Sem Course

)(Scanning Electron Microscopy
)(Resolution

Resolution

/ m ) 0.1 mm
(.

mitochondria m

)(Resolution

Magnification
.
Rayleigh Equation
0.612.
=d
) n.Sin(
= n
=
aperture angle
= d

=
(
)
Lens Defects
- Spherical aberration
Chromatic aberration

-
-
Diffraction
Astigmatism

Lens Defects
optic axis
Aperture
image plane
Spherical
aberrationP2
Chromatic
aberration
Diffraction
Lens Defects

)(Contrast
Is I0
(Is-I0)/Is

)(Contrast
) (Rose criterion

(Is-I0)> 5n
n ) (Counts ) (Background
0.95
0.5
0.4
0.3
0.25
0.1

)(Contrast

) (Airy Disc % .
Aperture
Diffraction

)(Contrast

) (Rayleigh criterion

)(Contrast

) (Rayleigh criterion
0.612.
=d
n.Sin
) Si (

)(Contrast
400 nm

1.7 150 nm
17
.
0.612.
=d
) n.Sin(
Lens Defects

Spherical Aberration
d0 : gun crosscross-over
diameter
aperture
Lens Defects

Lens Defects

Cs

3
d 2 = Cs .
)(SEM

d0

d1 = d0.(v1/u1).WD/u2
WD= Working Distance
d1=0
u1
v1
u2
WD
d1
)(SEM

ds=2.Cs. 3
dd=22 . (0.612
(0 612 / n. Sin
) Si
d1 = d0.(v1/u1).WD/u2
d=(d12+ds2+dd2)1/2
d d1=0 ) (
dmin=K. 3/4.Cs1/4
K
)(SEM

dmin=K. 3/4.Cs1/4

(=0.0086 nm) 20KV
SEM

Cs=20mm =5.1x10-3 rad 0.3
dmin=2.3
=2 3 nm

) Pease (Nixon
3/8
9 I .T
d = d min 7.92 10
+ 1
j

)

T

I
( j ) (100-200 A.
Lens Defects
Chromatic Aberration
)(Magnefication

100
100
10
10
111micrometer
micrometers
nanometer
nanometers
centimeters
micrometers
centimeter
nanometers
1 meter
source:
source:
CERN
http://microcosm.web.cern.ch/microcosm
source: CERN
CERNhttp://microcosm.web.cern.ch/microcosm
http://microcosm.web.cern.ch/microcosm
.

.

(
)

.

.

Brogly
e=h/m.v
=h/m v
E=e.V=1/2.m.v
E
e.V 1/2.m.v2

0.0054 )
0 0054 nm

( =0.9 n=1
0.21 ) 0.2 (.
)(SEM

SEM_Scanningg system
y

Busch
)(TEM

) (Transmission Electron Microscope-TEM .

TEM
) (electromagnetic condenser lens
.

.

) (objective
) (projectors
)(TEM
TEM_Overview
)(TEM

.
TEM_Itroduction I&II
TEM_Overview
)(TEM
)(TEM
)(SEM

. SEM .
Introduction To SEM
SEM
.
SEM-Scanning system
)
7nm

SEM
)(SEM

X20
)(SEM

SEM Overview
SEM_Overview

STEM
Resulted Image
Image recording
)(SEM

)(The electron gum

.

%

)(

) (wehnelt
SEM-Electron Gun P1&2
) (High voltage

(SEM)

Filament heating supply
Filament
W h lt cap
Wehnelt
Cross--over plane
Cross
Anode
High voltage
supply (200
(200 v- 30 kV)
)(SEM

Bias on Wehnelt cap

.

.

.

) accelerating
(voltage .
Wehnelt cap
0-500 V negative
)(respect to the cathode
0
+
Convergence of the
beam to a crossover of
dimension d0
Anode 0-30000 V
Divergence angle
)(SEM

Bias on Wehnelt cap

.

.

.

)
)(grid cap

(( .

) bias(
Wehnelt cap
0-500 V negative
)(respect to the cathode
0
+
Convergence of the
beam to a crossover of
dimension d0
Anode 0-30000 V
Divergence angle
(SEM)

Bias on Wehnelt cap

Low bias voltage
0
+
Optimum bias voltage
0
+
Hi h emission
High
i i
large spot
High bias voltage
0
+
N emission
No
i i
Sufficient emission
small spot
TEM SEM Electron Gun (P3)
TEM_SEM
Lines of constant
electrostatic field
potential
If negative field gradient is weak ib increases d0 increases is not optimum

If negative field gradient is too strong ib = 0
(SEM)

Crossover
)
(
0
+
The current density in the electron beam at

crossover represents the current that could be
concentrated into a focused spot on the
specimen (without aberration considering)
J b ( A / cm 2 ) = 4.ib / .d 02
Jb=Maximum
Maximum intensity of electrons at crossover
ib=emission current measured from the filament (~100-200 A)
d0 = crossover
)(SEM

J b ( A / cm 2 ) = 4.ib / .d 02

.
But the most important is the current
density per unit solid angle which is
fixed by the aberrations of the final lens
Which is called electron beam
brightness
g
)(
0
+
(SEM)

Aberration
Electron beam brightness
g
() = Current density
yp
per unit solid angle
g
= J c .e.E0 / .k .T
= 4.ib /( .d 0 . 0 )
Maximum value for by Langmuir Eq.
J b ( A / cm ) = 4.ib / .d
2
J b = J c .e.E0 . / k .T = . .
2
0
Jc= 1.75 (A/cm2) at 2700K

E0=Accelerating voltage
T=Temperature
0=solid angle
2
0
2
0
(SEM)

Bias on Wehnelt cap

-

Maximum brightness can be obtained by
1 Adjusting
1Adj ti
filament
fil
t to
t grid
id spacing
i
or
2- Bias resistance (at Wehnelt cap)
/ (A/cm2)

J b ( A / cm 2 ) =
Typical values for EPMA and SEM

For W filament at 2700K with Jc=1.75 A/cm2
d0=25-100m
2
= 4.ib
4.ib / .d 0
0=3x10-3 8x10-3
=60000
60000 A/cm2.steradian
Ib = 100-200 A
In a conventional X-ray tube ib is 15-25 mA
/( .d 0 . 0 ) 2
(SEM)

-
-
I
Increasing
i off (increasing
(i
i off resolution)
l ti ) iis possible
ibl by
b
1- Increasing of ib for the same beam size
2- Decreasing of d0 for the same ib
= 4.ib /( .d 0 . 0 ) 2
J b = J c .e.E0 . 02 / k .T = . . 02
= J c .e.E0 / .k .T
Increasing of E0 is limited (normally 30 40 KV)

Increasing of Jc
Tfilament = 2700K Jc= 1.75 A/cm2 = 60000 A/cm2.steradian