. Due to
the resistive nature of the electrolyte and
the properties of the hydrodynamic flow
surrounding the impingement region, the
spread of the deposit is limited. Whilst
Selective Jet Deposition is not a new technique, the principle being patented by
NASA' in 1974, there has not been a
significant commercial exploitation of the
process. The NASA patent refers to feeding
an electrolyte at high pressurethrough a jet
nozzle onto the surface to be selectively
plated. An image of the pattern to be plated
was scanned using a video scanner in a
raster fashion in the same way as an
electron beam is scanned on a television
screen to obtain pattern defining signals.
The nozzle was scanned in the same way
and the pattern defining signals controlled
the amplitude of the plating voltage. Thus,
in regions where plating was required, the
voltage was modulated to give the plating
current. In this way, the pattern was built
up in a similar way to a dot matrix printer.
A forced flow selective plating system
was described by R. Haynes el a12 in 1978
and Dorey ef al used a modified version to
gold plate conncctors3 in order to evaluate
thermocompression bonding characteristics
of the deposits produced. The maximum
flow rate used was 39 cm/sec and current
densities of up to 1.3 A/CM2. With a nozzle
diameter of 0.5 cm, the flow under these
deposit
However,
is
laminar.
circumstances
quality deteriorated at current densities in
formaby
A/CM2
0.86
nodule
the region of
tion. It was claimed that nodular deposits
did not necessarily reduce bondability.

Dopergiven at 1991 IMF Annual Technical

Conference, April 1991, Torquay, UK.

Bocking, Trans. Insi. Metal Finish., 1991,

69(4). 119.

Safranek4 describesjet plating systems in

involve
but
these
all
a
operation
commercial
non-conducting mask. The selective plating
is
in
plants
commercial
some
of connectors
jet
deposition
on
using
currently carried out
a step and repeat basis using masks and
2m/sec.
to
up
of
electrolyte velocities
There have been a number of papers and
monographs

that

describe

the

hydro-

dynamic behaviour of a free standing jet of

fluidS.6,7.8.9.These deal mainly with mathematical models together with experimental
verification of the fluid flow from a free
standing jet. NakoryakOV6 describes the
mass transfer in all regions of the jet and
impingement region together with the
hydrodynamic characteristics of the jet.
The system used for verification of their
calculations was an alkaline ferri-ferrocyanide solution. As well as developing a
mathematical model of the free standing jet
related this model to
system, Alkire el a11O
the ferri/ferrocyanide system and to the
deposition of copper from an acid sulphate
system, both with and without the addition
of a more noble ferric/ferrous redox
couple. The measurementsthat they made
on the mass transfer characteristics in the
jet impingement region agreed well with the
work of Chin el all I who measuredthe mass
transfer characteristis of a submerged jet.
The Alkire/Chen model included a prediction of the selectivity of the process. Selectivity may be described as the ratio of
reactant production in the impingement
region to the reactant production in the
surrounding region, which is known as the
wall jet region. Whilst the theoretical model
was able to accurately predict the selectivity
for the redox system, it was not as accurate
for the acid copper deposition reaction12.
No mention was made of the morphology
of the deposits produced.
There are a number of commercial
systems that utilise high speed jet deposition both with and without masking but
information on the maskless system is
comparatively rare. This is presumably due
to commercial confidentiality reasons.Gold
deposition using small bore jets (Imm to
0.25 mm diameter) was examined by
Bocking13. lie examined the morphology of
the deposits produced and related these to
the electrolyte velocity. The current efficiency of the process was also assessed.
Also described was a "direct write" facility
whereby the jet could be moved in relation
to the substrate by means of a computer
controlled X-Y table thus producing tracks.
This work is designed to examine the
selective plating of small areas using a
nozzle diameter of 400 jLm. It is part of a
BRITE* collaborative project on the
improvement in the control and attainment
of high speed electrodeposit ion processes.
it is not the purpose of this paper to verify

119

the relationship between the mathematical

models put forward by the aforementioned
authors and experimental observations, but
is an initial examination of the relationship
between the deposition conditions and the
deposits
the
topography
of
and
size, shape
produced. An acid sulphate copper, a
citrate based cyanide gold electrolyte and a
phosphate based cyanide gold electrolyte
have been examined. The structures and
dimensions of the deposits have been
examined and related to the prevailing
hydrodynamic conditions. The selectivity
This
initial
described.
is
also
of the process
designed
to esabwas
the
project
phase of
fish the basic principles of the system using
followed
by
and
was
system
copper
an acid
for
the
electrolyte
gold
of
the optimisation
DC
deposition
a
using
conrates
maximum
trolled current.
EXPERIMENTAL
Figure I shows a schematic diagram of the
Jet Plating system together with the control
jet
The
consisted of a platinum
equipment.
The
lead-soda
tube.
into
glass
a
tube sealed
dosing
diaphragm
type
pump
a
pump was
70
1/hour.
to
delivering
up
capable of
Delivery rates could be adjusted with a
2%.
The
better
than
reproduceability or
Fitted to the jet
from
was
the
pump
output
flowmetcr
and a pressure
via a precision
transducer. Also fitted to the Pump outlet
damper
to
maintain a
pulsation
was a
constant pressure during use and a pressure
relief valve. The maximum safe continuous
7
Bar
the
was
pump
of
working pressure
8.25
Bar.
to
set
was
and the relief valve
The jet was fitted to a computer controllcd X-Y table. This allowed a number of
be produced on a
to
spots
clcctrodeposited
by
a step and repeat
single substrate
with
a
A
used
was
computer
process.

in
RIIB-0304Parnersh'P With
*BRITEPrOject
Italy
Materialli
of
and
Svillupo
Centro
Loughborough University of Technology.

control
program developed "in-house".
The computer program could also take plot
Files from computer aided design packages
(CAD) and convert them to output f iles for
the X-Y table, allowing very elaborate
designs to be directly written by clectrodeposition.

The jet was connected to the positive

terminal of the controlled current power
supply and acted as the anode. Due to the
resistive nature of the thin electrolyte jet,
the power supply was custom built and was
capable of delivering up to 350 mA at a
voltage or up to 57V, with a resolution of
0.01 mA. During deposition, the cell
voltage was monitored using a chart
recorder. The plating current could be
preset via a short circuit switch prior to each
deposit spot produced. The current was
monitored using a calibrated digital multimeter.
The electrolyte flow rate was calibrated
for each different electrolyte used. The
pump output was controlled by both a
numerical handwheel that set the length of
the diaphragm stroke and a thyristor motor
speed controller. Calibration consisted of
measuring the volume of electrolyte discharged and allowed an accurate setting of
the flowmeter for differing handwheel and
motor speed settings. The output pressure
was then related to the discharge and a
calibration curve drawn.
The electrolytes were prepared using
Analar grade reagents dissolved in double
de-ionised water. After preparation, the
solutions were carbon treated for 2 hours
and filtered twice. The electrolytes were
then analysed using X-ray spectroscopy to
establish the metal ion concentrations. ror
each electrolyte, the viscosity was measured
using an Ostwold Viscometer in accordance
with BS 188 (1977) at the relevant operating
temperatures. The density or each electrolytc was also measured using a density
bottle at the relevant temperatures.
COPPER DEPOSITION
The copper electrolytes used were 0.8M,
0.20M and 0.08M with 0.51M sulphuric
acid in each case. Electrodeposited copper
spots were produced from these electrolytes

Figure I. Schematic ofjel plating unit

I-

"I

TABLE

MICRI]COMPUTER
II
II
II
II
II
I

T
STEPPER
MOTORCONTROLLER

TtOIF---- r -------------- FL-o,;

I
I
I

ET

iI
'.

DAAOPER

Li

TRANSLATOR/DRIVER

I
CONVANT CURRENI
PowEP SUPPLY

--------------

PUMP /

clwc, 1, ,
SwIll .

r"Ire

.tc..

tp, lit

using various electrolyte velocities and

current densities. Each sample group of
spots was plated onto OFHC copper strips.
The strips were prepared by polishing to a
mirror Finish and then cleaning in a proprictary soak cleaner for 3 minutes using
ultrasonic agitation. This was followed by
cathodic cleaning in a cyanide based cold
cleaner for I minute. Immediately before
use, the substrates were given a bright dip
to lightly etch the surface and finally given a
further I minute in the cathodic cleaner.
The substrates were then thoroughly rinsed
in de-ionised water and carefully dried.
Trial deposits produced from the 0.8M
electrolyte were plated over a range of
between 0.25 and 50 A/cm2 in order to
identify the useful current density (C. D. )
range using a total charge of 0.017
Coulombs per spot. The nominal thickness
of these spots was calculated to be 5 pm.
Subsequent deposits from this electrolyte
were produced using a total charge of
0.068 C per spot, giving a calculated thicknessof 20 itni. Deposits produced from the
0.08 M and the 0.2 M solutions were plated
over a current density range of between
0.25 and 3.0 A/cm2 as very poor quality
spots occurred above this maximum. A
total charge of 0.068 Coulombs was used
for thesedeposits, giving a calculated thickness of 20 pm. assuming a cylindrical
deposit growth. In addition, a series of
spots were prepared at a constant current
density and velocity but with increasing
time to establish how the deposit structure
varied with increasing thickness.
All deposits were produced at a temperature of 25*C. The jet to substrate distance
was maintained a( 0.5mm. Electrolyte velocities ranged from 2m/sec up to 18 m/sec.
These related to Re. values ranging from
546 up to 6970. Thickness measurement of
the spots was carried out using a Sloan
Dektak 3030 Surface Profilometer. This
gave a profile across the centre of each
spot. As deposited spots produced by
selective jetting show a broad gaussian
profile'), with the maximum thickness at
the spot centre the average thickness at the
centre of the spot was recorded. All thicknessesand plating rates mentioned in this
paper are based on the thickness at this
position. The surface morphology was
examined using both Scanning Microscopy
as well as optical microscopy.
The structures of some of the thicker
deposits were examined using standard
microsection techniques. In samples that
showed a significant porosity, the percentage gross porosity was calculated using data
obtained from an Optimax video contrast
system. The resultant percentageswere subtracted from the thicknesses measured and
the corrected thicknesseswere recorded.
GOLD DEPOSITION
Table I shows the basic formulations of the
electrolytes used in these trials. The
viscosities of the electrolytes were measured
at the chosen deposition temperatures
25*C, 40*C and 55*C + 0.2*C using a calibrated U-tube viscometcr. The conductivities of the electrolytes were also measured
at the temperatures stated. Gold spots were
produced on poli%hed, nickel plated substrates with a 0.1 pm gold flash (to prevent
immersion deposits). The spots were pro-

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- I

1)(HAWkIlli
L Nalildc)
Ih jlola111111

SIS

IIN(Ilop. (-Il phoNplialt.

di

40 1) pI

I)Ilo%phalc
liNdlokitic

10 0 1,
it) III 10

0 7NJ)

(aN pol; kwulli

1 (0 17KI)
II),
yidd k N.midt. )
I )I'llu moliIIIIII
fmho, cfl killaft,
.1 (I ), I
I () f. ,I
( 1111t acid
Vol. vo, min h%'dfo\idc1ii
1,11 6.0

(4)(mid

I
( M1111 R 11111,14JISI
"S
I fit, II IvcI (11( urrent Dell"il.. '

dclisily
] lit, cI 1c, I ()I lilt lcallly illc LuIlcill
looking
hk 11111111.111wdh\
al tile
-III
dcpoll
to[ all tile
'. 11110111c". Ill )"clicial,
Ockliolvic",
111Cdcpo"11" ploduced
i'llowed
OW
lilt

lick-all"v

tile

e(julawd

ollmillal

D.

C.

111C

cl,,

(hplic

"lallites

W1111

"MILMIC"

milERSHMEME

laige

(hpirc 3)
numb(. 1 (if lim Ical loll
(oill'ic'
lJo(illkil N1111clille" "ith
it
limew numbel ol nucleation
sIles.
0 o'llit. 4)
nodillal
Willi
(1) ( oalse,
"IlliCtilles
C%Idt-Ill I dillicil"lonal
nuk Ical toll, hill
I- Nidem
c %% Illik Ical Ion
-'Itc%.
5)
(Figille
Nvkoll(LIIN (Icildilic".
c) Po%%dcf.
(It'l)(11111C
"lluclutes.
(I tgoic 6)

2 (a) Aft. rm", Ilwl

I ll'im.
)/ a coppel
III '110 %II.
kI Wo
(b) Sil I/, /, I- %fw p)? (, to 1!1. oI the sa Ifle
10
1cm " Rc
11,-1 %III)
'1
.
I ?f'

/
,X

.1(,,
1000
(b)

dep, m/
I "'

) %1,,

ito,, oI I, olyper
%f0f)"holos-v
of

1)

oS At

(1(,I)o%tl.
%alm,

61R

iAlpb4-Ax

)J9
:

(a)
(hi
1' -

I.

dI-.

lotill

Illa'o, of cach Spot waN

ill Illc lef-lon
10 1 P. file cillicill
of 9\
c1likit-lik
not Ile Incamiled
kotild
oil tile
SillIII I) IC Ill i 4111kCd ilk )%VII
\A,
' ;I', ncccvarv
to pit-pait- cillict
it mplv Npot plalt-d fill a
little
cow'llit-1-1111v
of
01 it wile"
Ill
Idt.-IIII-d
polN ()It it "Illyle
"llhNifitic.
10 1111111flust.%lib"flale
plas%
oldet
ctlckl",
%%CIV J)Illlvlcd
%kith 0.04 /Aln of
shile"
follo%%cd h\ 0,1 pill of pold, 1 fitchlolliIIIIII

it',

SITUCIUIC',

I ca"cd.

( old (; I pol; j""11111)

4 0 g/l
(0.28m)
glild t-villildt. )
1) 1.11]
1Illoll III III
lmlloj,
I () , I
111.11c
(
cll
( III lk at [d
1 01,1
livdfoxide
to Jill 6 ()
Polay,111111

dtI, -cd 11%1

dell"ll I"
11coxcell
it I, cillivill
0,? ', A cm' and 21) A cm'
Tilt. liflic of
a(IIIINIM 10 "Illilliv it tolal of
(1cpo"Illoll %%it',
0.039118 1 0, (XXX)S(011101111)"
[let ',[lot. Up
lit IS spol" "cIc dcpo"llcd onto it Inplc
I 1kh %cllt-, (if %1101%%kclc
%IIIl%II,IIi:
.
plodliced
c1cololvic Icillpelatille% of
2S''('. 40 A and SYA "I
lic cleolok Ic
VeiocIIIc% wwd %kcir 2m/, w( . m/m%. M
ni/wk- and IN in/%ck. Anollici
wiic,. of
%pols N%il%picimled al it coll"laill
cillicill
dell"lly and velok-IIN, bill %%,
till ;Il. a[VIII), let
to "llb"llalc (11"fallk.c.
tkilly, file 01)[111111111
lot Ilw
col)(1111011%
the ClIck. 1% of
fillo%philic
clecliolvic.
dr'sokcd
o\vf'CII W(-I(- c\, IIIIIIIctI hv pic
pillilly a Wile" of %pol" \%Illi Ow clecliolvic
de acialed bN bubbling mlioren throtigh ii
fit 10 IIIIIIII11c" 1111olIll phllll,
2 wm-N of q)of,, uNing file
A hitilici
and lellipcialilic
OPIllimill
%%cfc
I'm x
piclialt-ki lloill file cillillc clet'llokic
a fill of 'i I and 81 loctiallillit, OW ('11c't 'd
fill
"'LiIIIIIII)p vicklioll
lakell of wICLIc(I spol" OlmAIIII, illc lopo
glapliv of [Ile &-po"11%.

101101AIII)i

"

I.

\__
5.1'__...,

"r'
1

IT

';
"

"1:,

-"

t/I

. 1"%

1.

LI

'IL

'S

.
I.

"'";

"I
"I".

"

121

Y4
I

II 0 . lwi

w4

10 1,.

liN

.,

0O

11

OhI'.!IV fll(Ss

(a)

eleriviv

0 SM

V, I.. tv

IC
A S. l
V IIS. l.
')

tI /'

)."r

0
D

a,

A".

'I

(h)
'I , 4'pp"f dep"Nit.
'01 Ou. wisle

5 (a) %fl, I ...... Il, m

l'iyule
/(X)o Op) N-111(v
0 SA I,

/S 41

(, pper.

/4 111

dimcn%ionle%%(tvlance and is tile ratio of'

noMv radiu. % to iadial dislance hoin [lie
Centre ol* [lie let. 11 Call be %eenthat there
Was 110%ignilicallf effect of* cullcill density
oil selectivilv Willi (lie exception of tile
deposit pi oduced at 7.6 A /ctW. I his pi ot lie
indicates that Ihe deposit was lending
lowaid. %gicalct m*lcclivitv. At this cmicni
denmiv, tile dcl)o%ii became moic nodular
held
[lie
appaicnt
and
and
(mcnialcd
bck-anic
tile
plating
willun
late
preatei
(lie
legion
of ill(- cl(-k,tiic field ic. wilhin
has
this behaviour
clectiolvic
let. I lowever,
is disbeen cell Willi gold deposition
and
,
Cussed below.
Figme

11, f,, %,"fI,

6%

I Ivure

(I S%f,,,.

1j)oo

"I

9 compaiv.,, tile Dekial,

thickness
It call be
lilcaMilcolcills
%N1111
1111(lo'.cclioll.
seen 111al 111cic I% a Ica"ollaillc
kollclatioll.
1.10111tile 1111clolwk I loll". 11 call be scell that
C. D. 's above SA cnC ill(- deposit begins to
ill
exhibit
polo%liv
(lite to tile leductioll
but
not
liticlealloll
site% alld
growth,

a,

(I)II)01,

IP?'.

Ri-

I? (. "

D-0,

11 6r19
Ah.

10

(c)
iAurc 7. (a) PlaltrrR raft, vs current densils,
0.08M copper. (b) Plating raft, vs current densil w,
0.204M copper. (c) Plaiing
raft, vs current
densilY 0.8M copper.

-.

_-'i-_
.

4-.

\_.

'_.,

"I
ict

While

01

hel

tlc(i.
"pOI %N heing 1)1;
L-I L:

7(a), (11) and (c) show the

bt-1--cii thc plating rate and
lelittionship
101 C.tdl CICCItolvic. As tile
(IC111,11V
CIIIICIJJ
11"ed
I)CI
[)of
wits
Coldoillh"
Of
,
lItIllihel
be c\Pected 111M the
-)"Id
it
cOnstani,
tile
O\Cl
Ictilaill
%%ould
koll"lant
IMC
111jitillp,
be Seen I bill ilt
il
call
\III
(ICII,,
L-kilI ell(
tile pkilmr ralc I., IOw
IO%kLjmem
C.
D.
here
II
IllklCti'llilg
%%)III
iIII(I IIICIC-VC
lot this behaviour.
be
W\("JI
coidd
dcPOd1
tile
IO\%
IIMY
(IcII`iII(`,
A(
Mlelll
be thill a" the "pread of' tile spot
Io
Ipjlcal
be
[lit'
be
may
Ic.
scleclivilv
gicalci
lljjN
he ano(het teduction
Ilicic
maN
PO()I
IMIlogell
evolulion
or
W,
such
jcjcnorl
tile
V
effiOk'11111w.
,
IC(IlIkIlOll
...
get)
O\\,
depo"Illoll
proces's is
tile
COppcI
Of
ciellO,
IW"o M IO\N c1l"c"I dc"silles. then
I,, k"IlIkeIN (o be the
horell
c-11111011
b\,
Hic 1111111clitcof o\\p(. 11 Ickilloioll
C.11",

122

10 Ah. 'q
V70 At'. 'q
0 3.0 Ah. 'q
4 5.1 Ah.
X 16 Ak.

E-

V.I., Iy IQ0 01-

FiRure

8.

selectivity

ont

The effect of
O.NAf copper.

current

denNitv, ()n

was not examined for (lie copper system but

has been examined for the gold systelli.
Figure 8 shows a plot of the selectivity of
spot,,, at different current densities. R is a

110111 these slics. BY

of nodules
lilelging,
tile pCiccullagc
gross polosl(y,
Illeastiling
tile dimolling
ClIck-1 10 tile thickness %'sC. D.
I lie polo%ily
Curve Could be leduced.
was
Wilhill tile illiclo%ections
using ;kit
illeasuled
Video Contrast
Image Analyser.
Optimax
from
The
the
was separated
polosily
deposit
and file [)tousing image colillast
of I)oio%ilV to melal picsemcd
its a
portion
The thickness
measured
was
percentage.
bN this pelcelitagc
to give tile
thell ledliced
ciifvc ill Figure 9. It can be seen
resultant
that (lie slope ol this curve is considerably
for
reduced and is closer to (flat expected
deposiv% ploduced
will) .1 Constant 11111111wr
Fills porosity
(lie
explaill%
of, Coulombs.
tendency t'oi lite deposit (hickness to appear
density
was
to increase
as the current
increa%ed paNt tile optillillill
C. D.

The Fffect of Metal Concentralion

'I'lic incial ion content of tire electrolyte has
a Nignificam influence oil the depo"its. Low
nictal ion Concentration,, gave rise to low
maximum uscable current dcnsitic, above
which a dendlific, POWLiCly structure
formed, with pionounced 31) nucleation.
At higher inctal ion concent rat ions, higher
uscable curtem densities were obtained.
The deposits deteriorated above these
values by nodulc formation that became
incicasingly incoherent. 1-igme 10 shows a
plot of' the maximum ckment densities that
allowed colicient deposit,, to be obtained
for different values of Re. I lie deposit
I'llis
IlliAtiesses weic approximately 5 11111.

lHatVilikill)

ICIII

,M

kl('1111

k, 11,110\(

% CT

dcpCIIdcIIl on Ihc 011,klic of 111CdCpo', I1

helfir ohlailled
%kilh all Im lcilwki
('cc IIIc I- If cc( of
aIgI ca IcII 111tkII
III C1CVdlly

I tilt

lopoplapll

INIIC)

I 1'IJIC II
dcpoll
a -1 pill
for
tondllloll

of

IIIC

110'A

plodilk-cd
III(- 0.8\1

opiIIIIIIIII
CI CLAI( )IN W N( )IC HIC t III. tk L' ('It 11111)'Of 111C
hN I lic
bat I, \k&dl
file
Itlwd
(I CpIIIk
of
Oct (I OIN Ic.
III, ica"111),
I 11L. 111(.( al
loll
Io \ahlc
111all 0.8NI
colit: C1111MIoll
vicalcl
tindel

inclew,
dllilllp
cIN"'lal

ed

Ow

hkchllood

of

clogrillp

lIo//Ic

(111(. 10 tOI)I)Cl

IdIc pcilo(k
JoIllialloll

,UIJ)IIMC

I he I-Ifect ol Flecti-4111%
ic %ch)(AN
Ali

fl()%k iaw, m, jcipc(j (lie

loow
11 MIJA
po%%dcl
(IcIl"JIN
L"Illicill
dcpo,, I(,, lottiled
llmkc%cl,
'Ai(Il [Ile
mik
O. XNI clclwklc
did Illc cl()kllv
mplull
callik, Inkica"c Ow kullvill
(IC11"wN al %Nhich
dcpoIIN oll )ookl
It
%%Cl(-ploduccd.
1
10 (hill Ille 0.8m
Lilll be -,cL-ll llmll
11(m, j 111ca"mcd Illaximil
clectfolvic
al
lit Ilic

imicxx

lci, lon led 10 Hlk I c: 1, k dIm hidcll, C dtic 10

I 11CdII IC IC IIII it I Cl( K:I I\ hC I %CCHCCIII It' i III d
cd 1,c, IIII \k oI II (I ha\ c : ilt I cd it I ocil I ued
thilmillp
of IfIc kill I lINIon klcl ill Ihe edge
Of 11h, I III Pill, (, Illclll /011c, 11) m 1) it sit It&
It( m, Illidl
nod tI I(- I hal ll; ikI ,I ; II I ed to
'l M%

IIIcmI

"cl

m )(111 Iv
\k il

I'l C%k IIH 11 CI

of

I ap)(I

I u[ I 11cl

pllcl
I\

pI (-\\

(]]', I III)l

;I I) id I\

hk

I) I Ohil

(I He

hc
.I
cd

.
ck.,

I I( m()I
lc; ldlll,

10
I he

\s

lk 11 (1111 111( )II

II ok

(c

IlljOlk

Ioa

lulbulcm
;tkc III 111k.dilcolon
of I Io\\ .
I 111 Icd to it lullf1cl
11111111111P
of tile
dlllkjloll lil\(. [ III 111C
dilc(Ilon of IImN and
\k;t CIIIIA11IT(I III IIMI kIlICCHmi. A..,.
lakc plac al it "Illidi
phcllcill kilifil"loll
I; ldltl 111) al a lillc "cketal otdcl of
a
Illaplillildc pleillel 111anplallul dillilsion,
m-cdIc"111IL-Illic lapidk tomwd III Owdifec[loll of 11(m.
A no//Ic to 111)Ilalc di"(illice of I InIn
/ hufe

/()

1iu, u,, uu,uu

tffuI

/uh!

/t

uis/uI

2710, md Own lalk %%iih incteamng Re.

A mulm hcha%iom
i weii %%i(h gold and
,
I \aIlliflanoll
%%Ill be (ll, LtlYIC(l lM(I
of
I iytjic% 7(a), (h) and (t ) IioA lhal the slope
,
ol ill(- plaimp
talc, ( . 1). cum- v, ic(luccd
"'1111 mclcalnv
%(-10(11. h I,, likelv Illat [lie
dcpo,, il.-, Acic bckommy
mole compao
and
lcs pot oil% as I It(- %clok 11N, %%aincleawd
as
1111',Clf(Tl "'it, ICY, 11011CCithICjjN [lie IIIC(ill

12,1

1 iIII(I

14

llllkkllv

Inclea"ill),
( III [ell[

,V.!,.
IV,
11,
I, -

dvll,

howil

Il Nk

IloA
(Ilk-

of

IlOdWICS

nodule

III

\\1111111

"ho\kk'd
111

-lialo"

I(TIOll

HIII)III'CHICIII

dcpoltioll

IIIIIOUVII

tt

01 0.4 111111%%a
a dialliclel
1[. 11 \a, ' liol possible
Ilic pic"CIlLc ol afl dcpoNII b
OIC DAIA.

%,
kilh

ob"cl \cd
lo i(IL'Illll\
Illikkilk", 1

11
I.,

no

kffltljllkk

111011VIIIlllil(

I,

tomm,

IlICIL' k%IS
I
thit -Atit

iri

AAMEFMHR

I Ilickiles's

%%tl III

the

effect

I lie

t1cpo"w
CWCY,

of

of

thal

('011ducl\ c to ( olli-I (.111dcpoll ill a thick

1.3 /an)
lie%,,of 4 pm AI Im%
the dcpo"ll kollNckl (it "Illall nodwile",
lalp'k-IN, 1111conlic'Icd, of ithoul 2 14111111
(himiclei. At I lhicknc,, of 12 jan ceilam
hild
lcildlllp

k%;i,, 111LIcawd.

I he I'll lecl ol hIcreasing

I 11"m C

I he I IfccI ol
kill-cm DcIv, iIN
Ilk, (. 1lk., ( ol
III Ik'lII dk-1111\ oil dcpo"It
III, kllc' I, \, -I%
Io Ilial of coppcl
Lovk L-Lillcill dcll,, illc (IA
'cfii-) ga%c riw
deir, 6 ol 0.25
\ timciii
io 11m) (lcpoh.

h(I/)/hC! u1,, uuiis

kc

collicill

P"Ii, lc toy ilic bulk ol

"', I"Hl', l i- i,,
11111
Wl k Al OWIC %kL'lk'no (fillicullwN "ith
III(. 110"Ac bt-mv cll'Illlcd h\ tile clectiolyte
AlIll 111ClllllklCML' 0I IIIL' 1,111101111(ti[Ig
d 11 no/Ac to whnalc
ill 1 1111111111;
\Nil(.Ic 1) Is tile llo//Ic

Mid

10
wc

Iumc

had

clljtllfcd

LoIlclcfi(
Illk-Icast.

-d

R.

othel"',

'111c

"Illichile.
1() applommalck

6 jan. Al it thickness of 0.' m. ilic iwdidc

"I/(. had Inctcawd to 2 pill
'01'1) DIAIII)SI
I
"S
1AI'v(. 1 ol Nol/It.
lloli'cd
dis(MICC

Of

0-

111al
111111 iCd,

I)altiLLIkilly

at

10%

velocities, to the lio//, Ic being engulfed

in [lie cleclio1vtc wash and thus behaving
its
a subincigcd jet. Ihis did not occur with
copper and I,, piobah1v due to diffeiences in
surface fension between the electrolytes. It
was theiclow
neccssaiv to use a greater
no//Ic to suhstiale distance. In order to
establish 11m% III],, Would 11111ticlice tile
gio%ih paticin of tile deposit, it series of"
spots were pioduced at dillering distances
over tile iangc 0.25 min III) to 3.5 min at
0.25 inin inicivals. A cuitem densifyol'3.0
A/cill. ' and a vc1ok-HYof 18 m/sec was used
at a levillma(me of 40' C using clec(rolylc
131.11 \&-asfound that at disiaticcs greater
than 1.75 mm, iadial needle snudiucs
started to 101111'1. III Figuic 15. Ihis was
due to tile oulci pall of the electrolyte jet
slowing doml (file to %Isko.
se djap, it', it
passed duough III(- aii. I lie gicam
the
distance, the gTcatcl [lie diar. \\'lie" tile jet
file IO\-.C1
1II)pjIIgcd Oil tile silb"Ilatc,
CIOc'II% jj IhL' Cd)'L- Of tile IIIlj)iugC1I1CIIl
%,

/I i'll wI/I
A /I f? l '.

)/111111it III
IIIht,

II )j 1/

1, '/ "I It.

A fl cssR27

copper

FiKlift' 12. I'lit, cf/v( I t)l mcrvusim lhickncN on

deo) sII nunpholoo.
C
m', Ih ickricv%
2? j, III, Rc / ?0. () S%f

hi! urv 14. The (Iflect o/ im reownQ MICA Flo'" On

,, (, f('

1)

57

.1/,

62.0 , m, Re 1365,0.8A f coppet.

/ jpjf,' 15 1
formed wili,ti /11(,
111,

it-pe %fruourv%[hill
(o m/m/rale dwance win
mm 0

MaNgARMORAUC

123

hydrogen
ion
a.
s
Such
react
ing
com pet
Jhe effect
reduction.
or
oxygen
evolution
by deestablished
was
reduction
of oxygen
by bubbling
nitrothe
electrolyte
aerating
it for 30 rninute,,
to
prior
through
gen
deposits
It %%a found
that
deposition.
dc acrated
did
oluhom
produced
deposit of 0.3 pin at
mewmah1c
a
produce
A/c,, )-' In addition,
0.25
an
of
a(
-D
in deposit
thickness
of approxiincrease
1), of'
101"o
to
up
a(
seen
"as
nialcls'
.
incicase
1.0 A/cm2
alter which no I'miliel
tiom

was Well.

in order to establish what was happening,

deposits
were produce(] oil
of
a nuinbcr
Dcpo,, it,, ill) to a
s
substiates.
gla,,
sputiciccl
current density of*7.0A/Cljj2 %Cie produced
0.576
of'
coulomb%
of
total
number
a
using
[lie
pioces,, was
of
tile
efficiency
all(i
bv
the
Plate, %cigh
nicaNorccl
ho\x,n in
the
are
elticiencies
,
method.
I lglile 10. It was possible to lucasuic file
deposit
[lie
file
OpliCd1k.
Of
Sl)[Cad
total
layer \&,;is thin
gold/chionic
%pullcled
light bealn.
liallsilm
a
strong
to
enough
ll()wcvci,
where deposition had OCCuircd,
tile light was extinguished arid this point
deposit.
identify
[lie
ot'llic
edge
to
,A,a%used
'I lie diamcfers of tile spots were measured
to
allachcd
a
ing
inicromeler
eyepiece
an
U%
.
Figure 17 shows
low p(mei microscope.
how file title diatnefeis varied with current
den%ilY. it is evident that a( low current
dellsims, I lie deposit sprcads over a greater
is
low.
higher
At
bill
(lie
efficiency
distance
is
ilicleascd
tile
efficiency
current cicusitic%,
to about 70% and [lie total spread of file
dcpo%ll coincidcs with that a,, incamued by
tile I)cklak.
file cathode efficiency bchaviom of file
is %initial to that seen under
Iioly(c,,
clc(.
(ICI)OSitiOll

C0jjVCljtiOljjI

conditions,

90

1'. p SbC

Y. l. ly le

i-

OH 01

(0

t)41

"0

101
0

)46
Cii

D.itily

Alt.

tq

hRure 16. Currem

0.17M citrate gnId.

carilly
current
deposits

structure
alfccted
densities

is signifiof' the deposit

density.
At
by current
the
above 0.25 A/cni-',

Figure

17. Current

Inaxinnort

denstit,

spread

11.1/d
if

/)

aw

60

opt/w,

p/l

%-%(lopo%il

v%,,
(/jjj

of %poi%.
wAll

/ Ipule
10 ( ... low
domiti
.
diflo-rew
pold corn cfill o/ 14,11

1,14 ltSI,.

platim,
Iti(Ile

for

taic

wll of vir.
41/4

l. I.,.

OOIM

" 01I

44

041

44

I.. p

(
I

S.

234
Ciii..

I Doilly

AIrs

.q
kv

. 11-..

'0 1
.
0-11,

Ah.

. 11 '...

40

1
Q

66

on

I10n
A 76

D41 M

a 11 .

I
.* [0

...........

Figure

N-ow

'rhe Effed

exhibits

ol current
(tensity
on
-1-he cll'cct
be seen ill Figure 18. It can be
can
selectivity
low current densities, the
al
filar
seen
is poor. As the C. D. is increased,
%eleclivitv

structure

than

gold

maximurn

maximum

was
the

creasing

plating
obtained
8.1 was

3.4

A/cm2.
in

obtained
structure

At
maximurn
current

19.

0.17M

this

series
of'
deposit
this

It

can
the

and

a slight
density
and

seen

much

plating

pi I
of'
rate
The

be

that
less

vent ional

late

at
density

experiments.
call

a
in-

to

clectiolytc

be

coil

tile

where

pialing

at a current
pin/sec
This
was tile highest

of

Figure

useful
current
The
maximurn
the

so

However,

the

rate.
from

ill
seen
jetted
(lie

angulai
deposit.

of" 0.28M,
tile
plating
rate was 2.9 uni/sec
a( a
density
]'his
of' 5.0 A/CM2.
effect
concentration

i,

21

Iffle
clifoll.

ertnt

ol

com ('1111411foll

(Off

Rold

wa" ako seen if) coppel &. 110"if1011. The

lea"Oll lot thiN Is that 111glicl Inctal loll concenflations
allow Indkidlial
IIodtIlCN to

density

at 0.17M
led

reached

1.1gurf,
Ae/tIclivill'.

increased,

was

concentration

in

reduction

6.0

content

useful
curient
increased.
rate

plating

derusils, t)ll

of Gold Conceniration

deposit

the

Is

improves.

As

61.0,

... d

18. The effect of current

selectivity 0.17M citraft, go/4r/.

tile selectivity

1'. 0 *,[

4,

1'. 0 Y, C

front S111001111
and (full to
changed
then to bright ;is the C. D.
arid
serni-brighi
followed
by either a
This
was
increased.
growth
or ncedle
arid
Structure
nodular
above 6.0 A/C1112 (lie growth pattern
finally
dendii(ic
a pronounced
with
becallic
I lowcver,
lield cuientated
growth.
dendlitic
(4] no dcndrific
electrolyte
of'
it, tile case
It should be remembered
seen.
was
growth
deposit
thickness
also increased
the
that
density
incicasing
current
arid this
illi
,A,
have had all influence
oil the deposit
would
(See tile Fflect of
and appearance.
structure
Thick ness).
Increasing

124

-11 [it,
1 /l/d/1111, fill"
Irml,
s(

8/

being

The

//1,

1Y

p/m/m
i'd fit Ifle Ilf"'ll".
(( ltrale
ele-, troh ie-,
A/cipy. '. Re, 0.078.
plation,

Wi(Il

low
al
Observed
low efficiencies
incicamny, a,, tile
densities
and
curiew
*Ilii.
iiicrcitscdl4.
%%%,
otil(ibc
(iciisityi,.,
cullcui
F" (rest potential) value of
[lie
as
expected
V. A( a pil of 6.0, the
is
about
-0.61
gold
V.
j:, 1 value of hydrogen is about
-0.3
a signiat low overpotentials,
'I-hereforc,
be
hydrogen
cowill
of'
ficant quantity
deposited, rcclucing as the overpotential is
been
it
has
In
shown
addition,
increased.
that the reduction of' oxygen also occur. %at
It
densities".
would appear that
low current
behaviour occurred under jetting
ilmlat
a
condition",.

denwi

%-%
rurrent

glow

laigel,

I III',

cffccl

IN alNo

Clillank-ed

VC10(.111C.
flial
N. llll
Inklikatcs
lucclialli"Ill
and law of nodule
glowth
dillivoon
connollcd.
I-iguic 20 shows tile plating
late,, lot
difTereril
conccimationN
of gold om
glealel

by

(lie
is
life
file

C. D. lange used. 11 call he

that al tile
seen
towel cutictill
densitic,,,
Ilic plating iates are
but
A/cm-',
coincidental
abo%e 10
tile
curves
no longet
coincide,
%vilh lower
cOncentl

at loll

Clectlokles

"llowing
all
1'111 wits
appaicnily
gicatei
plaiing
iatc.
lacl
to tile
(tile
flim
al high
ClIfIC111(
dcII1, IfiCS, (lie delIMIN' of' file deposit
fell as
delvimiated
tile deposit
qualif\
(life to an
inclease
ill %olds. 11 call he well Illat tile
CUIVCS I'01 thc 0.0411\1 and 0.28M
electrolytes show a "ignilicant
deviation
m (Ile Iligh

(1)'

Ilk

') II

11"

I I] I"CII

IhI

ill

I C1)1

01

II RIS

111C
%N1111
pool d(-po'l(N
11(1w depm II (I II; j IIik
k it I, ('' %%
Icill'Imcd
I\ )'41( dm
I c. I ' 11.11)
cl II It, IIIII, t 'h, m 11
Md III I'l III CtI III . 11111t)NIIllic'11 I clal I(
I WHIC

21

I Ilk.

till
I Ilc

IIJL'

NIIWA

CII('kj
Il

wIk-kIl\II\

'cI ('L II% II % I

twl

! hc -p

I lic

(h)

lwl

)', l hIt.
il
(
mil

ol

I(),,

1)

I Ilk

I
I ll(.

(k

p(

)111

tl lay

mc

N(.
k

ill

lit-,

;I

)I
I

Id.

11

p[

)d

11, cd

Ollw

"1111 pIt

11111),

11 11, Mw

Ilm%ll
ht.

(-Ilk"

III

"t-cli

II .
(

[I),
1"

I,

, .,
Ilt

)
Rc.

N (. 1),
R

I lic clfcL: I of wnipcialute

%a,,tiol piccvcly
for the same valuc,, of Re.
(-tiih[Mied
llo%kc%cf, Nome pCileral Colic I usioll call be
di; mn hom the morphological
diagiams it(
Inclea%illp
I lie
(1111clem
ICIIII)cl ill Mt. had il "IP111ficaw effect oil the
dcnillc.
I-ol
liliMilltill)
Ilwah1c
LIIIICIII

I.,

wurg, .15(a)
fitati, kold,

of I emperalure

L'IcLitokic. At 40''( fill,. increased to 3.8

At III-' and ill S5"(, to 4.0 A/ciW. I lie most
noticeable effect was oil 111cdepo,, it,, that
had it poor sliticlure. I lie 0.28\1 c1cmOlYle
pIodtIcCd dcpo', il will) a liall"mOll point
110111%Illoo(ll to IIcCd1c (vpc deposits 11
2s C hill ill SS"(' file lianilioii
wa to a

I plit

Af"rphofiwi,
lefrip.

Ilic

al thavi, im 1w 0 041 if

2s (

othel
mere

strucitiro
at ,, (

W
II

It lat IIIrtILIIIICA

,A)HI

(lie
illii\lllltllll
uwful
culrelif
den,
2S Cand all Re.
tl it[ it lempeialmeof
6(XX) %%ii 2.0 A, cm-' lot (lie 0.28M

k% a"

,II

1 11,111,
111.1t

. 111

I he V fled

uwahle

1N

cI t 1,11

a pAlIlk 111,11 111will

11111 c

2,

n 11 Ill

h IpIk
'Ind

clilliel

Icd

%vII)AIIN
It

Im

IIIIIIIIIIc.,

'wc

lit

AIII

111al
. 111c,

I", I

Ilodillal
I I\

hc

all

Ipfilllk'llllk

IIIv 1 M-41 Ill 1 lelflokit.

Ikt

11

"; t\ increa,, ed, ,o the maximum

, turcill defl%ilv increaNed.

M)d

I ItvLIf

1111111 It IC

wen

I"

Needle

clc,: ITokIcs,
onk

C'

at loA

Re.

It'

NCCT1

ivpc
altjcs

of III

1)0IIIIIILItIreS
\N.ttI[IIIIiIc
1111111'1ckl
; it a I)II (it 8.1 lot hoth 111(-0.28%1
I IIIN AlMkCd a
and Ilic 1). 17M
gicalcl
plaimp
Itic to he t1wd. I lvulc 20,
27 and 28 I)o\k (j(: pojj,, lioni ilic 0.28M
,
eleMokic
and 81 icj)cctal JAI S. 1,6.1
i%cl\. An inticawd
plaling iaicai ilichipher
JAI \; Iltle %kotild bc C\I)k. ctckl a Ihc I% altic
lot Imito. mi
( 0.5V) IIIIICLI 11OW1 10 IIIC
dCl)(1111011
101 )'Old,

I lic I-Aft-cl ol ( onducliNil

I lcmohlc
,%
ISI
%a

Olal

a lo%%

colldllcllll\
oltllioll (ould hc lc(Cd. Ilic
conducli%1IN wa aboul hall Ilial ol (tic
I

(,

it'/
lemp

fl"I
) (,

11,'/I
//

I ,t1,1/
(/

i-old i, imitt,

llm

__I_7"

.. 4" . ",

--

v , - -/// ;, T'l

Vi

"I

* \

1.
... 1h

-:.4

Ai
1W,i, \Nj Wt

lph 1. OlM,
1, - 1r
,,

A.
11,

/ 11!141(- '(II)
-'
(Iffalckold.

Aforld'oh
/em/p.

wl, al dwi-fam
40 (

for 0.04 / Af

I wim, 2' Ilw

io pl/
1)
ch" lr'h 1'.), j'/I e, I(
lemp s(.
I hi, Ati. " 1)

0 ?,VAf t!old wilrate

1 ', w', Re
/11

T,. p 40 C

A
N,, dl, 1".

N. d. U.

Iff
"l,

/", I 'If M-1, Wwei1, wb-!,

Wo

.",

1000

Inm

Rc
malc

/ igure 25(c). Aforphobwj,

( itrate gohl, 7t-nip. (

aldiavram

1w 0 041M

/ .... ... 28 Pic

t ,I plif () 2,,tf vold (I arafe
1) 1oI.
rit Rc
p1l SI(
ch" lf"lk
hl, Afic" /,S 1) III
I ctill', Ss
,I

EI
U

s"I'll

i)

II
4,W

llo

170DO

125

technique% are required.

photo-lithographic
By using direct writing, the latter process is
not required as the gold may he directly
written onto the mciallised substrate from
the CAD design. Figure 33 shows a simple
ring oscillator circuit produced by direct
writ ing.
I lie

%elective plating
omponents.

u 4aruiv
gold deposit from
conventional
tinder
vIt" produced
electrol.
C. D. 5.0 PnAlcrn2.0.06M
gold.
conditions.
ThicknesIv 18 vIn.
A

I 11furl, 3"
A 11flill"'I
,M lilt 1""Ild
direct
wramp
wi a if(dd (-t( h rcmt

held
belweell
Component%
i tibber
maA%. 'I lie direct write system will enable
to be produced
such componen1%
at very
high plOdtJCIiOo MICS Oil ;I L'OlIlintrous
basis
tile liced lot CXI)Cll%ive nla%k% as tile
without
The
spread of tile dCpO..,il is sell limiling.
of clcctrosize of tile plaill and tile quaillity
lytc ie(jukcd
will be significantly
reduced
leading
to lower
capital
and
expendilure
tile

II

tatci

throughput

linics.

4) Iltimp plating ol''FAII

Wrot Pe.,ity Alto sq

30. The effect of conductivity

rate, 0.28M citrate gold.
r-igure

on plating

FIKule

33. A imp ou-illalor

produced l?v (Iif(-( I wrifillj"

im(tiowave

(weitil

deposition
understanding
of' how
(ak"
place under free flow jetting
ill
collditiolls
terms of useable dcl)osi(
'I'lli%
situctuics.
will
cnablc
thc systcul
to be applicd
to
production
or prototype
processes. Some of*
tile possible applications
are listed below.
1) The

direct

printed

writing
of
boards.
circuit

c(ch

resist

for

The

densif of?
The
current
31.
of
effect
i., gure
,v
Lowconduclivit, electrol-vie.
selectivity.
30 shows a com1--igure
other electrolytes.
between the apparent plating rate
Parison
the
and
electrolyte
low
conductivity
of the
be seen that the
It
can
gold.
0.28M citrate
exhibited a
electrolyte
low conductivity
plating
rate.
apparent
greater
Much
Figure 31 reveals that the
of'
1.xamination
,
low
better
is
the
with
much
s, leclivity
electrolyte and this explains
conductivity
This electrolyte
rate.
plating
tile greater
best selectivity of all tile clectrotile
gave
R
2.5.
maximum
of
a
with
tested,
lyt's
deposit structure was not as
the
jIowcvcr,
higher
conductivity electrolyte,
tile
as
1ood
large incoherent nodules occurring at
with
densities as low as 3.75 A/CM2. At
current
density, a plating rate of 2.3
this current
/%cc was achieved.
,,,,
'A'I IONS
I(
APPI,
is to achieve a full
this
work
of
,1.1,c ptlrl, ()s(.

possibility
of the direct
writing
of a
metal etch resist for PCB prototyping
has
been examined
using gold as (lie resis( metal
(Figure
32). The
in this
tracks
written
example
were 3.6jan thick and written
al it
linear velocity
of" 1.0 nun/%cc. 1; xanlillation
*
of the tracks
revealed
a very good edge
definition
even when using it I'ciric chloride
etch. Whilst this process may not lend it. sell
to high volume
it is very
production
work,
for prototyping
low volume circuit
suitable
boards
direct
from
design.
a CAD
Eventually,
it is intended
to dcvelop a high
speed

tin

electrolyte

as

in

etch

resist

material.

2) The
direct
writing
of' Microwave
Integrated Circuit Substrates
Microwave

Integrated

recl-to-reel

I tit r. c volumes of %trip or pressed trip com,

i)oncnl% such as conneclor% and lead lramc%
ate ctitmilly
produced
cidict by contiolled
depth immersion
or by jet deposition
with

;. -

2v,

Of

Circuit

Substrates

are
throughout
used
the
teleconumini
I'or the mounting
cations industry
of' active
devices such as amplificts
etc. 'lliese
;nc
usually inade f*rom sintered alumina,
quaw
or PTFF
The
composites.
ciictfits
are
by niciallising
produced
by
the substrate
sputtering
in
and the nacks are pioduced
the conventional
by gold
way
clectiodeposition,
either by [lie addative
oi sit[)
Either
tractive
method.
way,
expensive

kknds

indusity
IFlic electronic
makc. % u.%c of
bonding of' thin gold
thermocompi-mion
Wiles from inlegimed chcuit% to the lead
franic connection% within tire IC housing.
This requires at gold "hunip"
to be plated
onto tire connecting leads of the lead franic.
At present, this is carried out using cithcr
pholo-lithography
or rubber masks. The jet
plating process will allow tire production of
tire need for
these "butups"
without
masking.
There arc a number of'other applications
of this technique Which are Company Confidential but it may be concludcd that any
selective plating [equilcuncill Inay be Carried
out Willi (lie direct Write jelling technique,
even on complicated geomeny componcrits
and Willi any metal or alloy, provided thal a
fotniulafion
suitable electrolyte
can be
pioduccd that allows high speed deposition
and is not chemically aggiessivc to either
file sub%trate or the dcposi( produced.
CONCLUSIONS
It ha% been shown that the behaviour of
both a simple salt copper sulphatc electrolyte and a complexed salt gold electrolyte,
behave in a similar way when deposited
high
under
sliced jetting
conditions.
However, (fie copper electrolyte exhibits a
slight chemical attack on the deposits
produced by the electrolyte wash.
The fac(ois that influence the maximum
densities
useful ctmew
and thus the
maximum plating imes that produce high
quality (icl)o,, it,, aic:
a) The electrolyte tempeiature - tile higher
tile temperature,
(tic greater the plating
had tile greatest
rate. This pitiametcr
itil'Itience oil (tic gold system, presumably
because ol' (tic reduction in thickness of* tile
dil'I'lision layet. It has yet to be established
wilethel Copper electrolytes exhibit it Similar
tempeiaturc dependence.
b) The electrolyte velocity
the greater the
velocity (of' Re), the higher (lie plating rate
that can be achieved.

c) I lie metal ion concentration

increased
ion concentration%
lead to higher
incial
plating late% but only tit) to ;I certain value.
Above

(III-, value,
no improvement
or a
Fcdtiction fit meful plating imes I,, ot)%crvcd.

Gold (ICI)O%il%MC A%0 inflUMCCd hV rile

pit of file clecliolvic, file 1110%I
%tillable plf
%&asfound to be H.A. A Imilici imica%c fit
pit wa' nor lc%lcti a% alkaline cickifolylc%
for c1ccliollic
alc Y.Clicialiv
application%.
I-of

both

v%IC111%,file dcpo, %iI s1rucillic

%,
tifidergoes Coll%ldclabli: change. %ill Illorpho
logv as file curmil
den,. ity k inctca%cd ill) to
it point %&-here(lie %It t1clurc deteriorate% due
to i%ol; lt(. (l 110(lille formation.
I lie %ClCkIIN ll' 01 file I)IOL'C%%WV, not
by file above pala
affected
%1glillwantly
HICIC11. Willi the exception
of file Cillicill
Low
(Icll%itv.
current
(Icrl%ilic%
OA/cin)
Oiow it gicaici
(-I
%picad of the
depo%il,
[lie llllckllc,, of [lie
although
deposit oii(%Itl(. the 1111pillp.c1licill legion I%
As file k tit tent dvn%ti v i% mcrca%cd,
verylow.
%ClCkti%'ity i% 1101 %ir.11111k;
MON ;lfICL'tCd.
I IoWcvcf
demlly
i%
(tic
fell[
lilt lca%cd
(ill
, it%
pa%t the point at which deterioration
of the
dcl)o%it occur%, the gtowth of [lie depo%it I%
influenced
incrca%ingly
by the electric field
is limited to
within tire jet and [fill,, gtowth
within the jet stream.

The selectivity v. most innuenced by the

conductivity of file electrolyte. This is due
to the fact that (tic electrolyte within the
wall jet region is extremely (hill and (herefore has a high electrical resistance. By
the wall jet
reducing the conductivity,
region bcconic% more rc,,i,,Iivc and therefore
tire degice of laicial dcpo%ition i% reduced.
Maximum planny, late% have been cs(ab
khed lot both sy%tcms. I-or (lie copper

system, at 25'C, (he maximum plating rate

was found to be 1.6 jim/sccond a( a current
density of 6.5 A/crn' ming a O.HM copper
The nicasurcd Reynolds
concentration.
number was 2730. The maxinitim plating
title for gold using e1ccli-olytc 141at a pl I of
9.1 and a icnipcrature of SS"U ww, found to
be 3.4prii/%ccond. 'I tic rncasutcd Reynolds
numbei was 12,078.
Thi% work
rcprc. %crit% the initial
results
from a longer Iciin study of (tic
obtained
let Flectrodeposition
Ifigh Speed Selective
analysis of' the restilis and
pioccss. Ftirdicr
is
of the %ainple% produced
examination
and will be prcscntcd
cotilinuing
at it fillet
datc. NVOlk will continue
oil the cliflance
Flicill of [tic plating tale% lot the gold and
0111cl 111clal and alloy %V%Iclll".

3)

4)
5)

0)

7)

8)

ACKNONVI

11-

Oic IoI hillik MI lan Gu lit cl,

'I licit it I lit t %%I
Hirst
Research
61oup,
of the Mctallmgy
for his invaluable
Ccntrc,
assistance in tlic
design of tire contiol
c(It6pinent
and the
that
thk
programming
madc
computer
also go to staff of
work po%%iblc. 'llianks
Assessinctit
[tic Malciials
and Componews
Ifirst Rescarch Ccnirc and the
I ahoratoiy,
Unit of 111C LoughMicroscopy
Flectron
for
borough
Unimsily
of Tcchnology
thc SUM micrographs
prcscnted
producing
here.

Rf-'Fl-: Rl-: N('I-'. S

I) US Patent No. 3,810,829, May 1974,
James C. Fletcher, NASA.
2)

K. Ramachandran
R. Hayncs,
I inebefg,
"'I'lle
I echniquC
How MwAing
Selective
We.%tvrn Electric
Engineer,
(1978).

& D. J.
of Fluid
Dit,
22,61,

9)

R. E.
Dorey
Haynes.
J. K.
11, R.
Sinitski & R. F. Woods, "ThcrmocomSpecd
Ifigh
Bonding
Using
prcssion
Mal. & Surf.
Plating-,
Selective (iold
Fin. 67,81,
(1980).
Speed FlectroW. H. Safranek,
"Ifigh
Ibid, 69.48 (1982).
plating",
I-A. 'Natson,
-The Radial Sprcad of a
J.
Platic",
Liquid
Over a Horizontal
I-Imel Afech. 20,3,491.
&
6. G. Pokusaev
V. F. Nakoiyakov,
F. N.
I royan,
"Impingenicni
of all
Jet oil a Barrier,
Axisymmetric
Liquid
21,1175
MI. J. Heal Mass Transfer",
(1979).
1. 'Imi,
Layer".

Junlp in tile Boundarv

"Willer
4,212
J. Phy. s. Soc. Jpn.,

(1948)
T.
'I a na kit
"Fxpeimmital
Turbulent
Jet",
792 (1970).
If.
Schlichimp.,

F.
Ta nak it,
&
Study
of' a Radial
19,133,
Bull. JSAM,
Layer
"Boundmy
Nc%
Mc(; raw Hill,

Theotv",
4th cd.
Yolk (1900).
J. Clicn, "llighSliml
10) R. C. Alkirc&'l
Single
Selective
1; lectroplaling
Willi
,
Soc..
J. h7ectrochern,
Circular
Jels-,
129,11,2424
(1982).
I]
Tsang,
"Ma11) D-T.
Chin
&C
Jet
Tran. -d'er
Impinging
to
all
Flectrode",
Ibid. 125,9,1461
(197M).
Uni12) ,FA Chen,
Ph. D. Disscrtation,
UrbanaIllinois
vcrsity
at
of
Champaign,
11. (1981).
13)

14)

Enhanced
C. C. flocking,
"Laser
and
Ifigh Sliced Jet Selective Dcposition"
Tran. v. IMF, 1988,66,50.
Gold
RA
Page,
Review
"A
of
.
Llcctroplating
Part 4".
Solutions
Met. Fin. J. 20,229,4
(1974).

127

EdelmetalleModerne Technologien
Anwendungen
und

tra U41I

eLlf Of)VdII%,
academy
of surface
technology
schw,ibisch gmund

If wnIi kil 0I
iA )( 11-11
hvv.)bl( h C'mund v V.
I utivri G Lewiv Veilaq.

f,

B est,,
",
I.

.,

Available

-Co

py

The High Speed

Selective Jet Electrodeposition of Gold
By C. Bocking,F I.M.F, Wembley,Middlesex(England)
Selektive elektrolytische StrahlHochgeschwindlgkeitsabscheidung
von Gold
Die selektive elektrolytische Strahl-Hochgeschwindigkeitsabscheidung ist ein Verfahren, bei dem
eine selektive Abscheidung ohne Abdeckung erfolgt Das Prinzip besteht darin, da ein freierStrahl
desElektrolytenmithoherGeschwindigkeitaufdas
Substrat aufprallt und dabei ein elektrischer Strom
fliet Durch die elektrochernischen und hydrodynamischen Eigenschaften wird Metall nur an der
Aufprallstelle des Strahls und in deren Umgebung
abgeschieden. Auf diese Weise wird eine Ausbreitung des Metallberzugs begrenzt. Ist eine geeignete Anordnung vorhanden, kann der Strahl computerkontroffiert so gefhrt werden, da unmittetbarLeiterbahnen und -punkte u. a. gezeichnet werden. Im Aufsatz werden die Faktoren diskutiert, die
auf die Abscheidung der Goldschicht Einflu haben, wie diese aufwchst und wie ihre Ausmae
gesteuert werden knnen. Ebenso werden Faktoren diskutiert, die die Abscheidungsgeschwindigkeit beeinflussen. Mgliche Anwendungsgebiete
werden aufgezeigt.

High speedselectivejet electrodepositionis a process wherebymetalsmay be depositedin a selective mannerwithout the need formasking. Theprinciple is that a free standingjet of electrolyte impinges on a substrateata high velocityandan electric currentis oassed.Due to both electrochemical
and hydrodynamicpropertiesof thejet, metalis deposited only within the impingementregionand the
immediatelysuffounding region. In this way, the
spread of the deposit is limited. By use of suitable
engineering,thejet can be moved under computer
control allowing the direct writing of tracks, spots
etc. This paper discussesthe factors that govern
the way in which a gold deposit produced in this
way grows and how the dimensionsof the deposit
may be controlled. Thepaper also discusses the.
factors that control the rate of depositionand possible applicationsof the technique.

Introduction
High Speed Selective Jet Electrodeposition
(HSSJE)is a process in which metal may be
deposited selectively without the need for
masking. The principle of the process is that
a free standing, non-submersedjet of electrolyte flowing at a high velocity impinges
onto a substrate.The applicationof a suitable
voltage betweenthe substrate (cathode)and
the nozzle(anode)causesmetal to be deposited within the impingement region and the
immediately surrounding region. Due to the
properties of the hydrodynamic flow sur-

rounding the impingement region, the electrolyte forms an extremelythin radial layeras
it flows away. Becausethis layer,termed the
wall jet region (I], is so thin, the electricalresistance of the electrolyte is comparatively
high. This means that under certain conditions, deposition is limited to the impingement region, with little deposition occurring
within the highly resistive wall jet region. In
this way selectivity is achieved. Figure I
shows a schematic view of the electrolyte
flow. Due to high electrolyte velocity, high
current densities can be applied and therefore high plating rates can be achieved.
I

III

NOZZLC

I 41-JET
II

SUBSTRATE
HYDRAULIC JUMP

Fig.1: A schematic diagram

of the non-submerged jet
ZoneI Freejet;Zone11
Impingement
zone;ZoneIII:Walllet

Selective Jet Deposition is not a new process, with the principle being patented by
NASA [2] in 1974. This patent described a
forced electrolyte flow system in which the
nozzlewas scannedacrossthe substrateand
current applied at appropriate times in accordancewith a control pattern. In this way, a
plated pattern could be written, much in the
same way as a picture is formed on a dotmatrix printer. The process described here
however uses a "direct write" system more
like the way a plotter produces an image.
Since 1974, there has been comparatively
little information published on the subject of
HSSJE,possibly due to commercial confidentiality reasons. Hayneset al [3] described a
forced flow jet plating system in 1978 and
Dorey et al [4] used a modified version of this
equipment to gold plate connectors for the
evaluationof the thermocompression bonding characteristics of the deposits. The
maximumflow rate used was 39 crn/sec. and
current densities of up to 1.3 A/cM2. They
found that the deposit quality deterioratedat

20

Bocking.,
TheHighSpeedSelectiveJetElectrodepositionof Gold

current densitiesin the region of 0.86 A/cM2

by noduleformation.However,it was claimed
that nodular deposits did not detract from
bondability.Therehavebeena numberof pa-

to correlate
DerS DublishedafteMDtina
-plating

systems
rnathenatlcallmodels oi let
with experimentalresults [5,6,7,8].However,
little work has been published on the morphological characteristics of deposits produced in this way.
Bocking [9] describedselectivepure gold deposition using both laser enhanced jet deposition and HSSJEusing small bore nozzles
or
w.
m
th.
mn
_
--i
1.
- -.. " "J. I--..
I. - I I.w.
phology of the deposits produced and reUlUbt: i -LU 'LIM
t: ItA; LlUlYLt;
VUIUULY.
lilt;
-M.IdLVU
-. -A ---

Rg.2: The effect on current density on selectivity,

0,11
7M citrate gold

current efficiency of deposition was also described. He went on to show a "direct write"
facility wherebythe jet could be moved in relation to the substrate by means of a computer controlled X-Y table, producing plated
tracks and lines.
The selectivedeposition of both copper and
gold deposits has beendescribedin depth by
Bocking [10] focusing on the relationshipbetween depositionand deposit morphology.
This paper describes pure gold desposition
using HSSJE.The morphologiesof deposits
produced are briefly described. The way in
which these deposits grow is discussedand
the factors that control the dimensionsof the
deposits are given.
Previous Studies
Previouswork by the author [10] had enabled
the relationship between the conditions of
deposition and the deposit morphologiesto
be established.It will be helpfulto summarise
the results of this previous study in order to
provide a starting point for the results of this
work.
It was found that the deposits produced had
a gaussianprofile.This shape can be seen in
Figure 2which showsa typical selectivityplot
of deposits produced under different conditions. Selectivity is a measureof the deposit
thickness within the impingementzone compared with the thickness produced in the wall
jet region. The dimensionlessdistance, R, is
the ratio of the radialdistancefrom the centre
of the impingementregionto the radiusof the
nqzzle. By plotting the thickness against the
dimensionlessdistance,the selectivityunder
different deposition conditions can be compared irrespective of nozzle size. A dimensionlessdistanceof 1 indicatesthe end of the
impingementregion and the start of the wall
jet region.

Fig.3: Gold deposit produced at maximumusable

currentdensityand platingrate -

Temp. - 55*C; 0.117M

C.D. -6 AIcrn2; 3,4 #Wsoc; pH - 8,111:
citrate gold electrolyte;Re - 12078;Thickness- 18 ; Lm

FigA Gold deposit produced from a citrate gold

electrolyteby conventionaldeposition
C.D. -5 Atcrrt2;0,06M gold: ThIcImess- 18 ILm

Bocking.TheHighSpeedSelectiveJetElectrodepositionof Gold

Where thickness measurementsare quoted,

these refer to the thickness at the centre of
the impingement region. Unless otherwise
stated, the nozzle diameter used was
0.4 mm. Currentdensitiesquoted are based
on the surface area of the impingementregion only ie. on the surface area of the cross
section of the jet. The spots were all produced using a total chargeof 0.03938 0.00008
coulombs each. The maximum plating rate
that produced acceptable deposits was
3.4 jzm/sec. at a currentdensity of 6.0 A/cmI
using a 0.17M citrate gold electrolyte at pH
8.1. Figure3 showsan exampleof a gold deposit produced under the above conditions.
For comparison,a conventionalgold deposit
of the samethicknessis shown in Figure 4.

1. Theeffect of currentdensity,
temperatureand ReynoldsNumber
The structure and spread of the deposit is
significantly affected by the current density.
At low currentdensities(< 1.0 A/cm the deposits were found to have a poor selectivity
and low thickness. Deposits were up to 11
rirnin diameter but had thickness in the region of about 1 Am or lesswithin the impingement region, reducingto less than 0.1 Am in
the wall jet region. This thickness reduction
appears to be asymptotic. At higher current
densities, (> 2.0 A/cm the selectivity was
improved with a diameterof between 1.1 and
1.2 mm, depending on the precise conditions. Thicknesses were in the region of
18 Am, again dependingon the precise conditions used.Figure5shows the effect of current density on the current efficiency.At low
current densitiesthe efficiency is low (approx
40 %) but increasesto about 70 % with increasing current density. Neither temperature or flow ratehad much effect on the selectivity.

21

Figures6 to 8 show morphologicaldiagrams

for the 0.28M citrate gold system. These relate currentdensityto ReynoldsNumber,(dW
v) a dimensionless measure of electrolyte
flow, where d- the nozzle diameter in cm,
V- the electrolyte velocity in crtVsec and
v= the kinematicviscosity in cm2/sec.It can
be seen that the structure of the deposit is

Fig.& Morphological diagram for 0,28M citrate

gold. Temperature25*C
io
Top. 40 C

uta149

IHM

V---v

thodif type

soms

2DOO

4WD

60M
wq. w N&

ON

loom

12ma

Fig.7: Morphological diagram for 0,28M citrate

gold. Temperature400C

too Twp. SSC

0

18 M/IK

i-I
to

60

50

I
30 1
012345
Curroalknoty

A/cm 54

Fig.S: Current efficiencyvs current density; 0,17M

citrate gold

Fig.8: Morphologicaldiagramfor 0,28 citrate gold;

Temperature550C

Bocking.The High Speed Selective Jet Electrodeposition of Gold

22

achievedwith a smallimprovementIn deposit

structure.
5. Theeffect of nozzleto substrate distance
For most of the experiments, the nozzle to
substrate distancewas maintainedat 1 mm.
However,decreasingthis distance improved
the selectivity slightly. Increasing the distance had little effect on selectivity but the
morphology of the deposit altered. The deposit becamemore nodular towards the wall
jet region and random needles appeared
orientedin the flow direction.
For any particular set of conditions, it was
found that the overall deposit width was reproducibleto better than 1.8%.
In order to establisha meansof improvingthe
deposition rate further, it was necessaryto
have, at least, an empirical understandingof
the way in which the deposit grew and more
importantly,the reasonsfor the deterioration
of the deposit when higher plating ratesthan
the current optimum were attempted. Part of
this work attempts to establish an empirical
mechanism of growth and deterioration of
gold deposits.

very dependenton the current density,temperature and flow rate. High flow rates and
temperatures allow high current densities
that still enablesmooth, pore free depositsto
be produced.However,it was noticed that at
very high flow rates or ReynoldsNumber,the
maximum current density was slightly reduced.
2. Theeffect of gold concentration
It was found that increasingthe gold concentration of the electrolyte increased the
maximum current density and thus the plating rate at which smooth deposits could be
produced. However,at concentrationsmuch
above 0.17M, the maximum current density
and plating rate was reduced slightly. Selectivity was not significantly affected by the
gold concentration.
3. Theeffect of conductivity
Electrolyte conductivity influenced both the
selectivity and the structure. Reducing the
conductivity by half improved the selectivity
such that the deposit diameterswere in the
region of 0.9 mm. However, the deposit
structure deterioratedat much lower current
densitiesand a maximumplating rate of only
2.9 jzrn/seccould be achieved.
4. Theeffect ofpH
The effect of pH was studied over the range
5.3 to 8.1. It was found that at the higher pH,
slightly higher plating rates could be

Experimental
A complete description of the equipment
used has been given in a previouspaper [101.
However,a schematic diagram of jet plating
system is shown in Figure 9. The nozzlecon3
X-Y-Z

TABLC

MICROCOMPUTER

I
r- -------.
I

STEPPER
M0713RC13NTR13LLER

r-'

II
II
II
II

/M RIVER
7RANSLA713R

-'----------------

*-*

702RTE-*
I

r-r
PWSSL*C
TPMACA

!I

I;
!i...

:
.............

........

1-,

I
L1i

CONSTANTCURRENT

RPiY

:H
-

"0

G---4-

FZW61T i
SWITCH

1i1

.1H

------------------------------------

Fig.g: Schematicof jet plating unit

FILTER

PLAIM
CLCCIRCL"t

Bocking:
The High SpeedSelective JetElectrodeposition of Gold

sisted of a 400 Am platinumtube sealedinto

a lead-soda glass tube. The nozzlewas fitted
to a computer controlled X-Y table. This allowed electrodeposited spots to be produced on a single substrateon a step and repeat basis. The computer also controlled the
magnitude of the currents and times of deposition, allowing a largenumberof deposits
to be produced under different conditions
automatically. The control program also
enabled computer aided design (CAD) plot
files to control the X-Ytable allowingcomplex
designs to be directly written by electrodeposition.
The deposits were produced either on
polished, nickel plated substrates with a
0.1 Am gold flash (to prevent immersiondeposits) or onto glass substrates sputtered
with chromium/gold conducting layers.
A series of depositedspots were produced at
current densitiesof 6,7 and 10 A/cM2for different times, between 0.05 seconds and 10
seconds, on the sputtered glass substrates
with Reynoldsnumbersof between3355 and
12078. This gave a representation of the
growth mode of the deposits with respect to
time. The electrolyteformulationused for the
current work is given in Table 1.
The thicknesses and profiles of the electrodeposited spots were measured using a
Sloan Dektak3030 SurfaceProfflometer.The
crystallographic orientation was measured
by X-ray diffraction. Examinationof the deposits was carried out by means of optical
MicroElectron
Scanning
and
microscopy
scopy.
Polarisationmeasurementswere carried out
using a WenkingHP72 potentiostat and a
pulse generator.Theworkingelectrodewas a
400 Am diameter copper wire embedded in
an epoxy block so that only the end face of
the wire was exposed.Adjacentto this was a

platinumwire, 200 ILM in diameter also embedded and separated from the working
electrode by a distance of 100 gm. This
acted as the reference electrode. Prior to
measurements,both the working electrode
and the reference electrode were polished
and pre-platedwith gold at current densityof
5 mA/cM2for 2 minutes. Whilst this type of
referenceelectrode was not ideal due to its
poor reversibilityin the system understudy, it
was justified by the necessityto use a small
diameter,flush mountedreferenceso that the
flow patternswere not disrupted.
Polarisation curves were produced by
sampledcurrent pulse voltarnmetryat different electrolyte velocities. Because the deposit growth was so rapid at these high current densities, conventional steady state
polarisationtechniquescould not be used. It
was foundthat a steadystate condition could
be achieved within 20 to 40 milliseconds
underjetting conditions.A series of potential
pulses of 40 milliseconds duration were
applied and the current measuredat the end
of each pulse.The substratewas re-polished
and re-plated prior to each measurement.
Prior to the application of the pulse, a preelectrolysisfor 30 seconds at 0.3 volts vs the
gold referenceelectrode (GRE)was applied.
Results
DepositMorphology
Figures 10a to 10e show a typical range of
structures produced by the jetting process.
Lower flow rates and temperatures also affected the type of structure but they all followed a typical pattern. At low current densities (< 1.0 Alcm the deposits were of a
plate-like structure as in Figure 10a.As the
current density was increased, the deposits
adopted a closed, pore free structure with
few surfacefeatures.Highercurrent densities

Table 1: Electrolyre formulations

[1] Gold(aspotassiumgold cyanide)

Diammoniumhydrogencitrate
Citricacid
Potassiumhydroxide
Kinematicviscosity

[2] Gold (aspotassiumgold cyanide)

Diammoniumhydrogencitrate
Citric acid
Potassiumhydroxide
Kinematicviscosity

23

54.09/1(0,28M)
45.09/1
25*C
40*C
55*C

15.0 9A
to pH 6,0
0.012284cml/sec
0.009221 cm'/sec
0.0076567 CM2/sec

55'C

33.5g/1(0,17M)
45.0g/l
15.09/1
to pH 8,1
0.005906cm2/sec

24

Bocking:
The High SpeedSelective Jet Electrodeposition of Gold

Fig. 10: A typical range of structures produced In ascending order of current density. Whilst the deposits were produced under different sets of
conditions, they present the growth changes as the current density is inmased for any single set of conditions

produced a surface with smooth hemispherical mounds of low amplitude. As the

current density was increased further, the deposits showed an enhanced growth at certain
sites as some of the rounded structures grew
faster than their neighbours; creating a cauliflower like appearance. Increasing the current density further, or reducing the flow rate
caused these nodules to act as precursors for
the growth of needle like structures that grew
in the direction of flow, particularly towards
the edge of the impingement zone. Still
further increase in current density led to
growth of dendritic structures in the direction
of the electric field along the wall of the electrolyte jet. Lowering the temperature caused
an increased rate of nodule and needle
formation at lower current densities.

The series of deposits produced with increasing time show this pattern of growth
develop. Figures 1la to 1ld and 12a to 12f
show typical deposits produced at 7.0 A/cM2
and 10 A/cM2 for increasing deposition
times. Both samples show that certain sites
produced faster growing nodules. Depending on the current density, these then developed into either needle like structures in
the radial flow direction or field oriented dendrites in the direction of the jet in the case of
the higher current density. The lower current
density samples simply produced larger
nodules that eventually became powdery and
non-adherant. At low temperatures, dendritic
growth was less field oriented and adopted a
finer, filamentry structure as in Figure 13.

Bocking:
The High SpeedSelective Jet Electrodeposition of Gold

25

FFM

Aulk

., -1

?i
-, -

TI

.-.,

--

Mot
31- Allk
l"
tm

_aq;

Fig.11:Thegrowth of deposit with increasingtirne

C.D. - 7A/cnv'; Re.-3335; (a)1.5 som (b)3,0 sece(c)3 -5 secs..(d)5 -0 sacs.;0,17Matrate

gold

increasingtime
Fig.12: The growth of the deposit with
(b) 1.5

C. D. - 10 A/cm2: Re. - 12078; (a) 0,6 Secs.

secs. 0,1 7M atrate gold
secs.; M8-0

SOCS. (c) 2,0 seC3. (d) 3.5 secs.

(e) 6-0

26

Bocking.TheHighSpeedSelectiveJet Electrodeposition
of Gold
evidence of preferred orientation of the deposit Under these conditions, no needles or
dendrites were produced. Figure 15 shows a
typical diffraction pattern. Deposits produced at higher current densities showed
evidence of a decreasing grain size with increasing current density, the maximum grain
size occuring at a current density of 0.75 A/
cm 2.

Fig. 13: Deposit produced at low temperature

C.D.- 4,75Alcm2;Re.- 5686;0,28Mcitrategoldelectrolyte

PolarisationStudies
Figure 14shows the polarisationcurves for a
0.17M citrate gold at velocities of 2,10 and
20 m/second. It can be seenthat at a velocity
of 20 m/second, up to a current density of
2 A/cM2, deposition proceeds under activation control. TheTafel slope is -355 mV/dec.
Above this value, mixed activation and diffusion control occurs. No clearly defined limiting current is observed.This could be due to
the fact that hydrogen evolution competed
with gold deposition and the limiting current
plateau was hidden or that mass transfer
within the jet was so high. However,it can be
seen that the deposit beganto deteriorate in
the mixed control region. This applied to the
other velocities except that deteriorationoccurred at lower current densities.

Mg.15: Atypical x-ray diffraction pattern produced

by jet electrodepositedspots

C. D. -I

A/CM2

Discussion
Based on the evidence obtained to date, a
mechanismof growth and deteriorationof the
depositscould be postulated. It is beyondthe
scope of this paper to develop a rigourous
mathematicalmodel of the growth mechanisms involved.However,a l5ossiblemechanism could be empirically clevoloped.At low
current densities (< 1.0 Alcm) the mechanism of growth was similar to conventional
gold. Because the deposit spread was so
0VRe. 13515
20 M/Re. 33SS
7 V-SM/W
these low current densities (up to
great
at
Re. 1342
.1 V-2m1w
11mm diameter)It Is reasonableto assume
that the true current density was much lower
T-p 55C
than that based on the impingement zone
area. This was confirmed by the marked
similarityto conventionaldeposits of gold of
similar thickness that have been published
-I previously.It is likely that the spread observed here was due to the long time periods
used to pass the required number of cou0lombs
(up
to 140 seconds). This allowed a
100
10
01 Ncrent DNvty A/CMsq
001
build up of deposit beyond the Impingement
However,
it
be
that
zone.
must
remembered
Fig.14: Polarisationcurvesfor a 0,117M
citrate gold,
this
deposit
surrounding
was extremely thin
Temp. - 55'C
(< 0.1 Am). It can also be seen from the efficiency measurementsthat secondary reactions such as oxygenreductionand hydrogen
X-ray diffraction Studies
X-ray diffraction studiesshowedthat overthe evolutionwere occurring.
As
0.75
to
the current density was Increasedabove
between
density
of
range
current
1 A/cM2,all of the deposition occurred wi7.0 A/cml and a Re. of 12078,there was no
.0

Bocking:
TheHighSPeedSelectiveJetElearodeposition
of Gold
thin a region of 3 times the jet diameter, the
actual spread depending on the prevailing
conditions of deposition. Most of the deposition occurred within the impingement zone.
The deposits produced at these higher current densities showed a slight hemispherical
surface texture. It can be seen from Figure 14
showing the polarisation curves that in the
case of the curve corresponding to a Reynolds number, Re. of 13545 that deposition
assumed mixed activation-diffusion control
at a current density of about 2.0 A/cM2. Lower Re values showed this transition at lower
current densities.

27

thickness occurs in the centreof the impingement zone. This is known as the stagnation
region as axialflow is negligible.Dawson[14]
has estimated the transition between the
stagnationzone and the walljet to be x/d - 4,
where x- radial distance from the centre of
the jet and d- the jet diameter.In the present
case, this transition occurred at r- 50 i4m.
Beyondthis region,the boundary layerthickness increaseduntil it obtained the thickness
of the walljet At this point,the hydraulicjump
[12] occurred.
The behaviour of the diffusion layer is complex under these circumstances. Although a
measure of the thickness of the diffusion
layer cannot be made directly, as the value of
the limiting current density, I,, could not be
obtained, a maximum value can be estimated
approximately from the polarisation curve. At
a Reynolds number, Re. of 13545, high quality deposits are obtained up to a current
density in the region of 6.0 A/cM2. It is known
that deposits produced above the limiting
current are dendritic or powdery and nonadherant. Therefore, if a value of 7.0 A/cm' is
taken arbitrarily as the limiting current, the
thickness of the diffusion layer can be found
from a derivation of Ficks first law of diffusion;
DCb
nF
0

Thestructureof thesedepositsalso indicated

that the mode of growth was by 3D nucleation. It can clearly be seen in Figures 11cand
11d that fresh nucleation occurred on exlsting grainsforming a cauliflower-typestructure. This type of nucleationgenerallyoccurs
at high overpotentialsin the region of mixed
activation/diffusion control. The polarisation
curves show that relativelyhigh overpotentials are required to achieve the current
densities applied and that deposition is occurring under mixed control.
X-ray diffraction studies showed that there
was no evidence of preferred orientation in
the samples examined. However, these
k
samplesdid not includeany depositsexhibiting needlesor dendrites,which havea strong where n- valency of Au, F- the Faraday
preferred orientation. It is well known that constant, D- the diffusioncoefficient In cmz/
certain crystallographicplanestend to grow sec, Cb- the bulk concentrationof Au in mol/
faster than others. Inspectionof Figures I la
cm3 and IL- the limiting current density in A/
to 1ldshowed that somenodulesgrewfaster cm2 and 8- the diffusion layer thickness in
than others. It can be seen in Figure 1la that cm. The effect of migration has been ignored
nodulation was particularly prevalent in the but as the gold is in the form of an anion,the
region of surface imperfections such as net effect would be negative. For the purscratches etc. This is not surprisingas these poses of this approximation, the diffusion
sites presented the lowest energy require- coefficient of 1.68 x 10-5cm2/secat 600Cas
ments for nucleationand subsequentgrowth. given by Cheh,has beenused.This valuewas
Jt was at these sites that growth occurred evaluatedfrom a citrate type gold electrolyte
most rapidly, at least in the initial stages. with a gold concentration of 0.007M. It Is
Above a cdtical ratio of flow rate to current known that an IncreaseIn concentration dedensity, the growth of these noduleswas ac- creases the value of D but this is relatively
celerated,especiallythose towards the edge small and will be Ignored in this Instance.
of the impingementzone. To unterstandthe Values of D for the concentration of gold
reason for this, it Is necessaryto understand being used are being estimated at present.
the behaviour of the flow and the diffusion Underthe conditions specified,the maximum
layer during deposition under these condi- diffusion layer thickness would be 4 Am.
tions.
However, this value Is likely to be high beThe hydrodynamicsof an impinging free jet cause of the arbitrary choice of the limiting
high
the
D.
Realisthas
decurrent
flow
been
value
and
to
the
value
of
normal
a
surface
on
ically,
diffusion
layer
thickness
to
In
a
[1,11.12,13].
of
closer
by
authors
several
scribed
Is
2
likely.
more
flow
jet
hits
the
the
Am
brief, when the
surface,
decelerates rapidly in the axial direction and Whilst a fast growing nodule exists within the
acceleratesin the radialdirectionformingthe diffusion layer, its growth will be controlledby
wall jet. This gives riseto a regionwherea vis- planar diffusion. Its growth will be enhanced
low,
but
layer
boundary
slightly by the fact that Its local
of
constant,
cous

28

Bocking.
The High SpeedSelectiveJet Electrodeposition of Gold

current density will be higher than the surroundingdeposit. If the nodulepenetratesthe

bulk diffusion layer,a local diffusion layerwill
develop around it. If the radius of the nodule
is much less than the thickness of the local
diffusion layer,then a regimeof sphericaldiffusion will take over. As spherical diffusion
occurs at severalorders of magnitudefaster
than planar diffusion, then the growth of the
nodule will be accelerated even further. As
the nodule grows, the field intensity will increase and the local current density will increase,acceleratinggrowth even further. On
penetratingthe static hydrodynamicboundary layer, the nodule will disrupt the flow,
causing a local increase in turbulence in its
wake.This will leadto a further increasein diffusion in the direction of the flow. In this way,
a structure such as that seen in Figure 10d
will develop. Examinationof the structures
shown in Figures 12b, c and d showed that
some nodules exceeded a height of 3; Lm
whilst others have enhanced growth to the
point of needleformation.
If the current density is sufficiently high, then
as a fast growing nodulepenetratesthe diffusion layer,the deposit will grow in the direction of the electric field and thus will grow in
the axial direction of the jet along the jet wall
as well as the radial direction. Such growths
are dendritic in nature and the structure assumes a crown-like appearance as in
Figure 10e. Current densities higher than
those that producethis latter structure leadto
a second type of field oriented growth where
the dendrite or dendrites grow within the
central core region of the jet. Whilst the main
growth front will be towards the nozzle,semlradial needleswill grow in the direction of the
flow towards the surface for the same
reasons as described above. This will give
rise to a structure as seen in Figure 12f This
behaviourarises when a radial needle grows
adjacent to and above the stagnation region
and into the flowing centralcore of thejet. Residual radial needles can be observed adjacent to these field orientated growths. In
many of the examplesshown, it will be noted
that in the stagnationregion, there is no flow
directional growth apparent. The radius of
this region is about 50 1Lmand supports the
claim of Dawson of the dimension of the
transition betweenthe stagnation region and
the wall jet as mentionedpreviously.
Temperature and metal Ion concentration
also influence the morphology as they both
influence the diffusion coefficient and thus
the limiting current density. Smalldifferences
in morphologyhavebeenrecognisedat lower

temperatures and concentrations but these

are not important for the empiricalmodeldescribed here.
With an understandingof the way in which
the deposit deteriorates,ways of Increasing
the usable current densities and therefore
plating rates may be investigated.
Applications
High Speed Selective Jet Electrodeposition
has numerous potential applications. It can
be applied to any situation where selective
deposition is an important requirement.
Some possible applications are described
below.
1) Thedirect writing of MicrowaveIntegrated
Circuit Substrates(MICS).
MICS are used extensively throughout the
telecommunicationsand defence industries
for mounting active devices such as
amplifiers, delay lines etc. These can be
made from sintered alumina,quartz or PTFE
composites. The substrates are metallised
using sputtering or electroless plating and
circuit tracks are produced eitherby the additive or subtractive routes using photolithographic methods.Theseprocessesareexpensive. However, by using the direct writing
facility, the circuits can be written without the
need for masking directly from the CAD designs. the thin seed layers can then be removed by etching with virtually no attack on
the written gold layer. Rgure 16shows a simple ring oscillator produced by direct writing.

Id't.

rj,

Fig.16: An exampleof a directly written microvave

ring oscillatoron an aluminlasubstrate
I

2) Theselectiveplating
of reel to reel components.
Largequantitiesof strip or pressedstrip components such as connectors and lead frames
are currently being produced either by controlled depth Immersionor by submersedjet
deposition with the reel being held between

Bocking.
The High SpeedSelectiveJet Electrodeposition of Gold

either fixed or moveablerubber masks. The

direct write systemwill enablesuch components to be produced at very high production
rates without the need for the rubber masks.
The size of the plant requiredand the volume
of electrolyte will be considerably reduced,
thus reducingthe capital expenditureand reducingthroughputtimes. Hard gold is used in
the majority of reel-to-reel processing and
work to develop hard gold solutions suitable
for jet plating is currentlybeing undertaken.
3) Bump plating.
Tape Automated Bonding is a techniquethat
is acquiring importancein the electronics industry. The process consists of the production of lead frames on a metallised plastic
strip, similarto a 35 mm photographicfilm. In
order to connectthe integratedcircuits to the
lead frames, ultrasonic bonding of gold or
aluminiumwires is used. To facilitate this, a
gold bump is requiredat the end of each lead.
There are a number of difficulties in using a
photoresist technique for this. However,
selectivejetting can overcomemany of these
problems.
4) Thedirect writing of etch resist
for printed circuit boards.
Printedcircuit boards havebeendirectly written using gold as an etch resist. Figure 17
shows an exampleof this method. No masking was used.This technique can be used for
small prototype boards where turn-round
times can be extremely short. The process
can take CAD designs and write the resist
pattern in a matter of minutes, the time depending on the complexity and size of the
board. The example shown took 15 minutes
to produce and 5 minutesto etch. Edge definition is good and undercut is minimal. By
the use of multiplejets, many circuits can be
written simultaneouslyallowing the process
to be used for small to medium sized
batches.
The process is not limited to gold. Other
metalshave been examinedand work is continuing on processes directly relevant to the
electronicsindustry.It may be concluded that
this process offers a significant step forward
in selective plating due to its high speed and

29

cost savings in the elimination of masking

processes, relatively low capital cost and
simplicityof operation.

Fig.17: An exampleof a directly written etch resist

patternfor a printedcircuit board afteretchingwith
a coppercladding
Acknowledgements
The author wishes to thank Mr Ian Gunter of the Metallurgy
Group. Hirst ResearchCentre. for his invaluable assistance in
the design of the control equipment and the computer programming that madethis work possible.Thanksalso go to staff of the
Materials and Components Assessment Laboratory, Hirst Research Centre and the Electron Microscopy Unirt of the
LoughboroughUniversityof Technologyfor producing the SEMI
micrographspresentedhere.
This work is part of a BRITEIEURAMproject No. RI1B-0304. in
partnership with Centro SvillupO Materialli of Italy and
LoughboroughUniversityof Technologyand thanks go to them
for their agreementto publish this paper.
TheAuthor also wishes to thank CirD. Gabe and Mr 1.Christiefor
their helpful comments.

References
[I I M.B. Glauert.J. Fluid Mach. 1,626 (1956)
(21US Patent No. 3,810,829,May 1974.James Fletcher.NASA
[31R. Haynes,K. Ramachandran& D.J. Fineberg,The Western
Electric Engineer,22,61, (1978)
[4] J. K. Dorey11,R. Haynes,R.E. Slnltskl and R.E.Woods, Plat. &
Surf. Fin.67.81 (May 1980)
[51R.C. Alkire & T.J. Chen. J. Electrochern.Soc. 129,11,2424,
(1982)
[61K-L Hsueh& D.-T. Chin, Ibid, 133.1.75. (1986)
M D.-T. Chin & C.-H. Tsang, Ibid. 125.9,1461, (1978)
18]R. Alkire & J.-B. Ju. Ibid, 134.2,294, (1987)
191C.C. Bocking, Trans. IMF, 66,50, (1988)
[101C.C. Bocking, Proceedingsof the 59th Intnl. Conf. On Surf.
Fin.Torquay.2,51. (1991)
1111E.J. Watson.J. Fluid Mach., 20,3,481, (1964)
(121H. Schlicting, "Boundary Layer Theory", 4th ad., McGrawHill, Now York 0 960)
[131V.E. Nakoryakov.B.G. Pokusaev& E.N. Troyan. Int J. Heat
Mass Transfer.21.1175. (1978)
[14] DA Dawson & 0. Tress, Can. J. Chem. Engng, 44,121.
(1966)
1

.1-

130

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

OF GOLD AND COPPER
C. BOCKING
(HSSJE)is aprocessby whichmetalsmaybe
High SpeedSelectiveJetElectrodeposition
in a spatiallyselectivemannerwithout theneedformasking.Thispaper
electrodeposited
discussestheprinciplesthat underlieHSSJE and thefactors that influencethe ratesof
deposition,selectivityand depositqualityforboth copperandgold. Alsopresentedis an
hydrodynamic
the
ofhow
and electrochemicalfactorsinfluencegrowth
model
empirical
mechanismsand limit depositionrates.Potential applicationsof the processare also
.discussed.
1. INTRODUCTION

NOMENCIATURE
B

Proportionality

constant of Fick's first law

Concentration
(Mol/CM3)

of ionic species of interest

Cb

Concentration of ionic species of interest in

the bulk electrolyte (mot/cm3)

CO

Concentration of ionic species of interest at

the surface (mol/cm3)

Diffusion

Jet diameter (cm)

Faraday constant

Current density (A/CM2)

iL

Limiting

AD

Diffusion

n
R
Rd

coefficient (cm2/s)

current density (A/cm2)

flux (mol/s/cm2)

Number of electrons in electrode reaction

e--;
iv iR gas constant
U niv

Pimen iI

ssspreadparameter,y1r'
r

Re

I
Rtynolds number

Stagnationzoneradius(cm)
Nozzle radius(cm)

Temperature (K)

Distance from electrode (cm)

Radial distance from the centre of the

impingement zone (cm)

Yd

Radial edge of deposit (cm)

Diffusion layer thickness (cm)

Kinematic viscosity (cm2/s)

Electrodeposition, otherwise known as electroplating, is a processinvolving the coating of a material with

a layer of metal. It is a widely used method of modifying the surface characteristics of a material in order to
confer specific surface properties. These properties
include corrosion and wear resistance, electrical conductivity, or simply an improved appearance.The technology is applied throughout the engineering and
electronics industries as well as for decorative purposes. The principle of electrodeposition is simple.
T'he workpiece is made the cathodic electrode in an
electrolyte containing, amongst other things, ions of
the metal to be deposited. This is achievedby connecting it to the 'negative' terminal of a low voltage DC
supply. 'nie circuit is completed by means of a second
electrode, the anode, connected to the 'positive' terminal of the supply. The anode is usually made of the
same metal as that to be deposited although an inert
material can be used. By the application of a suitable
voltage from the supply, the metal ions adjacent to the
cathode surface are electrochemically reduced to the
metal thereby producing an electrodeposit. Oxidation
reactions occur at the anode.
The rate of deposition is controlled by both the
magnitude of current per unit area, or the current density (C. D. ) and the time of deposition. I lowever, there
is a limit to this rate, as it is a function of the electrochemical characteristics of the electrolyte and of the
prevailing hydrodynamic conditions during electrodeposition. 1be upper limit is set by the maximum rate of
masstransfer of metal ions to the surface of the cathode. In the region of this limit, the deposit becomes
powdery and poorly adherent. There is obviously a
commercial advantage in maximizing the rate of
deposition and, for many applications, a significant
amount of research has been carried out to this end.
Generally, high rates of deposition can be realized only
under conditions of vigorous agitation or high flow
rates of the electrolyte. This assistsin the transport of
the metal ions to the surface. For many processes,the
maximum rate of deposition for acceptable quality
coatings is around 0.5 to 1.0 gm/s.
It is not alwaysdesirable to deposit a metal over the
entire surface of a component. In particular, in the

GEC JOURNALOF RESEARCH,VOL 9, NO 3,1992

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

OF GOLD AND COPPER

electronics industry, gold is frequently usedbecauseof

its inert character as well as its high electrical conductivity and low contact resistance. However, it is an
expensivemetal and in order to reduce costs,it is often
restricted to where it is needed. This is normally
achieved by masking those regions where the deposit is
doing
There
this
of
ways
numerous
are
not required.
including photo-resists, chemically resistant lacquers,
from
neoprene or silicone
made
masks
or pre-formed
rubber. Each method has its advantagesand disadvantages, but they tend to be expensive. They can also
involve complicated engineering practices particularly
for continuous, automatic plating processessuchasthe
reel-to-reel plating of connector components. Such
practices are termed selective plating.
High Speed Selective Jet Electrodeposition
(HSSJE) is a process in which metal may be deposited
for
fast
the
need
masking.
without
rate
at
a
selectively
The work described in this article aims to establish an
factors
the
which control the morof
understanding
deposits
of gold and copper
of
and
structure
phology
produced using this technique. These metals were
chosen as they are widely used throughout the electronics industry. They are also representative of the
two main classesof electrolyte used in electrodeposition. These are simple salt electrolytes, in the case of
in
the caseof
salt
electrolytes
copper, and complexed
BRITE/EURAM
is
The
project
of
a
part
work
gold.
(number R1113-0304)entitled 'Improvement in the
Control and Attainment of High SpeedElectrodeposition Processels,.The partners in the project are Centro
Sviluppo Matefialli (CSM) of Italy and Loughborough
University of Technology.
2. FUNDAMENTAL CONCEPTS
In IISSJE, a free-standing, non-submersed jet of
impinges
high
flowing
onto a
a
velocity
at
electrolyte
substrate. The application of a suitable voltage
between the substrate (cathode) and the nozzle
(anode) causes metal to be deposited within the
impingement region and the immediately surrounding
region. Fig. I showsa schematic view of the electrolyte
flow. The properties of the hydrodynamic flow surthat
the
impingement
are
such
region
the
rounding
JET
ZONEI FREE
ZONE
ZONE11IMPINGEMENT
ZONEIII WALLJET

131

electrolyte forms an extremely thin radial layer as it

flows away. Because this layer, termed the wall jet
region('), is so thin, the electrical resistanceof the electrolyte is comparatively high. 'Ibis means that under
certain conditions, deposition is limited to the
impingement region, with little or no deposition occurring within the highly resistive wall jet region. In this
way, the desired selectivity is achieved. In order to
understand how high rates of deposition can be
obtained, it is necessaryto establish the mechanisms
that control the mass transport of metal ions to the
surface.
2.1. Mass transport and the diffusion layer
For a metal to be deposited from an electrolyte,
metal ions need to be present at the surface to accept
electrons and become incorporated into the growing
surface. During deposition, metal ions are discharged
at the interface. These are replaced by metal ions
reaching the surface from the body of the electrolyte
by means of hydrodynamic flow, migration and diffusion. Hydrodynamic flow results from the movement
of the bulk electrolyte by stirring orforced flow. Migration occurs as the result of the electric field acting on
the charged ions. For example, CU2+ ions having a
positive charge will migrate under the influence of the
electric field to the cathode. However, a complexed
anion such as the cyanoaurate anion, Au(CN)2- (the
metal ion species in gold plating electrolytes) will
migrate to the anode. The influence of migration can
be affected by the quantity of other charged speciesin
the electrolyte that do not take part in the electrode
reaction, as each charged species is responsible for
carrying a portion of the current. In the presence of a
large excessof charge carriers other than the electroactive speciesof interest, the influence of migration on
each individual electroactive ion is minimized. Most
plating electrolytes contain these excess charge
carriers.
Diffusion occurs because a concentration gradient
has been set up. Ions outside the interface region will
tend to diffuse to the lower concentration region near
the surface, under the influence of the concentration
gradient. 'I'lie region over which this directional diffusion occurs is known as the diffusion layer. 71liethickness of the diffusion layer is very dependent on the
prevailing hydrodynamic conditions within the bulk of
the electrolyte, namely the flow. In unstirred solutions, the diffusion layer thickness can reach typically
50gm, whereas under conditions of high electrolyte
flow, it can be as low as 2.Ogm. The diffusion flux, JD,is
related to the current density and it can be found using
Fick's law of diffusion. If migration is ignored, because
of the presence of an excessof other charge carriers,
then
InF

JD - -D(dc)
&x0 ..

(1)

Tlis can be put in terms of the concentration at the

interface as
fig. 1. Schematicdiagram of the electrolyteflowfrom
jet
impinging
an

17

(cb
JD

- -D

- Co)

(2)

GEC JOURNAL OF RESEARCH, VOL 9, NO, 3,1992

132

C. BOCKING

Solvingfor i gives
(Cb

i=

- CO)

-nFD

(3)

ff the current density is raised sufficiently, diffusion

will not be able to re-supply the metal ions and the concentration at the interface will drop to zero. This
represents the limit of current density that can be
applied under any set of hydrodynamic conditions, as
given by eqn. (4).

nFDch
IL = -6

(4)

Any further increasein current densitywill result in a

secondary electrode reaction such as hydrogen
evolution.Also, the diffusion coefficient is temperature dependent,as canbe seenfrom
dc
dc
J= -D -E - BRT t,

(5)

where B is a constant.
It can be seen from eqn. (4) that the magnitude of
the limiting current density is controlled by the thicknessof the diffusion layer, the concentration of metal
ions and the temperature. There is a certain limit to
the metal ion concentration that can be used. This is
dictated by the solubility of that particular species in
the electrolyte. However, the thickness of the diffusion layer is dependent on the degree of agitation of
the bulk electrolyte.
It follows that for high speedelectrodeposition, high
metal ion concentrations in conjunction with high
rates of agitation and high temperatures would appear
to give the highest rates of deposition.
Despite the fact that the limiting current density
determines the maximum deposition rate for a particular set of conditions, it has been found by a number of
workers(") that the deposit quality begins to deteriorate at some value below iL. This deterioration is
apparent froni the formation of either dendritic
growth or nodular powdery deposits. It is important,
therefore, to ascertain the fraction of the limiting current density at which deposits begin to deteriorate
rather than the limiting current density itself.
There is a further factor that limits the maximum
deposition rate. For many electrodeposition reactions,
not all the current is used for depositing the metal.
Some of the current is expended in reducing hydrogen
ions, which are plentiful in aqueous electrolytes, to
form hydrogen gas.There are a number of reasonsfor
this, but these are beyond the scope of this paper.
However, the tendency for this side reaction to occur
increases with increasing current density because of
the resulting reduction in the surface concentration of
metal ions. The current efficiency of the reaction is a
measure of this secondaryreaction and can be defined
as the. fraction of the current used for metal deposition, given as a percentage. This is a further reason for
maintaining as high a surface metal ion concentration
as possible by means of agitation.

2.2. The relationship between overpotential and

current density
Much information about the behaviour of an electrochemical system can be gained by observing the
denbetween
current
relationship
overpotential. and
in
is
The
the
required
sity.
overpotential
extra voltage
order to drive an electrochemical reaction and allow
current to flow. This relationship is best shown in the
form of a polarization curve, where the current density
is plotted on a log scaleagainstthe overpotential. Fig. 2
by
These
produced
are
shows such a curve.
curves
applying incremental potential steps to the cathode
(known asthe working electrode). The potential of the
working electrode is controlled by means of a potentiostat. 11is is a feedback device that maintains the
applied overpotential to the working electrode with
reference to a third electrode known as the reference.
For each value of applied overpotential, the current
flowing is measured.From this, the current density can
be obtained.
It is beyond the scope of this paper to derive the
mathematical relationship between the overpotential
and current density. However, some aspectsof a polarization curve will be mentioned.
The linear part is known as the Wel region and
represents the overpotential range in which the kinetics of the electrode reaction control the overall rate
of reaction. This is often referred to as activation control. Beyond the Tafel region, mass transfer begins to
by
is
the
the
controlled
affect
rate
rate of reaction and
both activation and diffusion. Eventually, as the limiting current density is reached, the rate is controlled
purely by mass transfer. Beyond this point, providing
secondaryreactions are absent (for example, hydrogen
increasthe
with
constant
evolution),
current remains
ing overpotential and this is known as the limiting current plateau. Under conditions of vigorous agitation,
however, this plateau does not always appear because
of the very high rates of mass transfer.

-5
-4

li Re.= 13550
3350
&Re.
=
,
o Re.= 1350
TEMP=55C

-3
-2
-1
04001
.

61 -0.,
. CURRENTDENSITY/A/CM2

10

100

Fig.2. Polarization curves of the 0.17M gold

electrolyteat various values of I?eynoldsnumber
Overpotential measuredwith respectto the gold
reference
electrode

CFr

InURNA

I nF PF-VFA RCH

ML

QNO. 3.1992

OF GOLD AND COPPER

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

133

of jet plating systemswith experimental results("').

However, little work has been published on the morphological characteristics of deposits produced in this
way.
Bocking(II) has described selective pure gold deposition using both laser-enhanced jet deposition and
HSSJE using small bore nozzles (Imm to 0.25mm).He
examined the morphology of the deposits produced
and related these to the electrolyte velocity. The current efficiency of deposition was also described. He
went on to show a'direct write'facility whereby the jet
could be moved in relation to the substrateby meansof
a computer controlled X-Y table, producing plated
tracks and lines.
The selective deposition of both copper and gold
deposits has been described in depth by Bocking(II),
relating deposition conditions to deposit morphology.

3. BACKGROUND
Selective jet deposition is not a new process, with
the principle having been patented by NASAM in 1974.
This patent described a forced electrolyte flow system
in which the nozzle was scannedacross the substrate
and current applied at appropriate times in accordance
with a control pattern. In this way, a plated pattern
could be written, much in the sameway as a picture is
formed on a dot-matrix printer. Tlie processas subsequently described, however, uses a 'direct write' system in the manner that a plotter produces an image.
Since that time, there has been comparatively little
information published on the subject of HSSJE, presumably for reasons of commercial confidentiality.
Haynes et al.(6)described a forced flow jet plating sys0)
Dorey
in
1978
et al. used a modified version
tem
and
for
to
the
plate
connectors
gold
this
equipment
of
bonding
thermocompression
the
charof
evaluation
flow
The
deposits.
the
maximum
velocity
acteristics of
densities
39
the
current
and
were up to
cm/s
was
used
1.3 A/cm2. In this work, it was found that the deposit
densities
in
the region
deteriorated
at
current
quality
formation.
However,
because
A/cm2
0.86
nodule
of
of
it was claimed that nodular deposits did not detract
from bondability. There have been severalpapers published that attempt to correlate mathematical models

4. EXPERIMENTAL DETAILS
Fig. 3 showsa schematic diagram of the equipment
used in this study. A platinum tube nozzle with a diameter of 400gm was sealed into a lead/soda glass tube.
This was connected to the pump outlet and was
mounted onto the X-Y table. The table was driven by
two stepper motors in half-step mode allowing
increments of 2.5gm/step. The controlled current

...............

:I,

***"*****I*.
X-Y-ZTABLE

II
Iii
Iii
II
Iii
II,
Iii
II,

r-

-.

-I-----I.
II-

IIi_
IL....
----

--

---.

-.
i--. Im.

%.-M-

rLUMNIt IW

-----

II.

:iI

I; -. ---,
PRESSURE

.
-TRANSDUCER

III
II,
I Ij
II,
Iii
II
IIj
II,

--

1,'PULSErD-AMPER

I,

Li1
%JFILTER

::

f. %- .-.

--

-. ---0
RELAY.
_..
__
----------I

_j

II

SITO-RT
11
I

CIRCUIT;
SWITCH'
- _-Il

Flg. 3. Schematicdiagram of the expefimentaljet plating unit

,

GEC JOURNAL OF RESEARCH, VOL 9, NO. 3,1992

134

power supply, with a resolution of O.OImA, provided

the plating current. The motion of the X-Y table, the
magnitude of the plating current and its duration were
controlled by the computer. This allowed a number of
deposit spots to be generated on a step-and-repeat
basis. The facility was amenable to computer aided
design (CAD) control, thus permitting complex
designs to be directly written by electrodeposition. To
explore the operational limits of the process, deposit
spotswere produced over a wide range of current densities, metal ion concentrations, temperatures and
electrolyte velocities. In all cases, a constant total
charge was used. A more graphic description of the
equipment and experimental detail is given in
reference (13).
The thicknessesand profiles of the electrodeposited
spots were measured using a Sloan Dektak 3030 Surface Profilometer. The crystallographic orientation
was determined using X-ray diffraction. Examination
of the deposits was carried out using both optical
microscopy and scanning electron microscopy (SEM).
Some samples were also examined by standard
micro-section techniques. Polarization measurements
were carried out on one of the gold electrolytes using a
Wenking HP72 potentiostat and a pulse generator.
The working electrode was a 4OOgmdiameter copper
wire embedded in an epoxy block so that only the end
face of the wire was exposed. Adjacent to this was a
platinum wire, 200gm in diameter also embedded and
separated from the working electrode by a distance of
100gm. This acted as the reference electrode. Prior to
measurements, both the working electrode and the
reference electrode were polished and pre-plated with
gold at a current density of 5mA/cm2 for 2 minutes.
Whilst this type of reference electrode was not ideal
because of its poor reversibility in the system under
study, it wasjustified by the need to use a small diameter, flush-mounted reference so that the flow
patterns were not disrupted.
Polarization curves were produced using 'sampled
current pulse voltammetry' at different electrolyte
velocities, as described below. Because the deposit
growth was so rapid at these high current densities,
conventional steady-state polarization techniques
could not be used. It was found that a steady state
condition could be achieved after between 20 and
40ms under jetting conditions. A series of increasing
potential pulses of 40 ms duration was applied and the
current measured at the end of each pulse. The substrate was re-polished and re-plated before each
measurement. Prior to the application of each pulse, a
pre-electrolysis for 30s at 0.3V with respect to the gold
reference electrode (GRE) was applied.
The electrolytes used, together with some of their
relevant physical details, are given in table 1. It should
be noted that the copper electrolytes represent a class
known as simple salt systemsbecause the metal ion is
in the form of a cation, CU2+. The gold, on the other
hand, is typical of a complexed metal ion system,being
present in the form of an anion, Au(CN)2-.

C. BOCKING

Table 1
Details of electrolytes used
1. Gold electrolytes
sample [1]

sample [21

sample [31

Gold (g/litre)
(as potassium
gold cyanide)

54.0
(0.28 M)

33.5
(0.17M)

54.0
(0.28M)

Diammonium
hydrogen
citrate (g/litre)

45.0

45.0

1.0

Citric acid
(g/litre)

15.0

15.0

1.0

Potassium
hydroxide

to pil 6.0

to pI 16.0
(initially)

to p1l 6.0

Parameter

Kinematic
viscosity
(CM21s)

Conductivity
(MS/cm)

0.012284 (250C) 0.005906 (550C)

0.009221 (401C)
0.0076567 (550C)
55.3(250C)
97.6(55'C)

88.2(55

fl
28 2 (25
O)
8
48.8(55
.
_

2. Copper electrolytes
Copper
(as copper sulphate)

0.08M
0.204M
0.8M

Sulphuric acid

0.51 M (for all copper concs.)

5. RESULTS

5.1. Criteria for assessment

It was found that the deposit spots exhibited a gaussian profile with maximum thickness at the centre of
the spot. Where thickness measurements are quoted,
these refer to the thickness at the centre of the spot.
Current densities quoted are basedon the surface area
of the impingement zone, in other words, the surface
based
Deposition
are
rates
area of the nozzle aperture.
by
the
divided
the
the
the
thickness
spot
centre of
of
on
time of deposition and are given in gm/s.

The selectivity of the process has been established

by means of distribution plots. Because the deposits
half
of
the
profile
the
thickness
over
were symmetrical,
deposits
as
for
the
been
has
of
the
some
plotted
of
spot
from
the
distance
function
the
the
radial
ratio of
of
a
the
of
the
impingement
to
radius
the
zone
centre of
nozzle. 11fis gives a dimensionless spread parameter,
Rd. This method of presentation is useful when comRd
SigA
=1
different
of
value
sizes.
nozzle
paring
if
no
impingement
and
zone
the
the
of
edge
nifies
deposition occurs past this position, complete selectivthis
beyond
deposition
Any
been
ity has
achieved.
point is a measure of the reduction of selectivity.

is
in
m/s,
The electrolyte jet exit velocity, measured
different
electrocomparing
of
means
an
accurate
not
lytes. This is because of the differences in viscosity

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

OF GOLD AND COPPER

between
frictional

them, which gives rise to different shear

forces and it does not describe the true flow
conditions. In order to make satisfactory comparisons,
the dimensionless Reynolds number (Re) is used. The
Reynolds number takes into account the kinematic
viscosity of the electrolyte and is defined as dVI-o,
the nozzle diameter in cm, V=
the
where d=
the kinematic
electrolyte velocity in cm/s and v=
viscosity in CM2/S.

51. The influence of deposition conditions

S.Z1.7he

effectof current density

Both the copper and gold electrolytes exhibited a

similar behaviour as current density was increased, all
other conditions remaining constant. At low current
densities (< LOA/cm2) deposits were thin compared
to the higher current density samples and showed a
poor selectivity with X values approaching 27. However, the thickness of the gold beyond the
impingement zone was negligible (about O.Igm).
increasing the current density above this value led to
improved selectivity with an Rd value of 3. The morphology of the deposit wasalso significantly affected by
the current density. 'ne actual current densities at
depended
occurred
changes
on
morphological
which
the prevailing conditions of temperature, electrolyte
velocity and metal ion concentration but the following
At
densities
observed.
current
pattern
was
general
below 1.OA/cm2, deposits were similar in appearance
to those produced by conventional electrodeposition.
Increasing the current density led, initially, to a very
few
features.
A further
surface
with
smooth structure
increase in current density produced small, hemiAs
features.
density
the
current
was
spherical
increased still further, a nodular structure formed.
Finally, a wide variety of dendritic structures was
formed, ranging from radial needles to dendritic
columns.
The way in which current efficiency varied with
increasing current density for a given flow condition
fig.
in
be
4
can
seen
and
measured
also
was
100 TEMP= 55*C
Re.=12100
901
pH= 8.1
80
z,e
670
z

S.ZZ

135

7he effectof metal ion concentration

It was found that increasing the metal ion concentration of the electrolytes increased the maximum current density and thus the plating rate at which smooth
deposits could be produced. However, above a certain
value of concentration, the maximum current density
and maximum plating rate were reduced slightly. This
can be seen in fig. 5 which showsa plot of the maximum
useful current densities against Reynolds number for
different metal ion concentrations of copper. Similar
effects were observed for gold, particularly at a temperature of 250C. Selectivity was not significantly
affected by the metal ion concentration.
S.Z3.7he effectof electrolytePelocity
'Me velocity of the electrolyte, or more precisely, its
Reynolds number, has a significant effect on the morphology of the deposits produced. Figs. 6 to 8 show a
seriesof simple morphological diagramsfor the 0.28M
gold system.These relate the Reynolds number to the
current density and show the range of morphological
structures observed. Other gold concentrations
showeddiffering morphological habits but the general
trends were similar. Increasing the velocity allowed a
130.8MCOPPER
* 0.204MCOPPER
* 0.08MCOPPER

Z
LU
Z
LU
Ir

.9

-6

lObO2600 30bO40'005600 60bO7600

REYNOLDS
NO,
Fig. 5. Maximum current densities for acceptable
deposits from various copper concentrations, as a
function of Reynoldsnumber
10

TEMP=25*C
E
.2

Z
ui
Z
LU
cc
cc:

ui
960
&AU-

LLJ50
0
-0

40
304
01278
CURRENTDENSITY/A/CM2

Currentefficiencyvs currentdensity,0.17M
4.
Fig.
,
gold

2000

4000

6000 8000 10000- 12600

REYNOLDS
NO.

Fig. 6. Morphological diagram of the deposits

producedfi,om the 0.28M gold electrol)le at 251C as a
function of depositionconditions (current density,C.D.
and Reynoldsnumber)

GEC JOURNALOF RESEARCH,VOL 9, NO. 3,1992

136

C. BOCKING

10

TEMP= 40'C

30

FIELD
ORIENTATED
CO
z

0.28M GOLD,K- 48.8MS/CM

o LOWCONDUCrIVITY
CONDUCrRM0.17MGOLD,K= 88.2mS/cm
a NORMAL
Re- 12000
TEMP
= 550C

NEEDLE
TYPE

LLJ
a 5
FNODULAR
z
LLI
tr
cc.
SMOOTH
01..
0

2000

4000 *, 6000 *, 8000 "

REYNOLDS
NO.

' 12600
io6oo

Fig. Z Morphological diagram of the deposits

producedfrom the 0.28M gold electrolyteat 400C as a
function of depositionconditions
101
FIELD
ORIENTATED

TEMP
= 55'C

V5
Z 5.
w

z
w
cc
cr

123
R,DIMENSIONLESS
DISTANCE

Fig. 9. Typical selectivity plot of the low conductivity

and the 0.1 7M gold electrolytes

little
had
distance
Increasing
the
selectivity slightly.
deposit
the
but
the
of
effect on selectivity
morphology
altered. The deposit becamemore nodular towards the
wall-jet region and some needles were observed,
oriented in the flow direction.
S.Z6. Ae effectof electrolyteconductipity

C-)

040

2000

4000 6000
8000
REYNOLDS
NO.

10000 12000

Fig. & Morphological diagram of the deposits

produced from the 0.28M gold electrolyteat 550C as a
function of depositionconditions
greater current density and thus a higher deposition
rate to be used. There is little influence on selectivity
by the electrolyte velocity.
5.2.4.7he effectof electrolytetemperature
The effect of temperature has not been evaluated as
yet for the copper system. The gold system has not
been directly evaluated but the overall effect of temperature can be seen from the morphological diagrams. Temperature has a very marked effect on both
the maximum usable current density and the deposit
structure beyond this maximum. For a temperature
increase of 300C, the maximum current density is
doubled. The effect of electrolyte temperature on
selectivity has yet to be established.
5.2.5.77se effectof nozzleto substratedistance

Ile effect of the nozzle to substratedistancewas

establishedusingthe 0.17M gold electrolyteonly. For
mostof the experimentswith the gold electrolytes,the
nozzleto substratedistancewasmaintainedat 1mm.
However, decreasing this distance improved the

TI,.e influence of the electrolyte conductivity was

established only with a gold electrolyte. Conductivity
influenced both the selectivity and the structure.
Reducing the conductivity by half improved the selectivity, with Rd = 2.5, as can be seen in fig. 9. However,
the deposit structure deteriorated at much lower current densities and a maximum plating rate of only
2.9gm/s could be achieved.
5.2.Z 77seeffectof electrolytepH
It was not possible to adjust the pH of the copper
electrolytes as this would have significantly altered the
composition of the electrolyte. The effect of pH was
8.1.
5.3
to
the
the
range
gold systemover
studied using
It wasfound that at the higher pH, slightly higher plating rates could be achieved with a small improvement
in deposit structure. No significant influence of p1l on
selectivity has yet been established.
S.Z& Optimum conditions obtainedto date
It was found that the maximum useful current densityfor copperwas 6.5A/CM2giving a deposition rate of
1.6gm/s at 250C using a 0.8M metal ion content and a
in
is
deposit
A
2750.
shown
Reynolds number of
typical
fig. 10. It can be seen that there is a significant degree
by
caused
of surface etching of the sample, which was
flowthe
deposit
rapidly
to the wash of
exposure of the
ing electrolyte. Me degree of etching is dependent on
the length of exposure,with approximately 1gm of the
deposit being removed in 1 hour. However, there is a
boundthe
for
to
at
tendency
enhanced etching occur
lead
to
an
This
individual
can
the
sites.
growth
aries of
increase in gross porosity, particularly for thin
for
that
deposits. Selectivity plots for copper showed
the conditions above, an R value of 2.5 was obtained.

GEC JOURNAL OF RESEARCH, VOL 9, NO. 3,1992

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

OF GOLD AND COPPER

Fig. 10. A typical copper deposit produced at the

density
1.6
Is.
Current
of
ym
rate
=
plating
maximum
5.7AIcm2, Re = 2750, copper = 0.8M, thickness=
4. Opm.

137

Fig. 11. A typical gold deposit produced at the

maximum plating rate of3.4 Ion Isec. Current density 60AICM2, Re = 12100, gold = 0.17M, pH = &I,
thickness = 18.0,um.

In the case of gold, electrolyte [2] (see table 1) gave

the best performance. 'ne maximum useful current
density was 6.OA/cm2 giving a plating rate of 3.4gm/s.
8.1.
11
Fig.
550C
a
of
shows
and
pH
temperature
of
at a
deposit
these
produced
under
condiof
a
example
an
fig.
12which showsa
be
'nis
with
can compared
tions.
deposit of gold of the same thickness deposited conRj
Selectivity
that
an
value
showed
plots
ventionally.
of 3.0 was achieved.
5.3. Polarization studies
Fig. 2 shows the polarization curves for a 0-17M
350
13
550,3
for
Reynolds
of
values
number
citrate gold
T'his
the
1350.
of
overpotential
a
plot
shows
and
It
be
density.
that
at a
seen
can
the
current
against
Reynolds number of 13550and with a current density
deposition
OA/cm2,
2.
proceeded under
to
up
of
Tafel
The
slope was -355mV/deccontrol.
activation
diffusion
Above
and
this
activation
mixed
value,
ade
limiting
No
current
clearly-defined
control occurred.
hydrogen
because
'Mis
evolution
was
was observed.
limiting
deposition
the
and
gold
competed with
it
be
However,
hidden.
seen
can
was
current plateau
in
deteriorate
began
the mixed
deposit
to
the
that
6.
OA/CM2.
This
density
of
current
at
a
control region
that
to
the
except
other
velocities
applied
also
deterioration occurred at lower current densities.
SA. X-Ray diffraction studies
X-ray diffraction studies of the gold deposits showed
0.75
between
density
to
the
range
of
current
that over
7.0 A/Cm2 and a Reynolds number of 12100,there was
deposit.
the
of
orientation
no evidence of preferred
Deposits produced at higher current densities showed
in
decrease
crystallite size with
of
a
evidence
increasing current density.

Fig. IZ A gold deposit produced from a citrate

electrolyte under conventional conditions. Current
density - 5.OnL41CM2,
gold - 0.06M, thickness
I&O. Um.
6. MECHANISMS OF DEPOSIT GROWTH
6.1. Morphological aspects
Both the copper and gold systemsexhibited a similar
morphological behaviour. Whilst lower flow rates and
temperatures affected some morphological details,
deposit structures generally followed a typical pattern.
At low current densities (< LOA/cM2) the deposits
assumeda plate-like structure. As the current density
wasincreased, the deposits adopted a closed, pore-free
structure with few surface features. Higher current
densities produced a surface with smooth hemispherical mounds of low amplitude. As the current density
was increased further, the deposits showed an
enhanced growth at certain sites as some of the

GEC JOURNALOF RESEARCH,VOL 9, NO. 3,1992

138

rounded structures grew faster than their neighbours,

creating a cauliflower-like appearance.Increasing the
current density further, or reducing the flow rate,
causedthese nodules to act as precursors for the formation of needle-like structures that grew in the direction of flow, particularly towards the edge of the
impingement zone. A further increase in current density led to growth of dendritic structures in the direction of the electric field along the wall of the
electrolyte jet. Lowering the temperature caused an
increased rate of nodule and needle formation at
lower current densities.
Figs. Da to Of show typical gold deposits produced
at IOA/cM2 for increasing deposition times. These
show that certain sites produced faster growing nodules. These then developed into needle-like structures
in the radial flow direction. As the needles grew, they
developed in the axial direction in the form of fieldoriented dendrites. At a current density of 8.OA/cm2
there was no field-oriented growth and samples
exhibited an increase in radial needle formation. At
7.OA/cm2, increasing times simply produced larger
nodules that eventually became powdery and
non-adherent. At low temperatures, dendritic growth
was less field oriented and produced a finer,
filamentary structure.
61. Proposed mechanisms for the growth structures
Based on the empirical evidence obtained to date,
possible mechanisms for the observed growth of the
deposits can be deduced. At low current densities
(< I. OA/cm2) the mechanism of growth was similar to
that for conventional gold. Becausethe deposit spread
wasso great at these low current densities (up to 11mm
diameter) it is reasonable to assumethat the true current density was much lower than that based on the
impingement zone area. This was confirmed by the
marked similarity to conventional deposits of gold of
similar thickness that have been published previously.
It is likely that the spread observed here was a consequence of the long time periods used to pass the
required number of coulombs (up to 140s). This
allowed a build up'of deposit well beyond the impingement zone. However, it must be remembered that this
surrounding deposit was extremely thin (<0.1 gm). It
can also be seen from the efficiency measurements
that secondaryreactions such as oxygen reduction and
hydrogen evolution were occurring.

As the current density was increased above

LOA/cM2, all of the deposition occurred within a
region of 3 times the jet diameter, the actual spread
depending on the prevailing conditions of deposition.
Most of the deposition occurred within the impingement zone. The deposits produced at these higher current densities showed a slightly hemispherical surface
texture. It can be seen from the polarization curves in
fig. 2 that, in the case of the curve corresponding to a
Reynolds number of 13 550, deposition assumed mixed
activation-diffusion
control at a current density of
about 2. OA/CM2. Lower Reynolds number values
produced this transition at lower current densities.

C. BOCKING

The structure of both gold and copper deposits produced at current densities above 6.0 A/cm2 indicated
that the mode of growth was by 3D nucleation. Fresh
nucleation occurred on existing grains forming a cauliflower-type structure. Ibis type of nucleation generally occurs at high overpotentials in the region of
mixed activation/diffusion control. The polarization
curves show that relatively high overpotentials are
required to achieve the current densities applied and
that deposition is controlled by mixed mechanisms.
X-ray diffraction studies could not provide any cvidence of preferred orientation in the samples examined. However, these samples did not include any
deposits containing needles or dendrites, which have a
strong, preferred orientation. During electro-crystallization, growth occurs faster in certain crystallographic
directions than in others. Becauseof this, certain areas
for
faster,
deposit
sites
the
of
providing
grew
subsequent needle or dendritic growth.
It was also observed that nodulation wasparticularly
prevalent in the region of surface impetfections such
as scratches etc. This is not surprising as these sites
for
lowest
presented the
energy requirements
nucleation and subsequentgrowth. It wasat these sites
that growth occurred most rapidly, at least in the initial
stages. Above a critical ratio of flow rate to current
density, the growth of these nodules was accelerated,
especially those towards the edge of the impingement
it
is
for
To
this,
necessary
the
zone. understand
reason
to examine the behaviour of the flow and the diffusion
layer during deposition under these conditions.
The hydrodynamicsof an impinging free jet on a surface normal to the flow has been described by several
In brief, when the jet hits the surface,
authors('- 14-16).
the flow decelerates rapidly in the axial direction and
jet.
forming
the
in
direction
wall
accelerates the radial
This gives rise to a region where a viscous boundary
layer of constant, but low, thickness occurs in the
centre of the impingement zone. This is known as the
Dawsod")
flow
is
negligible.
stagnation region as axial
has estimated the transition between the stagnation
zone and the wall jet to be y1d = 4, where y- radial
distance from the centre of the jet and d- the jet
diameter. In the present case,this transition occurred
layer
boundary
5OAm.
Beyond
the
this region,
at r=
thickness increased until it reached the thickness of
the wall jet. At this point, a hydraulic jump(15)occurred
in order to conserve the electrolyte momentum.

The behaviour of the diffusion layer is complex

under these circumstances. Although the thickness of
the
directly,
as
be
diffusion
layer
the
measured
cannot
be
(Q
density
limiting
cannot
current
value of the
measured, a maximum value can be estimated approxiReynolds
At
from
a
the
curve.
mately
polarization
number, of 13550, high quality deposits are obtained
It
6-OA/cm2density
in
the region of
up to a current
this
value
found
deposits
that
above
produced
was
if
of
Therefore,
dendritic.
a
value
or
were nodular
7.OA/CM2 is taken arbitrarily as the limiting current
be
layer
diffusion
can
density, the thickness of the
has
from
(4).
The
effect of migration
eqn.
calculated
the
net
is
ignored,
but
been
anionic,
the
gold
as
again
this
of
For
be
the
purposes
negative.
effect would

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

OF GOLD AND COPPER

0)

b)

cl

dl

el

139

fl

0.1
7M.
12
100,
Re
density
OAlcm
Current
10.
gold
increasing
deposit
time.
with
Fig. 13. ThegroKlhof the
6.0s])
&Os
3.5s
d)
Os
2.
1.5s
b)
e)
0.6s
c)
a)

GEC JOURNALOF RESEARCH,VOL 9, NO. 3,1992

140

C. BOCKING

D of
the diffusion
calculation,
coefficient
1.68xIV cm2/sat 600C as given by Cheh(11),has been
used. This value was derived from a citrate type gold
electrolyte with a gold concentration of 0.007M. It is,
known that an increase in concentration decreasesthe
value of D but this decreaseis relatively small and will
be ignored in this instance. More accurate values of D
for the concentration of gold being used are being estimated at the present time. Under the conditions specified, the maximum diffusion layer thickness is
calculated to be 4gm. However, this value is likely to
be high becauseof the arbitrary choice of the limiting
current density value and the high value of AA diffusion layer thickness of closer to 2gm is more realistic.
Whilst a fast growing nodule is confined to the diffusion layer, its growth will be controlled by planar diffusion. Its growth will be enhanced by the fact that its
local current density will be higher than that of the
surrounding deposit. If the nodule penetrates the bulk
diffusion layer, a local diffusion layer will develop
around it. If the radius of the nodule is much less than
the thickness of the local diffusion layer, then spherical diffusion will take over as the dominant mass
transfer mechanism. As spherical diffusion occurs at a
rate which is several orders of magnitude faster than
planar diffusion, then the growth of the nodule will be
accelerated even further. As the nodule grows, the
field intensity will increase and the local current density will increase,accelerating growth even further. On
penetrating the static hydrodynamic boundary layer,
the nodule will disrupt the flow, causing a local
increase in turbulence in its wake. This will lead to a
further increase in diffusion in the direction of the
flow. In this way, a structure such as that seen in fig. 14
will develop.
If the current density is sufficiently high, when a fast
growing nodule penetrates the diffusion layer, the
deposit will grow in the direction of the electric field
and thus will grow in the axial direction of the jet along
the jet wall as well as in the radial direction. Such
growths are dendritic in nature and the structure
assumesa crown-like appearance,as in fig. 15.Current
densities higher than those that produce this structure

lead to a second type of field-oriented growth, where

the dendrite or dendrites grow within the central core
is
front
jet.
While
the main growth
region of the
towards the nozzle, semi-radial needles grow in the
direction of the flow towards the surface for the same
reasons as described above. This gives rise to a structure shown in fig. 13f and, ultimately, a structure such
as that shown in fig. 16 and on the front cover of this
issue.This behaviour ariseswhen a radial needle grows
into
and
the
region
to,
adjacent
stagnation
and above,
the flowing central core of the jet. Residual radial

Fig. 14. A typical radial needlestructure

Fig. 16 Atypical jet core dendfitic structure

Fig. 15. A typical field-or'entated dendritic 'crown'

structure

3,1992
NO
9,
VOL
GEC JOURNALOF RESEARCH,

HIGH SPEED SELECTIVE JET ELECTRODEPOSITION

OF GOLD AND COPPER

141

needles can be observedadjacent to these field-orientated growths. In many of the examples shown, it will
be noted that, in the stagnation region, there is no
flow-directional growth apparent. The radius of this
region is about 50gm and supports the claim of
Dawson(") mentioned earlier.
Temperature and metal ion concentration also
affect the morphology as they both influence the diffusion coefficient and thus the limiting current density.
Small differences in morphology have been recognized
at lower temperatures and concentrations, but these
are caused by differences in the ratio of the diffusion
and boundary layer thicknesses.

7.3. Bump plating

Upe automated bonding (rAB) is a technique that is
important in the electronics industry. The process
involves the production of lead frames on a metallized
plastic strip, similar to a 35 mm photographic film. In
order to connect the integrated circuits to the lead
frames, ultrasonic bonding of gold or aluminium wires
is used.To facilitate this, a gold bump is required at the
end of each lead. There are severaldifficulties in using
a photoresist technique for this. However, selective
jetting may be able to overcome many of these
problems.

7. APPLICATIONS OF HSSJE

7.4. The direct writing of etch resist for printed circuit

boards

High speed selective jet electrodeposition has

numerous potential applications. It can be applied to
any situation where selective deposition is an importfollowing
The
examples are being
ant requirement.
addressed but, at this stage, a full evaluation of both
the mechanical and electrical properties of the various
examples has not been completed.
7.1. The direct writing of microwave integrated circuit
substrates (MICS)
MICS are used extensively throughout the telecomindustries
for
defence
mounting
and
munications
active devices such as amplifiers, delay lines etc. The
from
be
sintered alumina, quartz
made
can
substrates
or PTFE composites. These are metallized using
sputtering or electroless plating methods and circuit
tracks are produced either by additive or subtractive
photolithography. These methods are expensive.
However, by using the direct writing facility probe
HSSJE,
by
the
might
circuits
written, without
vided
the need for masking, directly from the CAD designs.
A sputtered or electroless plated layer is still required
in order to make the insulator conductive. After the
direct writing process, these thin metallized layers can
then be removed by etching with virtually no attack on
the written gold layer. Initial evaluations of the microwave propagation properties of such tracks are encour17
Fig.
shows a simple ring oscillator produced
aging.
by direct writing.

Printed circuit boards have been directly written

using gold asan etch resist. Fig. 18showsan exampleof
this method. No masking was used. This technique
could be used for small prototype boards where
extremely short turn-round times are desirable. 'nie
process can take CAD designs and write the resist
pattern in a matter of minutes, the time depending on
the complexity and size of the board. The example
shown took 15 minutes to produce and 5 minutes to

Fig. IZ A ring oscillator

microwave
demonstratorproduced by direct writing

circuit

7.2. The selective plating of reel-to-reel components

Large quantities of strip or pressed strip compoframes
lead
and
are currently
as
connectors
nentg such
being produced either by controlled-depth immersion
jet
deposition,
being
the
by
reel
with
submersed
or
held between either fixed or movable rubber masks.
'Me direct-write system might enable such compohigh
be
to
at
produced
very
production rates
nents
for
The
the
the
masks.
rubber
need
size of the
without
be
the
of
volume
electrolyte
and
could
required
plant
considerably reduced, thus reducing the capital
Hard
is
times.
throughput
gold
used
and
expenditure
in the majority of reel-to-reel processing and work on
the hard gold system is currently being undertaken in
this project.

tu!

Fig. 19 An exampleof a directly written etch resist

patternfor a printed circuit board after etchingthe
coppercladding

GEC JOURNAL OF RESEARCH, VOL 9. NO, 3,1992

142

etch the unwanted copper clad layer. Edge definition is

good and undercut is minimal. By the use of multiple
jets, many circuits could be written simultaneously,
allowing the process to be used for small to medium
sized batches.
T'here are many other applications of the process
which are company confidential. The process is not
limited to gold. Other metals have been examined and
work is continuing on processesdirectly relevant to the
electronics industry. It may be concluded that this
processmay offer a significant step forward in selective
plating becauseof its high speedand cost savingsin the
elimination of masking processes, relatively low
capital cost and simplicity of operation.
8. SUMMARY
It has been shown that, by means of a high velocity
jet of electrolyte impinging on a substrate, gold and
copper deposits can be produced at high deposition
rates, some two to four times the maximum for conventional methods. For pure gold, deposition rates of
up to 3.5gm/s have been obtained. For copper
deposits, deposition rates of up to 1.6gm/s were
obtained. However, the electrolyte currently used
tends to etch the surface after the deposit has formed.
The relationships between deposition conditions
and deposit structure and selectivity have been established. Mechanisms for the growth and degradation,
based on empirical observations of the gold system,
have been proposed. It is hoped that an understanding
of these mechanisms will assist in achieving higher
plating rates.
Some potential applications have been described
and some demonstration sampleshave been produced
using the HSSJE in combination with a CADCAM system. These processes will be developed further to
establish a facility that will enable selective electrodeposition to be carried out on a faster, cheaper and less
labour intensive basis.
ACKNOWLEDGEMENTS
The author wishes to thank Mr 1. Gunter of the
Metallurgy Group, Hirst Research Centre, for his
invaluable assistance in the design of the control
equipment and the cbmputer programming that made
this work possible. Other staff of the Materials and
Components Assessment Laboratory, Hirst Research
Centre and Mr R Page of the Electron Microscopy
Unit of the Loughborough University of Technology
are acknowledgedforproducing the SEM micrographs
presented here.

C. BOCKING

This work is part of a BRITE/EURAM project,

No. R1113-0304,in partnership with Centro Sviluppo
Materialli of Italy and Loughborough University of
Technology and they are thanked for their agreement
to publish this paper.
The author also wishes to thank Dr D. Gabe,
Mr 1. Christie and Dr B. Cameron for their helpful
comments.
REFERENCES
I
2

GLAUERT,
M B., 'The Wall Jet', J. Fluid Mech. 1, p. 625,1956.
ROBINSON,
D. J. and GABE,DR., 'I figh SpeedElectrodeposition

of Copper from ConventionalSulphateElectrolytes',Uans.

Inst. Met. Fin., 48, p. 3591970.
GABE, D R. and WALSH,FC., 'Enhanced mass transfer at the
rotating cylinder electrode. 1. Characterization of a smooth
cylinder and roughness development in solutions of constant
concentration', J. Appl. Electrochem., 14, p. 555,1984.
4 BARKEY,D P, MULLER R.11. and TOBIAS,C. W, 'Roughness
Development in Metal Electrodeposition. I Experimental
Results', J. Elecirochem. Soc. 136,8, p. 2199,1989.
5 US Patent No. 3 810 829, JamesC. rletchcr, NASA, May 1974.
6 HAYNES,R, RAMACHANDRAN,
K and FINEBERG,D. J., Ile
technique of fluid flow masking selective plating. Part 1Development of the technique', Ile Western Electric Engineer,
22, p. 61, April 1978.
7 DoREY 11,J K, I IAYNEs,R., SINITSKi,RE. and WOODS,RE.,
'High-speed gold plating from dilute electrolytes'. Plat. andSurf.
Fin. 67, p. 81 May 1980.
8 ALKIRE, R. C. and CHEN, TJ., 'High speed selective
129,
Soc.
J.
Electrochem.
electroplating with single circularjets',
11, p. 2424,1982.
9 IISUEH,K-L and CHIN,DT, 'Mass transfer tocylindrical surface
from an unsubmerged impinging jet', J. Electrochem. Soc. 133,
1, p. 75,1986.
10 CHIN.DT and TSANG,C-1I, 'Mass transfer to an impinging jet
electrode', Ibid, 125, No. 9, p. 1461,1978.
3

with
11 ALKiRE,R. andJu,J-B, 'Iligh speedselective
electroplating
impinging two dimensionalslot jet flow'. Ibid, 134,2,
p. 294,1987.

12 BOCKING, C. C., 'Laser enhanced and high speed jet

clectrodeposition', Uans. Inst. Met. Fin., 66, p. 50,1988.
13 BOCKING,CC., 'Ifigh speed selective jet electrodeposition',
Proc. 59th Intnl. Conf. on Surf. Fin. 2, p. 51, April 1991.

14 WATSON,
E.J., 'Theradialspreadof a liquidjet overa horizontal
plane',J. Fluid Mech.,20,3, p. 48191964.

15 SCHLICTING, II., 'Boundary Layer Theory', 4th ed.,

McGraw-I lill, New York 1960.
16 NAKORYAKOV,V.E., POKUSAEv, B. G. and TROYAN, E. N.,
'Impingement of an axisymetric liquid jet on a barrier', Int. J.
I leat Mass Uansfer, 21, p. 1175,1978.

17 DAWSON,
DA. andTRAss,0., Can.J. Chem.Engng,44,p. 121,
1966.
18 CHEH, II. Y. and SARD, R., 'Electrochemical and Structural
Aspects of Gold Electrodeposition from Dilute Solutions by
Direct Current', J. Electrochem. Soc. 118,11, p. 1737,197 1.

GEC JOURNAL OF RESEARCH, VOL 9, NO. 3,1992

The Use of High Speed

Selective Jet
Electrodeposition of Gold
for the Plating of
Connectors
C. Bocking and
Dr B. Cameron
GEC-Marconi Hirst ResearchCentre,
Wembley, UK.

Paper received 5 October 1993

C. Bockingand B. Cameron,
Trans.IMF, 1994,72(l),33.

SUMMARY -High speedselectivejet electrodeposition (IlSSJE) is a process by which

electrodepositscan be produced at very high deposition rates, selectively, without the need
for masking. Previous papers by Bocking have described the principles of the process.
This paper describesthe adaptation of a commercially available hard gold electrolyte to
theprocess. Deposition rates of up to Z5 Lmlsecondwerefound to be possible under
jetting conditions. The properties of the depositsproduced under high speedjet conditions
have been defined and compared to conventionally produced deposits of the same type. A
prototype reel-to reel plating unit based on the principles of IlSSJE has been built which,
due to the compactnessof the nozzle unit andjet cleaning process, is a fraction of the size
of more conventional reel-to-reel plating units. Whilst the results of longterm trials are
not yet available, some initial results of the performance of connectors plated with this unit
are presented.

INTRODUCTION
Most electrical devices interconnect with
other devices and the outside world by
means of the ubiquitous electrical connector. Vast quantities of connectors are
produced throughout the world, many are
very low cost particularly in the Far East.
ne satisfactory performance of a connector is crucial to the overall reliability of
any piece of electrical equipment. It has to
have a low contact resistance, good corrosion resistance and good wear resistance.
This latter property is necessary because
connectors are frequently mated and unmated during the course of the equipment
lifetime. Many specifications require a connector to remain functional through up to
500 insertion/withdrawal cycles. In order to
achieve such a performance, they arc
usually electroplated with gold, alloyed
with small quantities (- 0.1-0.3%) of
This increases the
cobalt or nickel.
hardness whilst maintaining a satisfactory
contact resistance. Despite competition
from the Far East, Europe maintains a
healthy production record in connector
in
1990,
It
is
that
estimated
production.
6,869 kg of gold was plated onto connectors
in Europe alone'. The gold plating on a
connector constitutes a significant part of
the manufacturing cost. As a consequence,
there has been a trend to reduce the
quantity of gold used either by reducing the
thickness or by limiting its application to
the functional region by means of selective
plating or both. This paper describes a
further advance in the selective plating of
The method requires no
connectors.
masking and can deposit suitable gold
alloys at much higher speeds than have
been achieved previously.

ABRIEF IIISTORYOFTHE
SELECTIVE PLATING OF CONNECTORS
Early high reliability connectors were
plated all over with gold. It soon became
clear that by limiting the required
thickness of gold to the functional contact
area, great cost savings could be made. In
fact, by the use of selective plating of gold,
tonnes of the precious metal have been
saved. Non-functional areas were given a
much thinner coating to provide a degree
of tarnish and corrosion resistance. One
of the earliest and still commonly used
methods is the use of controlled depth
immersion, which is a relative simple
The conselective plating technique.
tinuous strip is fed vertically into a plating
electrolyte at a controlled depth. The
immersed region therefore gets plated
The
whilst the remainder does not.
solution level is maintained by means of a
weir at each end of the plating tank. The
electrolyte is pumped into the tank from a
reservoir to provide a rapid flow past the
work allowing high current densities to be
used. Hain el ar- described the advantages
of the system as being simple and versatile
but listed as disadvantages surface turbulcnce and capillary action which reduce
the selectivity. As a consequence, the fccdthrough rates have to be low. Also, as
many components such as connectors
require plating on one face only, and as
the whole of the immersed component is
plated, there is a considerable wastage of
gold.
The use of selective plating of continuous strip became popular in the early
In 1975,11ciestad' described a
'70s.
variety of selective strip plating cquipment

that he was involved in developing. These

included
control
anode
geometry
(shielding), stationary mask striping, tip
plating, moving mask stripe plating and
mask spot plating.
Stripe plating is a process in which a
stripe of metal or metals is plated onto a
continuous strip of metal ribbon. The strip
could then be punched and formed into
The stationary mask
the connector.
method made use of a rubber lipped Iongitudinal slot placed with the plating cell.
The moving strip was passed over this slot
and was tensioned against it to obtain a
solution seal. The electrolyte was pumped
at high velocity through the slot and onto
the strip. In this way, stripes of 2mm width
with a tolerance of 0.13 mm could be
achieved. Current densities of up to 600
mA/cm2 were used for gold plating.
The moving mask stripe plating was
achieved by means of synchronising the
mask and the strip as it was moved
through the plating bath. A split ring and
rubber belt combination was used for the
mask. However, its plating speed was
limited by poor anode positioning and
current densities of between 50 and 100
mA/cml were used. The process did have
the advantage of allowing the plating of
pre-punched strip lead frames.
Mask spot plating was achieved by using
a wheel mask constructed from G10
fibreglass with appropriate holes for delineating the deposit. This had problems
with speed and registration but showed the
principle of operation very well.
Strip speeds for the various processes
were described by Heiestad and range
from 6ft/min, for intermittent wheel spot
platers, up to 36 ft/min for the continuous
processing stripe plating of lead frames,
both receiving 50 pLin.of gold.
At the same time, Texas Instruments'
reported the use of a spot plater for
plating nickel gold onto continuous
contact strip. A Teflon mask incorporating a platinised tantalum mesh anode
was used. No mention was made of
whether the mask was stationary or
moving or of the strip speed used.
Menzies' described reel-to-reel plating
in 1978. The two techniques mentioned
are controlled depth immersion and stripe
plating, similar to that described preAt the same time, Rherig'
viously.
described a step and repeat spot plating
unit for the plating of lead frame bond
pads in which the spot plating was carried
out using a mask that opened and closed in
a clarnshell manner. The mask was constructed from silicone rubber.
Hain and Rudolf' reviewed selective
plating techniques. These included controlled depth immersion, fixed masks and
moving masks as well as fluid flow
masking. They commented on the various
advantages and limitations of the methods,
noting that fixed mask systems can create
problems of distortion and slow strip
speeds due to friction between the mask
and the strip.
In 1982, Turner' described the latest
techniques for the selective plating of connectors with gold. He described how high
agitation rates and high metal ion concentrations enabled high processing speeds to

34

be achieved. Current densities in the gold

bath were in the region of 250 mA/cm.
He claimed that a combination of
dielectric masking and fluid flow masking
(jetting in air) was the most successful
technique for high speed continuous strip
plating. Details of how this was obtained
are not given in this reference.
A more recent review of the selective
plating of precious metals for connectors
has been given by Wingenfeld'. He stated
that the moving mask system in conjunction with jetting of the electrolyte is
the most widely used selective plating
system. A wide range of configurations
were described for many connector set
types brush. He also described the use of
techniques for connectors, making use of
either a moving brush or a stationary
brush. The moving brush consists of a
cylinder, wrapped in an absorbent
material, partially dipped into the electrolyte. The cylinder, which is made from
platinised titanium, is used as the anode.
This slowly rotates and the connector strip
passes along the cylinder with only the
area requiring plating in contact with it. In
this way, selective plating is achieved.
Plating rates of up to 6 RmImin. of gold
can be achieved with this method. This
technique is becoming less popular as connector sizes become smaller, the area of
contact reduces and the required degree of
selectivity can no longer be achieved. It
has been replaced by the stationary brush.
The brush is aV shaped hollow platinised
titanium block covered with an absorbent
material. The angle of the V is such that
the point has a contact area of about 0.8
mm. The electrolyte is pumped at low
pressure into the block. A series of holes
allows the material to become wetted by
the electrolyte by capillary action. The
components are then passed along the V
of the block and where they touch, electrolyte gently oozes out at a slow but
constant rate. The block is mounted onto
an adjustment platform that allows the
position and the angle of tilt of the block
to be set. By tilting the block, larger areas
may be plated. Plating rates of between
5-6[Lm/min. are obtained with this
method.
Whilst all these methods can satisfactorily
produce
selectively
plated
connectors, they do have disadvantages.
Generally, the plant takes up a considerable floor-space, is of a complex
construction particularly in the case of the
moving mask system or is relatively slow
as with brush plating. The high speed
selective jet electrodeposition method
described in this paper addresses these
problems. The plant required is relatively
small and inexpensive, of a simple design
and there is no requirement for masking.
In addition, the jet velocity is such that significantly higher deposition rates can be
achieved, allowing a high throughput of
strip.
THE PRINCIPLES OF HIGH SPEED
SELECTIVE JET ELECTRODEPOSITION.
High Speed Selective Jet Electrodeposition
(HSSJE) is a process in which metal may
be deposited selectively without the need

for masking. The principle of the processis

jet
of
free
that a
standing, non-submersed
high
flowing
velocity
a
at
electrolyte
impinges onto a substrate. The application
of a suitable voltage between the substrate
(cathode) and the nozzle (anode) causes
the
deposited
be
within
to
metal
impingement and the immediately surrounding region. Due to the properties of
the hydrodynamic flow surrounding the
impingement regions, the electrolyte forms
floN%s
it
layer
as
thin
radial
an extremely
away. Because this layer, termed the wall
jet region, is so thin, the electrical
resistance of the electrolyte is comparatively high. This means that under certain
limited
is
to
the
deposition
conditions,
impingement region, with little deposition
highly
the
resistive wall
within
occurring
jet. In this way selectivity is achieved.
Figure 1 shows a schematic view of the
high elecDue
the
flow.
to
electrolyte
densities
can
high
current
trolyte velocity,
be applied and therefore high plating rates
can be realised.
Selective Jet Deposition is not a new
being
patented
the
principle
process, with
by NASA' in 1974. This patent described
in
flow
which
forced
system
electrolyte
a
the nozzle was scanned across the substrate and current applied at appropriate
times in accordance with a control pattern.
be
could
In this way, a plated pattern
written, much in the same way as a picture
The
dot-matrix
printer.
is formed on a
however
a
here
uses
described
process
"direct write" system more like the way a
image.
an
produces
plotter
Since 1974, there has been comparatively little information published on the
due to comHSSJE,
possibly
subject of
Haynes et
reasons.
mercial confidentiality
jet
flow
forced
plating
described
a
all"
a
Dorey
used
all'
in
1978
et
and
system
to gold
this
equipment
of
modified version
the
of
for
the
evaluation
plate connectors
bonding
characterthermocompression
istics of the deposits. The maximum flow
den39
current
cm/sec and
rate used was
found that
They
A/cml.
1.3
to
sities of up
the deposit quality deteriorated at current
by
A/cm2
0.86
in
densities
the region of
it
However,
was
formation.
nodule
did not
deposits
claimed that nodular
have
There
bondability.
detract from
been a number
of papers published
mathematical
to
correlate
attempting
experiwith
jet
systems
plating
models of
However, little
mental reSUItSI2.13.14.15.
the morphobeen
on
has
published
work
logical characteristics of deposits produced
in this way*

Bocking 16described selective pure gold

jet
laser
enhanced
deposition using both
bore
HSSJE
small
using
deposition and
He
examined
0.25mm).
(lmm
to
nozzles
deposits
produced
the
the morphology of
electrolyte
the
to
these
and related
depoof
velocity. The current efficiency
He went on to
described.
sition was also
the
facility
whereby
show a "direct write"
jet could be moved in relation to the subcontrolled
by
computer
a
of
means
strate
X-Y table, producing plated tracks and
lines.
both
copper
deposition
of
The selective
been described
has
deposits
and pure gold

in depth by Bocking17,18 focusing on the

deposition
between
relationship
conditions and deposit morphology.
He
found that deposition rates for high quality
pure gold deposits could be as high as 3.4
at a current density of 6.0
gm/second
A/CM2. The conditions required in order
to achieve these rates can be summarised
as follows. A high metal ion concentration
is required,
together with a rapid elecHowever, there exists a
trolyte velocity.
limit to both. For any particular value of
either parameter, an increase in one or the
other beyond a certain value leads to a
deterioration
of the deposit, effectively
lowering the deposition rate that can be
achieved. An empirical description of the
processes involved is given in Reference
is a high elec18. A third requirement
trolyte temperature.

HARD GOLD ALLOY DEPOSITION

USING IISSJE
Whilst it has been shown that it is possible
to deposit pure gold at very high deposition rates, there has been no literature
describing the composition, properties and

ZONE I
ZONE 11
ZONE III

quality of gold alloy deposits at deposition

rates in excess of about 0.5 l.Lm/second.
The work on pure gold deposition has now
been extended to gold alloys and some
results of these studies are discussed here.
It has been found that gold alloy deposits
of good morphological appearance and
functional quality can be achieved at deposition rates of up to 3.0 Lm/second. A
commercially available electrolyte was
chosen for this work, the Ronoval N
(Supplied by LeaRonal). This electrolyte
normally produces gold/nickel alloy
deposits with deposit nickel values of
about 0.15% at current densities up to 1.0
A/CM2 and deposition rates of up to 0.25
lim/second. It was designed for the more
conventional "high speed" jet plating
systems described earlier. As part of its
composition, a current density extender,
referred to as a "Booster" has been
included. This additive is composed primarily of an aqueous solution of
nicotinamide. For the purposes of these
experiments, the gold concentration was
increased to 20g/I to allow the higher
current densities to be used with HSSJE.

The deposits from this electrolyte

produced under high speed selective jet
conditions were examined for the following; (i) nickel concentration in the
deposit, (ii) hardness, (iii) structure and
morphology and (iv) wear resistance.
They were also compared with deposits
produced by more conventional routes.
Experimental Method
The experimental techniques used have
been described in detail elsewhere"-'".
However, a brief description of the
methodology used will be given. Deposits
of gold/nickel alloy were produced over a
range of current densities using a constant
number of coulombs (0.07876:t 0.0001 Q
for each set of conditions varied. For analytical and structural studies, the total
number of coulombs passed should have
produced deposits of 20 l.Lm thickness. For
examination of the topography of the
deposits more akin to normal production
thicknesses, 2.5 ttrn deposits were
produced, again using a constant but lower
number of coulombs for the series
(0-010944 t 0.000025 Q.
A 400 Rm

Free jet
Impingement zone
Walt jet

Figure 1. Schematic of the electrolyte jet interaction with the substrate.

Figure 3. Optical micrograph of a jet deposit ftom the Ronoval N

A16W, Ni in electrolyte = 2,2 g/l,
electrolyte. Current densit
,v=9.0
X1000.
deposit thickness = 17.5 un.

N
Ronoval
from
deposit
jet
the
Optical
a
of
micrograph
F*
re2
I
'!feuctrolyte.
2.2 g1l,
Ni
in
Alcm2,
6.0
density
electrolyte
=
Current
=
E
deposit thickness = 17 Lm.X1000.

Figure 4. Optical micrograph of a jef deposit from Ihe Ronoval N

electrolyte. Current density = 10.0 A/cm-, Ni in electrolYtt. = 2.2
g1l,deposit thickness = 17.4 pin X1000.

35

nozzle was used with a nozzle to substrate

distance of lmm. For this work, an electrolyte velocity equivalent to a Reynolds
Number, Re, of 10600 was used. This was
based on the results obtained from the
pure gold studies. The concentration of
nickel in the electrolyte was varied
between 0 and 3.0 g/l. The temperature
The
was maintained at 55'C t 2'C.
thickness of the deposit spots was
measured using a Dektak 11 Surface
Profilometer. The nickel in the deposit
was analysed using X-ray Fluorescence
spectroscopy (XRF) on arrays of 90 identically produced deposit spots. Hardness
measurements were carried out using a
Matzusawa microhardness tester fitted
with a Vickers Pyramidal diamond. A load
of 25g was used. The measurements were
carried out directly on the as-plated
surface, ensuring that the deposit thickness
was in excess of 16 [tm. Topographical
examination was by accomplished using
Scanning Electron Microscopy as well as
optical microscopy.
After establishing the optimum nickel

concentration in the electrolyte, more

detailed studies were carried out using this
optimised solution. The cathodic current
efficiency was measured using a weighplate-weigh method. A total of 90 deposit
spots were plated onto a weighed substrate
under identical conditions. The substrate
was then re-weighed and the efficiency calculated in the usual way. Deposit structure
was examined using both microsection
methods and X-Ray Diffraction (XRD).
The XRD was performed on a Siemens
S5000 X-Ray Diffractometer on arrays of
25 identically produced deposit spots.
Wear MeasurementMethod
Wear measurements were carried out
using the GEC Contact Tester CTII. This
is an instrument designed to allow the
measurement of contact resistance against
an adjustable contact force both prior to,
during and after a pre-determined number
of insertion/withdrawal cycles. Actual
pairs of contacts are used rather than the
pin and disc configuration which is
commonly used; the test geometry is thus

much more representative of the actual

individual
The
contact
wear situation.
halves are clamped between gold plated
jaws, one on each half of the test stage as
in Figure 18. One half of the test stage can
be moved in a reciprocating manner. The
is
half
test
provided with
the
stage
of
other
X-Y control for alignment of the contact
halves. The Z adjustment controls the
Ile
between
the
force
pair.
contact
instrument gives a true four point meadetermining
the
by
resistance
of
surement
voltage drop across the contact pair when
is
through
25
passed
milliamps
of
a current
the mated contacts. The force meabridge
strain
a
stiff,
surement system uses
Measurements
beam.
load
cell
gauged
100g.
55g
loads,
and
two
were made at
Contact resistance measurements were
then
initial
after
and
the
set-up
after
made
50,100 and 200 insertion/withdrawals.
The insertion/withdrawal rate was 40
cycles per minute. A number of contact
pairs were measured at each condition and
the contact resistancevalues presented are
an average for each set of conditions.

N,
Ej Ronovel N 60 mill booster no
Ni
booster
8o
N
no
Ronovel
mill
0

2.2 g/l Ni
booster
N
60
Rono'vel
ml/I
A
Ni
2.5
booster
g/l
N
60
Ron
MI/I
0vel
,7
Ni
3.0
booster
g/l
60
N
Ronovel
ml/I
+

Figure 5. SEM micrograph of a 2.5 VLmgold/hickel deposit

spot
produced by jetting at a current density of 10.0 AICM2with a nickel
in electrolyte concentration of 1.9 gli.

for
deposition
various concendensity
Current
Z
rate
Figure
vs
N
Ronovel
in
electrolyte.
booster
the
trations of nickel and

Plots do not include

S% error in Ni in soln.
determination

Figure 6 SEM micrograph of a 2.5 Vtm gold/hickel deposit

produced by jetting at a current density of 12.0 AICM2 with a nickel
in electrolyte concentration of 1.9 g1l.

36

/I
I
te
in
and
Figure 7. The relationship between the nickel so ution
densities.
nickel in the deposit for different applied current

The tests were carried out using male

and female connectors plated with both
HSSJE and conventional deposits, with
thicknesses of 0.5 and 1.0 Lrn. The jetted
samples were prepared at a current density
of 5 A/crn', using a Ronoval N electrolyte
containing 1.9 g/I nickel whilst the samples
prepared under conventional plating conditions were plated at 15 mA/cm'. The
nickel concentration of this electrolyte was
1.7g/l. For simplicity, the deposits were
produced directly onto the copper substrates with no intermediate layer of
nickel. Both male and female connectors
were microsectioned to show the distribution of gold over the mating surfaces. It
was found that the deposit thickness was
constant over the desired area of contact.
After testing, the wear scars were
electron
scanning
examined
using
microscopy with an energy dispersive Xray analysis facility. Copper X-ray maps
with accompanying micrographs were
produced of the contact regions to
determine the extent of the penetration of
the gold layer.
Deposit topography and appearance
The deposit spots were found to be similar
in profile to those of pure gold, ie a broad

symmetrical Gaussian shape. Examination

of samples produced using the greater
number of coulombs revealed that between
0.25 A/cm and 2.0 A/CM2' there was a significant spread of the deposit beyond the
impingement zone similar to that observed
This spread
with pure gold deposits.
reached up to 9 mm at a current density of
0.75 A/cm2. As these deposits were sublittle
in
thickness,
relevant
micron
be
information
topographical
could
obtained. Between a current density of 2.0
A/cm' and 9.0 A/cM2, the deposits were
much greater in thickness (> 16Lrn). The
deposit spread over this current density
range was found to be a constant 1.2mm.
It could be seen that the deposits were generally smooth and bright although small
hemispherical mounds were present at the
surface, increasing in size and prominence
At and
with increasing current density.
beyond 9.0 A/CM2' it was clear that the
surface no longer exhibited mounds but
This trend was
was distinctly nodular.
apparent irrespective of the quantity of
nickel in deposit. Figures 2,3, and 4, show
some typical examples. However, examination of deposits having a thickness of 2.5 [tm showed few surface features up to a
current density of 10.0 A/cml. Above this

value, numerous small nodules were quite

evident. This trend can be seen in Figures
5 and 6. Figure 5 is comparable to a conventional deposit produced from the
Ronoval N electrolyte.
Deposition Rates
Figure 7 shows typical deposition rates vs
current density for different concentrations of nickel in the electrolyte. Ile
nickel concentration did not appear to
influence the deposition rate. From the
above observations, it would appear that
for deposit thicknesses of 2.5 Lrnor less, a
maximum deposition rate of 2.8-3.0
jim/second could be achieved whilst maintaining a similar topography to that of
conventionally deposited gold alloys.
The relationship between the nickel in the
electrolyte and nickel in the deposit
Figure 8 shows the relationship between
the nickel in the deposit and the nickel in
solution over a range of current densities.
It can be seen that there is a linear relationship between these parameters for all
current densities and concentrations
examined. This would indicate that the
nickel in the deposit could be easily controlled by means of relatively simple

250
Nickel in SobL
05 g/l Irl
: 0.7 g/l Ni
Li
Ni
: 1.5 g/l Ni
2.2 9A Ni
: 7-5 gA DR
3.0 gA NI

200

c2,

100

4
50

68

20

12

14

16

18

20

10

05

Current density A/mn sq

15

-410

:5

30

35

43

C. D. nA/cm sq

deposit
in
between
the
the
and
nickel
The
Figure 9.
relationship
in
different
for
density
of
nickel
concentrations
the applied current
the electrolyte.

Figure 11. The relationship between the hardness and current

density for a conventional depositfrom a Ronoval N electrolyte.

*
t-11-41.
i#, '

iIQ

. '..

ao'*k'o
,

,-,,.

* 14
,,

J-1-1
,

-, '-

*. PL

-44
1

34567
Qa-rent densityA/cm sq

10

different
for
density
conhardness
current
Deposit
vs
10.
Figure
in the electrolyte.
nickel
of
centrations

-.

il#7.
-.

a-

-,.

k,
-b

--S

, -7

-C

I'

. 'N

ut...

.-,

0-

4 -. * 91-6

-, r

-'%'-

"-

Figure 12. A microsection of a jet depasiled goldInickel alq-.

Current density = 6.0 Alcin- ,, Ni in electrolyte = 2.2 g1l, Nt in
deposit = 0.17%. X2000.
37

analytical controls of the nickel in the electrolyte and the applied current density
(See the next Section).
The relationship between nickel in the
deposit and the current density

Figure 9 shows a graph of the nickel in the

deposit and the applied current density for
different values of nickel in the electrolyte.
A geometric regression has been applied
as providing the best fit for the data. It is
quite evident that for any value of nickel
in the solution, the nickel concentration
decreases with increasing applied current
density. At a current density of 2.0 A/cm,
the nickel in the deposit is about double
that present at 9.0 A/cM2.

I lardness of the deposits

Hardness

measurements
revealed
significant differences in the influence of
nickel additions between conventional and
jet deposits.
Ordinarily,
the addition of
nickel to a gold electrolyte
causes an
increase in the hardness of the deposit.
However, examination of Figure 10 shows
the opposite trend. The basic electrolyte
with no nickel produced deposits with a
hardness in the region of 200 kgIMM2-

deposits from the Ronoval N electrolyte.

Figure 14 shows the relationship between
the preferred orientation and the current
density for the conventional Ronoval N
The preferred orientation is
deposit.
indiintensity
the
in
the
of
terms
of
shown
vidual parallel planes as a percentage of
the sum of the intensities. The parallel
lines indicate the calculated relative intensities of a randomly orientated gold
that
is
It
a very
clear
quite
specimen.
is
(111)
texture
present over the
strong
This
density
range.
recommended current
(111) texture has been found in other hard
the
normal
within
samples"
gold
alloy
operating current density range of the
is
partialland
studied electrolyte
responsible for the properties of such
deposits. In addition, the role of the
to
been
has
extend
shown
nicotinamide
the current density range of the nickel
hardened alloy gold by maintaining the
(111) texture'9. Figure 15 shows the relationship between the preferred orientation
and current density for samples produced
that
is
a strong
It
HSSJE.
clear
quite
using
(111) texture is present up to a current
density of 9.0 A/cm above which the
deposit tends towards a more random

With the addition of nickel, this hardness

was reduced to an extent, dependent on
the concentration of nickel in the deposit,
down
to a value
of 110 kg/MM2.
Conventional hard gold deposits exhibit a
hardness in the range of 130 to 200
kg/MM2.
By
choosing the appropriate
nickel concentration in the electrolyte and
current density, deposit hardnesses similar
deposits could easily be
to conventional
For comparison
achieved.
purposes,
Figure 11 shows the hardness vs current
density for a conventional deposit from a
Ronoval N electrolyte.

Structure of the deposits

Etched microsection of deposit spots
showed very few features, indicating that
the deposit was fine grained. A typical
example is shown in Figure 12. At current
densities in excess of 9.0A/crn', at which
modulation occurred, fan shaped structures
associated with surface nodules could be
seen in the microsections. Macroporosity
was clearly associatedwith these structures
as can be seen in Figure 13.
The crystal structure of the deposits
obtained using HSSJE were compared
with conventionally produced (vat plated)
100
90
80
'70
60
5e
40
30

1*

20 -;:::
i7

10
15

10

23

C. D. A/cm sq

Figure 13. A microsection of a jet deposited gold1nickel alloy.

Current density = 12.0 Alcm-, Ni in electrolyte 2.2 g1l, Ni in
=
deposit= 0.098%. X2000.

Figure 15. The relationship between preferred orientation an

N electrolyte.
Ronoval
from
deposits
density
for
jet
the
current

100
90

100

so

--*-Ill

90

-a-220
-311

80

-4-200

70
GO

0 1.9g/I NIIn soln.

Temp, 55c
Re.No. 10500

50
40
60

30
SO

20

In.

10
0

40

10

20

30

40

C. D. nIA/CmSq

Figure 14. The relationship between preferred orientation and

current density for deposits from a conventional Ronoval N elecfor
is
each reflection as a
The
expressed
trolyte.
orientation
intensity
the
of
major planes.
the
total
reflection
percentage of

38

30

10A/cm

Current densitY

15

20

sq

and
efficiency
between
the
The
current
16.
Figure
-relationship
HSSJE.
N
using
for
Ronoval
density
electrolyte
the
current

structure. However, the texture is not as

pronounced as in the case of the conventional Ronoval N deposits although quite
comparable with other nickel brightened
hard gold.
The cathode current efficiency
Figure 16 shows the cathode current efficiency for the Ronoval N electrolyte under
HSSJE conditions. This is similar to that
of a pure gold electrolyte, with low current
densities exhibiting very low efficiencies.
However, with the Ronoval N, the efficiency falls after reaching a peak whereas
in the case of pure gold, it remains
constant. In the current density range of
practical use, the efficiency is quite
acceptable, in the region of 50%.
Wear characteristics of HSSJE samples
figure 17 shows how the contact resistance
varies with the number of insertion/withdrawal cycles under different contact loads
for both jetted and conventional deposits.
In all cases, the contact resistance fell from
the initial value during testing. In the case
loads
higher
jetted
contact
the
samples,
of

gave rise to lower contact resistances. The

conventional deposits only showed this
effect with the 1.0 Rm deposit. The overall
contact resistance for both types of deposit
was within generally accepted limits.
Figures 19 to 22 show micrographs and Xray maps of typical wear scarson both male
and female contacts. Figure 19 shows a 0.5
jLm jetted deposit after 200 cycles at a load
of 55 g. It can be seen that there is little
apparent wear and no penetration through
the gold to the copper. This may be
compared with Figure 20 which shows a 0.5
I.Lm conventional deposit tested under the
sameconditions. It is clear that significantly
more wear has occurred on this sample with
the gold evidently being penetrated.
Figure 21 shows a 1.0 Rm jetted deposit
after 200 cycles at a load of 100g. Severe
wear, apparently abrasive in nature and
penetrating the coating, can be observed.
By comparison, Figure 22 shows a similar
deposit produced under conventional conditions and tested under the same
conditions. It is clear that significantly
less wear has occurred although some
penetration of the deposit is visible.

Examination of these connector pairs

after 50 cycles showed that no wear had
occurred at this stage.
DISCUSSION
It has been shown that some of the
physical properties of hard gold deposits
produced by HSSJE are similar to deposits
produced by more conventional routes.
Hardnesses have been found to be of the
same order for each method and there are
structural similarities. However, there are
differences between the wear characteristics of the two types of deposit. It
appears that the jetted deposits are
superior at low loads (55g) and small
thicknesses (- 0.5 Lrn) but inferior at
greater thicknesses.
Reference to Figure 9 allows the estimation of the nickel content of the deposit
for the jetted samples. At the current
density used, 5.0 A/cm', a nickel content of
- 0.18% would be expected. The nickel
content of the conventional deposit has
been determined to be 0.23%.
Both
values are within expected levels for such
deposits and are unlikely to explain the

400.5 um/55g W
-0.5 um/IOD9 lot

14 um/53 g A
1.0 um/1009 Jet
M5 um/53 g com
-0.5 um/100 a corw.
- 1.0 um/55 g conv.
- 1.0 um/loog coew.

50

100

150

200

No of cyck)s

The variation of contact resistance with the number of

Figure]Z
insertion1withdrawal cycles for both jetted and conventional
deposits under different load conditions.
Figure 19. SEM micrographs and Cu radiation X-rav malm of a
contact pair, jet plated with 0.5 Vin goldInickel alloy after wear
testingfor 200 cycles under a load of 5.5g.

by
the
as
used
test
The
configuration
wear
18.
connector
Figure
test.
under
Testershowing
contactpair
an
actual
Contact
GEC

Figure 20. SEM micrographs and Cu radiation X-ray inaps of a

contact pair, conventionally plated with 0.5 tLin golit/hickel alloy
after wear testingfor 200 cycles under a load of 55g.
39

Figure 21. SEM micrographs and Cu radiation X-ray maps of a

contact pair, jet plated with 1.0 gm gold/hickel alloy after wear
testingfor200 cycles under a load of 100g.
differences in wear behaviour. By analogy
with the cobalt electrolyte, it is not the
that
alloy
concentration
absolute
influences wear characteristics but the proportion present in the form of a metal ion
If this holds true for the
complex"'.
gold/nickel system, the proportion of
complex may not be the same in each case
and may explain, at least in part, the difference in wear behaviour.
The micro-hardness of the jetted deposit
may be estimated from Figure 10. Under
the conditions used, a hardness of 140
kg/MM2 could be expected. In the case of
the conventional deposit, the hardness has
been measured on an 18 [tm sample and
found to be 192 kg/mm'. It has been sugthat good wear
gested by Antler"
resistance requires both. high hardness and
low ductility. This difference in hardness
between the two samples may explain the
poorer wear resistance of the thicker
jetted samples. The thin deposits may
behave differently due to the influence of
the substrate on the physical properties. It
is known that at low thicknesses, deposit
characteristics are largely controlled by the
influence of the substrate, particularly in
terms of internal stress, which may be
more significant than the deposition parameters,
The results presented here
were for
jetted samples produced
at an intermediate, but still high, current density (5.0
A/cm2). As Figure 10 shows, the hardness
increased with increasing
current density
and at the maximum useable current
density of 10.0 A/cml, deposits
of a
hardness in the region of 180 kg/mm'
can
be produced.

CONCLUSION
It has been shown that the use of HSSJE
with a modified Ronoval N electrolyte
allows high quality gold deposits with
similar properties to thoseobtained under
deposition
conditions. The
conventional
deposits exhibit strong structural similarities as well as hardnesses. The wear
from
differ
thoseof convencharacteristics
tional deposits when applied to real
of
conditions
simulated
under
connectors

X-ray
maps of a
Cu
Figure 22. SEM micrographs and
radiation
1.0
allo
V
goldlnickel
Lm
with
plated
contact pair, conventionally
100g.
load
200
of
cycles under a
after wear testingfor

use. The results indicate that deposit

hardness may be a significant factor in the
wear properties of plated deposits. Jetted
deposits of higher hardness are easily
achievable and will be the subject of future
work.
Deposition rates in the region of 3.0
Rm/second are realisable and because of
the self limiting nature of the HSSIE
process, a high degree of selectivity can be
obtained without the need for masking.
As a consequence, connectors can be
produced at a faster throughput than is
currently obtainable, on a reel-to-reel unit
that is a fraction of the size of conventional units. In addition, because there is
no need for masking, the engineering complexity of such plant can be greatly
reduced. A prototype plant is being constructed for large scale trials. To give
some idea of the size reduction, this plant
can be operated with a strip speed of up to
20 m/minute and with a footprint comparable to a large office desk.
Whilst the use of HSSJE of gold alloys
has been shown to potentially reduce the
cost of plant and processing, work still has
to be undertaken on both improved wear
characteristics and the production of
nickel coatings using the technique.
ACKNOWLEDGMENTS
This work was carried out as part of a
No.
BRITE
Project
RIIB-0304,
in the Control
"Improvement
and
Attainment of High Speed Deposition
Processes" in partnership with CSM
(Roma) and Loughborough University of
Technology. The authors wish to thank
the EEC and their partners for their kind
In addition,
agreement to publication.
thanks go to the staff of the Materials
Science Laboratory of the Hirst Research
Centre for their assistance in producing
the SEM micrographs, the XRD data and
the analytical results.
REFERENCES
1. "The consumption of gold products by
the West European Electronics and
Electrical Industries, third quarter and
whole year, 1991", C.G. Wedgewood

London,
Consultancy Service,
December,1991.
2. W.R. Hain and L.W. Rudolf, Western
ElectricEng.,1978,April, 91.
3. D. Heiestad, '8th Annual Connector
NJ.
Hill,
Cherry
symposium',
Electronic Computer Study Group.
337,1975.
4. "Texas Instrumentsusesspot plating
keyboards".
of
costs
of gold to cut
Plating & Surf. Finish., 1975,649).
846.
197&
Prod.
Electronic
Menzies,
5. G.
May, 38.
Eng..
Electric
Western
Rehrig,
L.
6. D.
1978,April, 48.
7. D.R. Turner, Thin Solid Films, 1981
95,1443.
91,
Connectors
Proc
8. P. Wingenfeld,
1991,91.
Na
Patent
U.
S.
NASA,
9. J.C. Fletcher,
May.
3810829,1974
DJ.
and
Ramachandran
K
10. R. Haynes,
Fineberg, WesternElectric Eng. 1978.
April, 22,61.
E.
Sinitski
R.
Haynes,
R.
11,
11.J.K. Dorey
Plating & Surf.
Woods,
E.
R.
and
Finish.,1980,May, 67,81.
J.
Tsang,
C-H.
12. D-T. Chin and
1461.
1978,125(9),
Soc.,
Electrochem.
1983.
Soc.
Electrochem.
1.
Sonin,
13. A. A.
130(7),1501.
1991.
ibid,
Agarwal,
M
Chin
14. D-T.
and
138(9),2643.
1%e
ibid,
Chen,
T-J.
15. R.C. Alkire and
129(11),2424.
1988,66,
IME,
Trans.
16. C.C. Bocking,
50.
Conf.
Intnl.
59th
Proc.
17. C.C. Bocking,
2,51.
April,
1991,
Fin.
Surf.
On
G.
Eugen
Report,
East
18. C.C. Bocking,
1992.
Saulgau,
Verlag,
Leuze
To be
Dineen,
C.
19. C.C. Bocking and
published.

Vanhumbeek
J.
20.R. DeDonckerand
Trans.IMF, 1985,62,59.
Coinponents
Trans.
IEEE
21.M Antler,
CBMT4,1981.
Tech.,
Man.
&
Hybrids
1,15.
Roos
R.
J.
and
Celis,
P.
J.
22. M.DeBonte,
Eugen
Report,
EAST
J. Vanhumbeck,
1992.
Saulgau,
Verlag,
G. Leuze

THE INSTITUTE OF METAL FINISHING

Paper to be presented at the Annual Technical Conference

at NEC, Birmingham 28-30 March 1994
;dvance, copy

Copyright

Reserved

THE STRUCTUREOF GOLD AND GOLD ALLOYS PRODUCEDUSING HIGH

SPEEDSELECTIVE JET ELECTRODEPOSITION.

C. BOCKINGGradEff,
C. DINEEN

MSc,BSc

nAff

GEC Hint ResearchCrxbv Elsove Way, Borthamwood

GEC Hirst ResearchCeivre Elirre Way, Borehamwood

ABSTRACT

Modem reel-to-reelplatingfacilities applyselectivedepositsof gold andgold alloysduring

These
theproductionof pressedcopperandcopperalloyor nickel-ironalloystripcomponents.
leadframes.Selectivity
components
arefabricatedintoelectricalconnectors
or semi-conductor
is usuallyachievedby theuseof someform of dielectricmasking.Recentdevelopments
have
shownthat suchcomponents
maybe platedwith gold or gold alloysat depositionratesof up
to 3.5 micronsper second,selectivelyandwithouttheneedfor masking.This paperdiscusses
the microstructureof suchdepositsfrom studiesusingX-Ray diffraction andotherphysical
testing methodsand comparesthem with those producedunder conventionaldeposition
conditions.

.1 INTRODUCTION
High SpeedSelectiveJet Electrodeposition(HSSJE)is a processby which e'lectiodepositscan
be produced at very high deposition rates, selectively, without the need for masking. In
HSSJE, a jet of electrol yte is pumpedat high velocity from a small nozzle (< Imm) through
'
'
an air gap onto the substratewhilst applying a suitable electrical potential. The nozzle is
is
deposited
is
Metal
in the impingementregion
the
the
substrate
cathode.
anodic
whilst
made
is
The
deposit
its
immediate
limited becausethe electrolyte
the
of
surroundings.
spread
and
forms a very thin radial layer as it flows away from the impingement region. Ibis radial
layer is highly electrically resistive in comparisonto the jet and the'ref6rem6st of the metal
is deposited in the impingement region. Bocking'." has described in detail the electrodeposition of copper and pure gold using this method. More recently, Bocking and Cameron4
have describedthe electrodepositionof nickel alloyed hard gold. Such depositsare widely
used for the selective electrodepositionof electrical connectors. They presenteddetails of
the hardnessandwear characteristicsof the depositsproduced. They also describedthe results
deposits.
It
initial
these
the
crystal
of
of
structure
studies
was establishedthat whilst
of some
there were manysimilarities betweenHSSJEdepositsandthoseproducedby more conventional

in
behaviour.
differences
the
there
wear
some
were
methods,
This paper describesthe results of the examinationof both pure and nickel aNoyedhard gold
depositsproduced by HSSJE using X-ray diffraction techniquesCARD) and comparesthese
by
Possible
those
conventional
more
methods.
reasonsfor the differences in
produced
with
the wear behaviour are suggested.

2BACKGROUND

References 1-3 give a complete background to experimental studies on the HSSJE of both
information
However,,
deposits.
some
necessary
on the mechanismsof
pure gold and copper
deposition and the types of deposit will be given here. When electrodepositionis carried out
jet
impingement
in
is
7le
deposit
HSSJE,
the
region.
spot thickness
produced
a
spot
using
85%
Gaussian
is
over
of 'deposition occurring within the
with
approximately
profile
impingementregion. The maximum depositthicknessis obtainedat thejet centre line. Figure
I shows the profile over one half of a typical deposit and is presentedas thicknessagainst R,
from
line
distance
the
defined
to the nozzle radius.
is
the
R
centre
the
radial
of
ratio
as
where

20

It was found that by using a citrate based electrolyte containing 0.17M, gold, pure gold
deposition rates at thejet centreline as high as 3.4 pm sec-1at a current density of 6.0 A cm-2
could be achievedwhilst maintaininga high quality deposit. In order to attain thesedeposition
rates, a high electrolyte velocity was required. Most of the work in thesestudieswas carried
jet
0.4mm
diameter
highest
deposition
out using a
rates were obtained with
nozzle and the
has
It
Re
120000.
18
Number,
This
Reynolds
to
velocities of
=
m sec-1.
was equivalent a
also been shown4that gold alloy deposits can also be produced at deposition rates of up to
3.0 pm sec-1at cuff ent densitiesof up to 9.0 A CM-2.
3 EXPERIMENTAL

Samples-of HSSJEpure -golddepositswereIpreparedusing the 0.17M electrolyte developed

in the' previous studies. For thegold alloy deposition, it was decided to use a proprietary
electrolyte.
A number of proprietary electrolytesdesignedfor high speedgold alloy electrodepositionare
currently available. A preliminary study of depositionratesand depositmorphologiesobtained
..,
using a number of theseproprietary electrolytes indicated that Ronovel N (supplied by Lea
Ronal) exhibited the mostpromising performance. It wasfound that a gold metal concentration
3.0
HSSJE,
20
dM-'3
to
(0.1
in
M)
highest
deposition
up
of
g
gave the
rates conjunction with
Ronovel
basic
The
All
this
sec-1.
subsequent
electrolyte.
studies were carried out with
pm
N electrolyte contains as part of its formulation 'an additive referr ed to'as "booster". This
additive is claimed to extendthe current density range of the electrolyte. lbree electrolytes
were prepared, one with no nickel, but containing booster, the other two containing booster
and 1.9 g dm-3and 3.0 g dm-3of addednickel respectively.
Glasssubstrates,1.5 X 1.5 cm, metallised using sputteredcoatings of chromium followed by
A
A
HSSJE
OW
Samples
low
gold
for
gold
of
this
and
study.,
respectively) were used
alloy depositsfor XRD examination were preparedover a current density range of between
3.0 and 16.0 A CM-2with differing quantities of nickel and/or addition agent (booster) in the
deposit. In the caseof HSSJE
density
range
pure gold, sampleswere produced over a current
of between 1.0 and 8.0 A CM-2.The samplesconsistedof an array of 25 identically produced
spotsplated onto the substrates. Prior to XRD examination, the chromium/gold layers not

Me Reynolds Number is dimensionless

the
diameter
into
And
the
fluid
nozzle
taking
term
account
that
a
motion,
expmeses
01"WYta viscosity. It is defined as Re - Ud/vwbem Uw velocity in cm wc-1, d- nozzle diameter in CM am vM the
electrolyte Viscosity in Cm2
WC-1.

21

deposited
by
the
spotswere strippedusing commercially availablestripping solutions.
covered
As the metallised layers were extremely thin, the stripping operation left the HSSIE spots
in
'Ile
thickness
the array was maintainedabove
the
centre-line
of
spots
virtually unaffected.
15.0,um and confirmed by measurementusing a Dektak SurfaceProfilometer after the XRD
examination had taken place.
For comparison, a series of1control samples were prepared for XRD examination by conOne
from
deposition
methods.
set
were
produced
a Ronovel N electrolyte
vat
ventional
3.0
density
40
1.7
din-3
ftirther
A
the
over
cuff
range
g
nickel
ent
mA
CM-2.
set
containing
density
from
Auronal
MRN bath
the
over
same
cuff
ent
range
produced
an
were
samples
of
is
identical
Ronoval
dm-3
N but contains no booster.
1.7
the
to
nickel,
g
which
also containing
These samples were used to study the influence of the booster. Pure gold samples were
0.06M
from
density
typical
itrate
electrolyte
containing
gold,
acid
over
a
a
current
produced
These
deposits
20
1.0
to
covered the same total surface area of the substrate
CM-2.
mA
of
range
as that covered by the jet plated spot array.

The X-ray diffraction datawasacquiredusinganSiemensD5000 X-ray PowderDiffractometer

(Bragg-Brentano geometry) equipped,with, a diffracted beam monochromator*((Cuka).
Measurementsof diffracted intensity were carried out over the 20 range3()*to 90r. Corrections
to the angularpositions andbreadthof the diffraction peaksderived from the samples,required
for various instrumentalandphysicaleffects were applied. -To determinethese
to compensate.
layer
in
dusted
fine
(@
11im
of
powdered
with
a
silicon
size).
was
eachsample
corrections,
The positions and Full Widths at Half Maximum (FWHM) intensity of the silicon peakswhich
bracketed those from the gold were used to calculatethe appropriate corrections to position
it
interpolate
lattice
known
Using
to
of
silicon
the
possible
parameter
was
precisely
andwidth.
lattice
for
thus
the
the
an
to
the
accurate
peaks
and
calculate
value
gold
of
position
a corr ection
for
broadening
line
by
Gaussian
for
line.
The
was
made
assuming
corr
ection
each
parameter
instrumental
diffraction
for
the
and
corrected
profiles,
profiles.
observed
models
Data was derived from an analysis of the position, intensity and FWHM of the first five
diffraction peaks recorded from the gold deposits. In the Bragg - Brentano geometry, the
diffraction pattern originates only from those crystallographic planes which are essentially
311
111,200,220
The
the
and
reflections are therefore
to
the
of
sample.
surface
parallel
derived from quite separateand distinct crystalliteswithin the deposit. Only the III and 222
Considerable
be
from
therefore
to
derived
the
care
crystallites.
needs
same
reflections are
do
from
true
data
interpreting
in
crystallographic random
exhibit
a
not
which
samples
exercised
orientation.

22

- edusing commercially available stripping solutions.

coveredby the depositedspotswere stripp
As the metallised layers were extremely thin, the stripping operation left the HSSJE spots
virtually unaffected. The centre-linethicknessof the spotsin the array was maintainedabove
15.0,um and confirmed by measurementusing a Dektak SurfaceProfilometer after the XRD
examinationhad taken place.
For comparison, a series of control sampleswere prepared for XRD examination by conventional vat deposition methods. One set were produced from a Ronovel N electrolyte
containing 1.7 g dM-3nickel over the current density range 3.0 - 40 mA CM-2. A ftirther set
of sampleswere produced over the samecurrent density range from an Auronal MRN bath
also containing 1.7 g dM-3nickel, which is identical to the Ronoval N but containsno booster.
These samples were used to study the influence of the booster. Pure gold samples were
producedfrom a typical acid citrate electrolyte containing0.06M gold, over a current density
rangeof 1.0 to 20 mA CM-2.Thesedepositscoveredthe sametotal surface areaof the substrate
as that covered by the jet plated spot array.
TheX-ray diffraction datawasacquiredusing an SiemensD5000 X-ray Powder Diffractometer
(Bragg-Brentano geometry) equipped with a diffracted beam monochromator ((Cuka).
Measurementsof diffracted intensitywere carried out over the 20 range30*to 90*. Corrections
to the angularpositions andbreadthof the diffraction peaksderived from the samples,required
to compensatefor various instrumentaland physical effects were applied. To determine these
corrections, each sample was dustedwith a fine layer of powdered silicon (@ Ipm in size).
The positions and Full Widths at Half Maximum (FWHM) intensity of the silicon peakswhich
bracketedthose from the gold were used to calculate the appropriate corrections to position
andwidth. Using the precisely known lattice parameterof silicon it was possibleto interpolate
a correction to the position of the gold peaksand thus calculatean accuratevalue for the lattice
parameterfor eachline. Ile correction for line broadeningwas madeby assumingGaussian
models for the observedprofiles, instrumental and corrected diffraction prof iles.
Data was derived from an analysis of the position, intensity and FW`HM of the first five
diffraction peaks recorded from the gold deposits. In the Bragg Brentano geometry, the
diffraction pattem originates only from those crystallographic planes which are essentially
parallel to the surface of the sample. The I 11,200,220 and 311 reflections are therefore
derived from quite separateand distinct
222
III
Only
deposit.
the
and
the
crystallites within
reflections are derived from the same crystallites. Considerablecare therefore needsto be
exercisedin interpreting datafrom sampleswhich do not exhibit a true crystallographic random
orientation.

23

I,

Lattice parameterswere calculatedfrom the angularpositionsof the first five lines'(111,200,

220,311 and 222) in the diffraction pattern from eachof the samples.
In order to demonstratethe difference in preferred orientation between the samples the
intensities of the first four lines of the X-ray diffraction pattern are expressedas a percentage
intensities
the
the
of
of theselines. The relevant intensities for a randomly oriented
sum
of
samplewere also calculatedand theseare shown ashorizontal lines in the Figures. 71is form
of presentationpermits a rapid graphical meansof assessingand demonstratingthe differences
in preferred orientation betweensamples.

For thepurposesof thispaper,crystallitesizewill bedefinedasa single,coherentdiffracting

region. This is not alwaysthesameasthetruecrystallitesize,D, aswill be explainedbelow,
but is usedfor convenience.Thefull width athalf maximumintensityof theKaline corrected
for instrumentalbroadeningwas usedto calculatethe crystallite size using the Scheffer
equation.
(O. gx)
(1cose)

where B =the broadeningof the diffraction line measuredat its half width maximum intensity
(radians),t =diameter of the crystal particle X= radiation wavelengthand0= angularposition
in degrees.
It was notedthat the crystal]ite sizevaluescalculatedfrom thebroadeningof the III reflections
using the Scherrer equation were significantly greater than the values derived from the 222
reflections. Ile crystallite izescalculatedfor the two planes should be the same; that they
are not, suggeststhat the Scherrer model employed, which attributes all the intrinsic line
broadeningto crystallite size effects, is anover-simplification. On the basisof this information
in
for
detailed
a
more
analysis
order to separatethe contribution to the
selected
were
samples
observedline broadeningfrom crystallite size and strain (RMS) effects.- 71is was undertaken
using the methodof Warren ad Averbachs. Ile successfulapplication of this type of analysis
However,
for
FCC
as
possible.
orders
of
reflection
an
unique
metal examined
as
many
requires
is
just
2,
the
reflections
with
the
of
accessible
multiple
orders
number
copper
radiation,
using

111 (222) and the 200 (400). In this study, line overlap problems combined with low peak
intensitiesruled out the useof the hOOreflections so that only the iII and the 222 peakswere
used for the analysis.
In order to accomplishthe analysisa better defined instrumentalline broadening standardwas
required. This was achievedby producing a pure gold powder and annealing it to the point
where no further improvement in the resolution of the ka, and k% lines could be achieved.
It is particularly difficult to obtain a suitable gold powder commercially and annealit in this
way due to its tendencyfor grain growth and sintering. Therefore, a powder was specifically
produced*. Ile observed diffraction lines were corrected for instrumental broadening by
dividing the Fourier Transform of the diffraction lines derived from the sampleby the Fourier
Transform of the appropriate line from the standardas describedby Stokes6. It Wasfound
necessaryto subtractthe signalderived from the blank glasssubstratesfrom that of the samples
prior to calculating the transform, in order to obtain a level baseline required for an accurate
analysis.
The full application of this analysis yields the mean column length (riA) and its distribution
and the RMS strain and its distribution. The apparentcell size is a3and no, the number of
cells in the averagecolumn length, is determinedby a linear extrapolation of the real part of
the Fourier Transform of the (000) reflection.
The cell size (a) is determined by the angular range over which the diffraction profile is
analysedand is given by: -

I- Ih = 2a3/Xsin(q)
1= 2a3tAsin(q)
I+ Ih = 2a3tAsin(q)

*A 50 & dm-, solution

by dissolving pure gold powder in aqua-regis and evaporating to Dear
of
sold
chloride
was
produced
dryness. Concentratedhydrochloric
acid was addedand re-evsporateduntil all oxides of nitrogen were removed. The solution
in
*48 then adjustedto the correct
a
size
de-ionisi:
It
with
to produce gold grains
4 water.
was
necessary
concentration
using
the region of 10 _ with
been
had
It
had
be
7his
to
they
very
slowly.
a well ordered structure.
nucleatedand grown
me-ant
shown that such a structure could be achieved by
100
A
nil
temperature.
the
using acetone &I room
reducing
gold
chloride
"nVIC Of the gold chloride was
placedon a magnetic stirrer at a temperatureof 35*C and 30 n-Jof acetonewas added. Stirring
&$continued for a period of 3 hours
days.
3
for
period
to
a
to
after which the sitniple was cooled ambient and allowed stand
At the end of this
period, a layer of gold powder was wen at the bottom of the beaker that had merged to form a thin film. A
Pieceof this film was
from
the
in
X-ray
diffraction
de-ionised
cleaned
Pattern
that
the
so
water and mounted on a glass slide
film could be
Ile resolution of the 6 doublet was determinedfor the first five lines in the X-ray diffraction pattern
recorded.
from the film- 'I'lle film
350*C until no further improvement resolution
then
vies
to
subjected
a
numberof
at
annealing
operations
Of the doubletswas
obtained. The total time of annealing to obtain this condition was 5 hours.

25

diffraction
is
q
the
cl
the
q
the
are
start
and
and
end
of
profile,
the
positionof
where
peak,
,
x is the wavelengthof the radiation employedand I is a reflection order as in MI. In order
to simplify the subsequentcalculations, it is convenientto choosescanrangesso that a3is the
same for all reflections used in the analysis. In this study, a cell size of 2.4 x d,,, was used.
Close and careful examinationof the diffraction patternsfrom thesesamplesshowedboth the
III and 222 diffraction peaksoverlappedwith their nearestneighbours,the 200 and311 peaks
for
This
true
the specially prepared reference gold sample used to
also
was
respectively.
determine instrumentalbroadening, In the presentstudy, data was collected over an angular
range of 10% centredabout the 111/200and 311/222 lines.
In order to obtain adequaterepresentationof the diffraction profiles in the *tails" of the peaks
(where mostof the crystalI ite sizeandstrain information is contained)avariety of mathematical
functions were fitted to the experimental data and the parametersfor the best fits used to
calculate model diffraction profiles. Pearson7, Split Pearson7 and three different pseudo
Voigt (mixed Cauchy and Gaussian)type functions were employed in the modelling.
The modelled III and 222 diffraction profiles were calculated at 1024 data points over an
Fourier
FI-7
20"
16
transforms
using
an
were
calculated
and
respectively.
of
angular range
diffraction'data
instrumental
Ile
to
the
contribution
was removed by'dividing the
routine.
,
FTof the samplesby the FTderived from the precipitatedand annealedgold powder described
000
The
Fourier
the
reflection were calculatedusing the extrapolation
of
coefficients
above.
procedures describedby Warren and Averbach'. This method enablesthe individual contributions of crystallite size and strain to line broadening to be evaluated. The contribution
is
independent
length)
(column
from
broadening
of the order of reflection
to
crystallite size
is
dependent
Because
from
the
on
order
of
that
of this, the two
reflection.
strain
whilst
contributions may be resolved. Ile mean crystallite sizes were calculatedby extrapolating
the linear region of the real part of the 000 transform to obtain N. The meancolumn lengths
(crystallite size) and RMS strains are listed in Table 1.
In addition to-crystallite size and RMS strain, layer sequencefaults on the III plane may also
faults
line
broadening
The
broadening.
line
to
twin
of
stacking
and
to
contribution
contribute
have
been
Ile
identified
be
the"strain
contributions
established.
effective
and
size
once
may
for
(I
11)
D.
the
plane
comprises
crystallite size, fr
I /D.

ff=

I/ D+

(I.

Sa+f3)*F3/4

where D is the true crystallite size, a is the stacking fault probability, p is the twin fault
probability and a is the lattice parameter. The stacking fault probability may be established
by measuringany relative shift betweenthe III and the 200 peaks. The probability may then
becalculated. Twin fault probabilities maybe calculatedfrom any asymmetryof the diffraction
peaks that have been reconstructedfrom the inverse Fourier transform produced during the
Warren and Averbach analysis. However, it was not possibleto accurately calculatethe twin
fault probabilities becausethe deposit was highly oriented in the III direction. Twin fault
probabilities are usually calculatedfor the 100 (200) reflections. Due to the high degreeof
texture, the 200 signal was very weak and could not be used for the analysis. Table I also
includes the stacking fault probabilities where thesewere significant.
Metallurgical Microsection was carried out on a number of samples in order to observe any
resolvable microstructures. The gold deposit was etched using a proprietary gold stripper
dissolved in an alcohol/water mixture.

4 RESULTS

The results of the XRD analysisare presentedin Figures 2 to 9 and Table 1. - As would have
been expected,there were considerabledifferences betweenthe pure and alloy gold deposits
so each will be presentedseparately.
4.1 Pure gold deposits
Figure 2 shows the lattice parameters and orientation of the major first and second order
reflections for a deposit produced under conventional conditions. The normal operating
current density range for this electrolyte was between3 and 7 mA CM-2.
Analysis of the data from Figure 2(a) showed that all plane generally exhibited the same
lattice parameter, although a slight increase was observed with increasing current density.
Ile averagelattice parameter of 4.077 was close to that of pure gold, which is generally
acceptedas being 4.0786 A at 25-C. It is thought that the single point of the 220 plane that
deviatesfrom this is due to experimental error.

27

It was noted that, on calculating the crystallite size using the Scheffer method, a significant
depending
This
the
observed,
on
reflection.
was particularly evident at the
was
variation
higher current densities. An analysisof this is difficult as the line broadeningobservedhas
been assumedto be purely due to crystallite size and ignoresthe existenceof strains and faults
that may also contribute. Analysis of the III reflection using the Warren and Averbach
method indicated that such an assumptionwas invalid as the crystallite size was found to be
(See
Table
1).
The
for
crystallite
size
actual
after
correcting
strain was
greater
considerably
in the region of 0.23 Wn. No evidenceof faulting was observed.
Figure 2(b) showsthe degreeof preferred orientation,of the deposit. It can be seenthat by
comparison with the expectedratios of the variousplanes(parallel lines) that there is a distinct
'31 Itexture over the normal current density range of`11-7 mA cm-1., Above this, the deposit
tends towards a more random orientation.
The RMS strain of the conventional deposits was independentof current density over the
be
low,
< e2>=0.000035.
to
calculated
comparatively
and
was
range analysed
The above measurementsof a conventionaldeposit were necessaryto compare and contrast
Whilst
direct
be
jetting
comparison
a
cannot
those
conditions.
made
under
produced
with
due to the orders of magnitude difference in the current densities applied, in terms of the
increasing
ie
that
the
changes
occurred
current
structural
with
characteristics
morphological
density, a comparisonwas consideredtobe valid. Figure 3 shows similar graphs for samples
-*producedfrom the 0.17M citrate gold using a Re.. No., of 12,000. The maximum current
density under which useful deposits could be produced was found to be 6.0 A CM-2. The
lattice parameterof eachof the crystallites was slightly smaller than the bulk, value, with an
A.
densities
2.0
A
below
However,
4.075
in
cm-2,the
the
current
at
region
of
value
average
lattice parameterexhibited a smaller size.
The crystallite size of the jetted sample calculated using the Scheffer equation was in the
'
A.
A
300
It
be
III
for
but
200
a
size
of
the,
showed
around
must
which
plane
all
region of
is
line
broadening
the
size
this
assumes
all
crystallite
that
of
estimating
method
remembered
III
222
fact
The
the
the
that
the
same
as
planes
were
not
planes
to
size.
attributable grain
.
indicate that this assumptionwas incorr ect. Further analysisof the line broadening revealed
that this difference was due to residual strain, which over the current density range measured
faults,
There
1275.
twin
evidence
of
either
or
stacking
no
>-=0.000
wasaveraged < e2
low
Ile
low
for
a
cuffentdensity.
crystallite size
at
probability of a=0.007
a very
except
*
found
be
between
Averbach
Warren
by
to
determined
III
and
the
method
was
plane as
of the
320 to 350 A.

Ile preferred orientation of the jetted samplewas found to be strongly 220 above a current
density of 2.0 A CM-2.Below this value, aIII orientation predominated,
The RMS strain observedin thesesamplesgiven in Table I was nearly an order of magnitude
greater than for depositsproducedunder conventionalconditions. There was, however, no
clear relationship with current density.
Polishedand etchedmicro-sectionsof jetted samplescan be seenin Figures 12 and 13. These
showedthat there were few structural featuresapparentat current densitiesbelow 6.0 A cm-1.
Above this value, fan shaped,cell-like structures could be observed. These cells became
apparentafter a thicknessof about 8 um had been achieved. Figure 13 shows examplesof
thesecells. Below 8 lim, the cell structure was integral with the rest of the deposit but as the
thickness increased,the cell "wall" exhibited a discontinuity. Extrapolation of the wall line
showeda coinciding point closeto the substratesurface. Topographically, thesecells appear
as nodules, increasing in size with increasing current density as well as deposit thickness.
Thesestructuresclearly resemblethe "rounded mounds"describedby Nakahara7whostudied
the structureand morphology of gold alloy deposits. He concludedthat suchstructuresformed
as a result of an inhibition processthat forced a small crystallite size to be produced as well
as forming the rounded mound structure. .
4.2 Alloy gold deposits
Figure 4 shows the data obtained from depositsproducedconventionally using a Ronovel N
electrolyte, whilst Figure 5 shows that obtained from the Auronal MRN. In addition to the
XRD data, the deposit hardnessis shown.
'T'heeffect of the booster can be clearly establishedunder conventional deposition conditions
by comparing Figures 4 and 5. Figure S(b) shows that in the caseof the Auronal MRN, a
distinct III texture is formed between 10 and 15 mA CM-2,the normal operating rangeof this
electrolyte. Indeed, below this range, the deposit appearancewas matt. Above this range,
the deposit showed signs of *burning* at the edgesof the sample. Figure 4(b) shows that
with,the addition of the booster, the III texture was predominant above 5 mA CM-2,with the
apparentsuppressionof other growth directions. Puregold, ashasbeenseenearlier, possessed
a distinct 311 texture under conventional deposition conditions. It would appear, therefore,
that aIII texture is one of the necessaryconditions for the effective performance of a nickel
hardenedalloy gold. Hardnessmeasurementsshowedthat the deposits with the boosterwere

29

15% harder than those withot, up to a current density of 15 mA CM-2. It'Can also be seen
that the booster reduced the effective lattice parameter compared to those deposits produced
in its absince.

The lattice parameterof the conventional depositswithout booster exhibited a mean lattice
less
0.27%
than that of annealedgold and remained essentially constantwith
parameter
current density. Ile values for all the planeswere comparablewithin the overall accuracy
of measurement. The lattice parameter of the conventionaldeposit containing booster was
being
-0.33%
less
lower
that
the
than that of pure
than
mean
value
of
annealed
gold,
also
gold and showeda small increasinglinear dependenceon current density. However the 220
larger
and were comparableto those of the electrolyte without
significantly
were
planes
booster.
In both cases,the crystAite'size of the III planes as determined by the Scherrer equation
The
for
for
III
than
the
calculated
the
value
other
planes.
measured
reflection
greater
was
A for depositsproduced at the lower current densities,decreasingto -200 A with
-350
was
increasedcurrent density. The crystallite sizescalculatedfor the other planesmeasuredWere
A.
in
100
In the caseof the samplesproduced from the electrolyte
the region of
typically
Warren
Averbach
booster,
the
and
analysis revealedthat'a
closer
analysis
using
containing
difference
be
from
Table
1.
In
RMS
to
this
as
can
seen
strain
contributed
addition,
significant
a slight asymmetry of the reconstructedpeakssuggestedthat some twin faulting was present
but as explained earlier, no accuratemeasurementsof their magnitudecould be made.
Figures 6 and 7 show the data calculatedfrom samplesproducedby jetting from electrolytes
but
dm-3
booster
80
Figures
6(b)
60
dm-3
respectively
no
nickel.
CM3
crn'
and
and
containing
7(b) show the preferred orientation. It can be seenthat with increasing current density, the
III componentof orientation risesrapidly to around60% at the expenseof the 220 component.
The contributions from the 200 and 311 remained fairly constant and close to their values
expectedin a random sample.Ibis is consistantwith aIII texture.
Figure's6(a) and 7(a) show the influence of the booster on the lattice parameter. There is a
for
increasing
in
lattice
the
all
trend
planes
with
current
parameter
a
of
reduction
general
density. It will be noted that the 200 plane exhibited a significantly smaller lattice parameter
lattice
distortion
being
This
the
that
a
of
the
suggest
was
created
would
than
other planes.
due to the incorporation of the booster (or breakdown product of it) within the 100 (200)
planes.

30

As was observedin the previoussamples,the III planesexhibiteda larger apparentcrystallite

sizp than the others as determinedusing the Scherrer equation. For both concentrationsof
booster, the III plane was found to be in the region of 300A whilst that of the other measured
A.
in
150
This may be attributed to both stacking faults as well as
the
planes was
region of
residual strain as can be seenfrom Table 1.
Figures 8 and 9 show the influence of nickel under jetting conditions. The addition of nickel
to the electrolyte appearedto reinforce the effects of the boosterwith a greater degreeof III
texture being seen.at current densities below 9.0 A cm-1. Above this cuff ent density, the
deposit tended towards a more random orientation unlike those samples containing booster
alone.

Ile presenceof nickelreducedthelatticeparameterof mostof theplanesexaminedto below

4.07 A at low currentdensities,increasingto slightly above4.07 A. 71iis latter valuewas
8(a)
Figures
for
booster
Examination
the
that
the
of
same
about
as
alone.
samplescontaining
density,
9(a)
increasing
fell
lattice
200
that
the
ent
the
cuff
revealed
and
parameterof
plane with
of
similar to that of the samples,
with boosteralone. With relatively large concentrations
nickelin theelectrolyte,the311andthe220alsoexhibitedreductionsin thelatticeparameter,
particularlyat high currentdensities.
The crystallitesizeof the III planesasdeterminedby theScherrerequationwasin theregion
A
A.
Again, further analysis
200
100
in
of
whilst that of the otherplaneswas the regionof
revealedthat both stackingfaultsandRMS straincontributedto this difference.
To summarise,boththe boosterandthe nickel inducedaIII preferredorientationbut it was
The
density
booster
influence
the
that
range.
clear
exhibitedthe greater
over a wide cuff ent
of
evidenceprovidedby the measurement
of the latticeparameterindicatedthat the presence
both boosterandnickel reducedthesevaluesto belowthe pure gold value, probablydueto
incorporationof the additiveswithin the lattice. Indeed,the evidenceindicatedthat certain
III
for
incorporated
the
The
larger
true grain size
planes
a
proportionof thesematerials.
jetted
for
the
indicated
for
faults,
that
all
plane,after correction residualstrain andstacking
A
had
The
300
in
200
samples,a smallcrystallitesize the regionof
nickel
to
wasproduced.
a slight influencein reducingthe crystallitesizefurtherunderjetting conditions. However,
underconventionaldepositionconditions,it appearedto be the main causeof the reduction
of crystallitesize.

Figure 10 showsthe effect of current density and nickel in the electrolyte on the hardnessof
thejetted deposits. It can be clearly seenthat a decreasein the current density as well as an
increase in the nickel in the electrolyte reduced the hardness. This is unusual as under
conventional deposition conditions, it is generally acceptedthat increasing the nickel in the
electrolyte leadsto an increasein the hardness.Figure II shows the relationshipbetweenthe
hardnessand the nickel in the deposit for different concentrationsof nickel in the electrolyte.
It is evident that the quantity of nickel incorporated in the deposit is not the only factor
governing the hardnessbut is also a function of the nickel concentrationwithin the electrolyte.
Figure 14 showsa microsection of a typical alloy gold deposit producedusing HSSJE. As in
the caseof a pure gold jetted deposit, fan-like cells leading to a rounded mound structure can
be seen. No other internal structural featurescould be resolved using optical microscopy.

5 DISCUSSION

5.1 Pure gold deposits

I

Someof the more important physical and structural properties of pure gold depositsproduced
using HSSJE have been examined during the course of this experimental work. These
properties have been compared to deposits produced under more conventional deposition
conditions. Conventional pure gold depositsfrom a citrate electrolyte exhibit a crystallite
for
faulting)
for
0.2
(after
III planes and have
the
strain
and
accounting
of
around
size
jum
hardnessvalues of around 100 kg mm-2. Thesedepositsexhibit a 311 preferred orientation.
Such a texture has beenobservedby other workers.9-9.It was not possibleto obtain data on
the 311 crystallites ashigher orders of reflection could not be obtainedwith this experimental
lattice
However,
the
parameterswould suggestthat no sticking faults
examination
of
method.
These
they
the
samplesexhibited the lowest RMS strain
same
size.
as
are
all
present
were
for the III planesof all the samplesexaminedover the current density range analysed.
When depositsare produced from the sameelectrolyte using HSSJE, both the structure and
from
both
intrinsic
This
results
changesin the deposit
altered.
are
significantly
morphology
interaction
flow.
deposition
due
the
the
to
the
as
as
well
with
conditions
electrolyte
structure
The intrinsic changesresult from the very high rates of deposition. Ile crystallite size is
A,
200
Such
in
tenfold
the
of
a
reduction.
a reduction
to
region
a
value
reduced
considerably
is the most likely causeof the increasein the deposit hardness,increasingto a value of up to

200 kg mm-2,the hardnessshowingan increasewith increasingcuff ent density.Despitethe

high hardnessobservedwith this type of gold deposit,it hasbeenshown2 that goodtherdeposits
bondingpropertieswereretained.Ile surfaceappearance
jetted
mocompression
of
is smoothand featureless,graduallydevelopingsmoothroundedmoundswith increasing
currentdensity.This roundedmoundmorphologyis similarto that developedin the caseof
alloyedgolds.
A 220 preferredorientationdevelopswhich, ashasbeensuggestedby Lin et al'O-in their
A
deposits,
be
by
the
species.
effectsof additiveson gold
may caused ads6rbed
studyof
slight reductionin the latticeparameteris observed,whichmaybe dueto the incorporations
of small quantitiesof foreignspecies. Ibis would not be surprisingat suchhigh ratesof
depositionasthe speedat whichgrowthtakesplacecaneasilybury surfaceadsorbedspecies
during
deposit.
in
The
the
size
the
that
the
crystallite
evidencesuggests
reduction
within
HSSJEis a result of inhibitionof crystallitegrowthasa resultof someadsorptioneffect.It
hasbeenshownby Eisenmann".thatduringgolddeposition,growthproceedsvia anadsorbed
AuCN speciesandCN-is producedfrom thereaction.It is knownthatCN-canstronglyadsorb
onto gold surfacesand it is likely that this speciesis responsiblefor the crystallitegrowth
jetted
for
here.
is
important
both
It
and
the
to notethat
conventional
mechanismobserved
for
deposits,
lattice
the
pure gold
parameterof eachof the measuredplaneswas consistent
fairly
deposition
well
This
was
that
the
each
crystallite structure
method.
would suggest
low
No
low
faults
for
detected,
current
at
ordered. structural
probability
except a very
were
densities.This meansthat D, =D andthe true crystallitesize is asshownin Table 1.
ff
5.2 Alloy gold deposits
In the caseof the alloy gold, conventionaldepositsproduced from the Ronovel N electrolyte
exhibited RMS strains higher than the equivalent pure gold samples. However, no evidence
of stacking faults was seenfrom studiesof relative peak shifts. There was a slight asynunetrY
of the peaks.Unfortunately, the twin fault probability cannotbe calculated from the III peak.
Therefore, whilst it is known that twin faults existed within the deposit, their contribution
could not be measured. It is therefore most likely that in this caseD. fr < D. it is possible
that a significant contribution to broadening is due to twin faulting. Nakahara7-has studied
transition metal hardenedgold depositsproduced under conventional deposition conditions,
usingtheTransmissionElectron Microscope (TEM) andobservedsimilar topographic features
as in this study, with the deposit surface exhibiting "rounded mounds" or small nodules. It

33

'rounded
mounds observed exhibited a strong III orientation with a
was found that''ihe
A.
between
200
300
it was concludedthat such a structure formed as
and
crystallite size of
a result of inhibition of lateral growth by adsorbedspecies, presumably transition metal
complexes. Mie sameinhibiting moleculesadsorbedon the top surface of the growing planes
and causedcontinuous nucleation leading to the small crystallite size and high hardness.A
high number of twins were observedwithin the structure. It is evident that gold nickel alloy
depositsproduced conventionally shareda numberof morphological featureswith bothjetted
deposits
but
gold
some significant differences were observed in the microalloy
and
pure
structure.
In the case of the jetted samples, similar values of Dff were observed for the conventional
Ronovel N and jetted depositscontaining only booster. The presenceof nickel however led
to a reduction of -25% in this value. There appearedto be no direct dependenceof D., on
is
increasing
density.
It
the current density in simple electrolyte
that
generally
accepted
current
systemsleads to a reduction in crystallite size. These results would suggestthat in the case
inhibition
by
deposits,
Nakaharawas operative.
the
as
envisaged
an
process
conventional
of
The fact that a similar crystallite size was observed under jetting conditions suggeststhat
inhibition processeswere also responsiblefor the small crystallite size and not an influence
is
density.
The
increased
this
of
unclear anddifficult to identify
cuff
ent
exact
process
nature
of
as there are a number of possible inhibiting species.These include AuCN, CN-, booster and
transition metal cyanide complexes.It is most likely that there is an'equilibrium betweenthe
depending
deposition
the
concentration
on
prevailing
and
alters
conditions.
which
adsorbates
Tbestructural propertiesare therefore altered,dependingon the natureof the inhibiting species
incorporated within the deposit.
One of the most significant .differences in physical propertiei between the conventionally
is
influence
byjetting
deposits
the
those
of nickel additions.
and
produced
alloy
produced gold
Conventionally produced pure gold depositsexhibit a hardnessin the region of 100kg mm-2,
in
200
kg
do
hardness
deposits
the
those
region
of
MM-2
as
a
manifest
whilstietted pure gold
When
booster.
from
nickel was added to a conventional
containing
electrolytes
produced
increased
hardness
from
kg
MRN,
100
in
Auronal
the
the
the
nun-2to
case
of
electrolyte as
between 150 and 200 kg MM-2.Similar hardnessvalueswere observedwhen nickel was added
In
booster.
the caseof the electrolyte containing
N
Ronovel
only
to the
electrolyte containing
increasing
hardness
deposit
increasing
for
current
with
there
tendency
an
was a
only nickel,
density. In the caseof the electrolyte containing booster and nickel, the opposite trend was
HSSJE,
deposit
is
hardness
The
using
the
produced
containing
reduced proof
nickel
seen.

portional to the quantity of nickel addedto the electrolyte, from 2W kg mm-2 down to as low
as 110 kg mm-2.There is no direct evidenceto explain this behaviour as the jetted samples
containing boosterboth with and without nickel exhibited similar structures in terms of RMS
strain and stacking faults. The main difference was the reduction in the crystallite size in the
caseof the nickel containing sample.This alone was insufficient to account for the changein
hardnessas no current density dependencewas seenin terms of the crystallite size. However,
a linearly increasing current density dependencewas observedin the lattice parameters.The
nickel in the deposit reduceswith increasingcurrent density and there is an empirical linear
relationship for alloys whose individual componentstructuresare similar between the lattice
parameter and the atomic percent of an alloy constituent (Vegards Law) This would imply
that some of the nickel was being incorporatedwithin the lattice in the form of metal atoms.
It is known that whentransition metalsare addedto a gold electrolyte, conventionally produced
deposits incorporate the majority of the transition metal in the form of a cyano- complex. A
changein the way in which the transition metal interacts with the deposit is the most likely
explanationof the reduction in hardnessobserved.It is clear from Figures 10 and II that the
deposit.
in
in
hardness
is
function
in
the
the
that
change
a
of the nickel the electrolyte and not
This tendsto confirm the inhibition mechanismas the main influence on the hardnesschanges
observed.
It is further suggestedthat the changein the inhibition processis responsible for the change
in the wear characteristicsobservedin the study by Bocking and Cameron 4. They found that
.
jetted depositsshowedsomereductionin the wear resistanceparticularly with thicker Coatings.
There was also evidencethat the wear mechanismwas abrasivein nature. Such abrasivewear
is not observed in gold alloy depositsproduced from properly controlled electrolytes under
in
deposition
have
that
Vanhumbeek'2DeDoncker
conventional
suggested
conditions.
and
the case of gold cobalt alloys, the wear behaviour is strongly related to the proportion of
cobalt presentas metal to that presentas a cobalt ion complex, with high values of the latter
being required,for good wear resistance. If the cobalt concentration in the electrolyte was
too high, the incorporation of the complex within the deposit was suppressedleading to too
high a value of metallic cobalt in the deposit. Suchdepositsexhibit abrasivewear behaviour.
In addition, Antler13-has found that in order to obtain good wear resistance,the deposit must
have a low ductility as well as a high hardness. Such a combination would not be expected
from a deposit in which the alloying constituent was present purely in the metallic phase.
Nakahara7hassuggestedthat it is the inhibition dueto the nickel complex and its incOrPOration
into the deposit that is
in
for
gold nickel
the
observed
crystallographic structure
responsible
alloys. It would seemto follow, therefore, that due to the high rates of deposition achieved

I
35

in HSSJE,the inhibition processis changed,with much lessof the nickel complexbeing

incorporatedinto the depositbut as metalwithin the gold lattice. Ilis would explainthe
'
Cameron.
by
Bocking
in
thewear
and
resistance
observed
reduction
I
6 CONCLUSION

It has been shown that theuse of HSSJE ran significantly alter the micro-structure of both
harder,
become
deposits
deposits.
Pure
to
the
much
proportional
gold
gold
alloy
and
pure
in
being
despite
density.
However,
there
a
reduction
crystallite size and an
current
applied
increase in RMS strain, no direct dependenceon current density could be observed in the
from
311
for
deposits
in
HSSJE
texture,
a
the
conventional
a
change
causes
micro-structure.
from
in
Such
jetting
220
orientation
preferred
results
usually
a
change
conditions.
to a
under
deposits
Gold
inhibit
the
that
process.
alloy
electrocrystallisation
the use of organic additives
Whilst
the texture
to
those
conventionally.
produced
the
compared
change
greatest
showed
both
deposition,
for
III
the
methods
of
orientation
a
preferred
generally
remained
found
It
that although the morphology and
was
altered
considerably.
micro-structure was
300A
in
200
in
being
for
both,
to
the
the
the
of
and
nickel
region
crystallite size was similar
deposit was similar, the microstructure exhibited significant changes. Under conditions of
HSSJE,a high stackingfault probability wasobservedwhich wasnot seenin depositsproduced
in
is
It
the surface
this
thought
that
as
a
comes
about
result
of
a
change
change
conventionally.
high
deposition
densities.
As
from
at
very
current
a
adsorption/inhibition processresulting
incorporated
is
into
deposit.
71is
the
in
form
less
the
complex,
of a cyano
nickel,
result,
incorporation
jetted
deposits
in
the
the
as
of
of
wear resistance
would explain the reduction
the non-metallic inhibitor is responsiblefor the good wear characteristicsof conventional
deposits of this type. On the basis of the evidencepresentedin this and previous work on
HSSJE, that whilst pure gold deposits were found to be harder and possessa finer grain
bonding
thermocompression
characteristicswere not
structure, physical properties such as
in
differences
the
the
However,
structure
of
observed
were
significant
affected.,
significantly
Indeed,
influence
their
to
of
physical
properties.
under
some
that
appeared
nickel gold alloys
HSSJEdeposits
4
in
resistanceof
wasreduced.
theprevious
wear
study,
thetest conditionsgiven
be
to
the gold plating of
the
applied
that
does
cannot
process
This
mean
not necessarily
is
however,
the
be
understanding
mechanisms
of
What
greater
a
required,
will
connectors.
by which the nickel and nickelo-cyanide complex is incorporated within the deposit and the
factors that control the ratio of metal to complex within the deposit.

REFERENCES

1.

C. C. Bocking, Trans. Inst. Met. Fin, 66,50,1988

2.

C. C. Bocking, Proc. 59th IntnI. Conf. On Surf. Fin. 2,51, April 1991

3.

C. C. Bocking, East Report, Eugen G. Leuze Verlag, Saulgau, 1992

4.

C. C. Bocking & B. P. Cameron, Trans. Inst. Metal Fin., 72,1,33,1994

5.

B. E. Warren & B. L. Averbach, Joum. Appl. Phys., 21,595,1950; 23,497,1952

6.

A. R. Stokes, Proc. Phys. Soc. (London), B61,382,1948

7.

S. Nakahara,Journ. Cryst. Growth, 75,212,1986

8.

M. Antler, IEEE Trans. Components,Hybrids & Man. Tech., CHMT-4,1,15,1981

9.

S.E. Craig Jr, R.E. Harr, J. Henry and P. Turner, J. Electrochem. Soc, 117,1450,1970

10. K-L. Lin, W-C. Liu, M. H. M. Lin & Y. W. Hu, J. Electrochem. Soc., 138,3276,1991
11. E. T. Eisenman,J. Electrochem. Soc., 125,717,1978
12. R. DeDoncker & J. Vanhumbeek,Trans. Inst. Met. Fin., 62,59,1985
13. M. Antler, IEEE Trans. Components,Hybrids & Man. Tech., CHMT-4,1,15,1981

ACKNOWLEDGEMENTS

This work was carriedout as part of a BRITE-EURAMproject No RIIB-0304-C(A) *ImThe

Processes
in
Control
Speed
Electrodeposition
Attainment
High
provement the
and
of
.
Authorswish to thankthe EuropeanCommission,partnersCentro SviluppoMateriali and
LoughboroughUniversityfor their kind permissionto publishthis work.

37

C.D.

SAMPLE

PureAu Conv.

3.0 mA/cml

D.,, k

D,, )L

D.. A

(111)

(111)

(222)

2352

744

540

< e3>
(111)

O.OOW35

Booster Hardness

g dnrs

cm,
dn3,-s

kg inrrra

n/d

101

PureAu Conv.

7.0 mAlcm2

2321

960

551

0.000035

u/d

Pure Au Jetted

2.0 Alcm2

324

326

198

0.00011

Pure Au Jetted

4.0 A/ml

350

349

206

PureAu Jetted

6.0 A/cml

335

327
1

Ka

cl
(111)

I
1

0.007

163.9

0.00015

n/d

198.9

215

0.000115

nld

203.5

304

205

0.000135

n/d

204.1

n/d

1.7

60

198

102.4

PureAu Jetted

8.0 A/cm2

329

Ronoval N Conv.

10.0 mA/cm2

261

104

128

Ronoval N Conv.

40.0 mA/cml

254

107

128

0.000135

n/d

1.7

60

130

Ronoval N Jetted

3.0 A/cm'

324

340

209

0.000115

0.021

60

200.1

Ronoval N Jetted

9.0 A/cm2

289

307

189

0.00013

0.022

60

212.2

Ronoval N Jetted

3.0 A/cml

191

182

104

0.00017

pocwpcak

1.9

60

127

0.00015
-

ramAdiou
1.9

60

170

Ronoval N J:;

9.0 Alcml

200

1 201

128

1 0.00015

1 0.027

TABLE 1. Crystallite size, RMS strain and stacking fault probabilities for some samplesfor
the (I 11) planes only. Note n/d = not detectable,n/m = not measurable.

38

Current DensityA/cm sq
0 0.75
2.0

,
,74.0

0 6.0
+ 8.0
03

012
R Dimensionless
distance

Figure 1. A typicalselectivityplot showingselectivityasa functionof the currentdensity.

39

4.1

-*-III
200
-*-a-220
-311
--w-222

4.09

4. OB

4.07

4.0&

a)
4.05 'III
05

to

15

20

25

30

35

40

C.D. FrA/cmsq
Wo
CA

80

200
220
-311

10 rl

4a E30

ION
15

05
10
Figure 2. (a) Lattice

20

25

30

35

40

C.D. M/cs sq

parameterand (b) preferred orientation data for conventionally produced

pure gold deposits.

40

a)

90 GO 10 -

200
-.*-220
-311

Go io -

40
30
20
le

b)
456
C.D. A/cmsq

Figure3. (a) Lattice parameterand(b) preferredorientation datafor HSSJEpure gold deposits.

41

100
go

0111
Re
-ZM
-311

S
S
a

so

-0

40
30
20

10

0t
0

10
b)

20
33
C.11 irA/cmsq

40

50

g
I

c)

Figure4. (a) Latticeparameter(b) preferredorientationand(c) hardnessdatafor RonovelN

depositsproducedconventionally.

42

'20

4.1

9a

:: 200
220
-311
-222

4.09

Z20
311

83
70

re

4. OB -9

60

4.07
39

.3

4.06

20

05M

15 20 25
C.0. M/cm sq

30

35

10

10

3)

3B

40

50

C.D. aVcm sq

le

z
IsLM 20
kk. sq

30

35

c)

Figure5. (a) Latticeparameter(b) preferredorientationand (c) hardnessdatafor Auronal

MRN depositsproducedconventionally.

43

4.1

4.0)

COB

4.07

4.06

a)
4.05
5

20 '

15

10
C.D. A/(m-,q

100
9a

-*-III
-200

so

-220
-311

40
30
201

10 r.

-_Zz

b)

--i---I
is

28

C.D. AVCM
Sq

data
for
HSSJE
Ronovel
N
(b)
Lattice
6.
(a)
orientation"
Figure
preferred
and
parameter
but no nickel.
depositsproducedfrom an electrolytecontaining60CM3dM-3booster

44

4.1 1

-*-III
-200
220
-311
-222

4.03
. -K

4.08

4.07
-J

4. Ob

a)

4.05

0
too

15

10
C.O. A/cmsq

20

90

-200
220
-311

80
70

60
50

40
30
20
to

b)

10

Is

20

C. D. "CM Sq

Figure 7. (a) Lattice parameterand (b) preferredorientationdata for HSSIE RonovelN

depositsproducedfrom an electrolytecontaining80CM3dm-3
boosterbut no nickel.

45

-1

a)

"0

o
b)

Figure 8. (a) Lattice parameterand (b) preferredorientationdata for HSSJERonovelN

boosterand 1.9 g dm-3nickel.'
depositsproducedfrom an electrolytecontaining60CM3dm-3

46

a)
20
sq

1a3
.33

-*-III
-200
220
-311

10
60
le
Z

40 33
23:
10

b)

15

la
C.o. &/Cosq

20

Figure 9. (a) Lattice parameterand (b) preferredorientationdata for HSSJERonovelN

depositsproducedfrom an electrolytecontaining60CM3dm-3
boosterand3.0 g dM-3nickel.

47

3456789

10

Cun-ent deasity A/cm sq

Figure 10. Ile effect of current density and nickel in the electrolyte on the hardnessof gold
*
nickel alloy depositsproduced by HSSJE.
-: ,I-

48

Figure11.Therelationshipbetweenthehardness
diff6rent
for
in
deposits
HSSJE
the
and nickel
concentrations
of nickel in the electrolyte.

49

Figure 12. A microsection of a pure gold deposit produced using HSSJE. Current density
6.0 A CM-2,Re. = 12000, Temp. = 55-C. X 1000.

50

Figure 13. A microsection of a pure gold deposit produced using HSSJE. Cuff ent density
7.0 A CM-2,Re. = 12000, Temp. = 55-C. X 1000.

51

Current
HSSJE.
using
deposit
prWuced
alloy
nickel/gold
a
of
dm-3.
Figure 14. A microsection
3.0
g
=
in
the
electrolyte
Nickel
55,
Temp.
-C.
10600,
=
Re.
A
=
6.0
cm-2,
density =
x 1000.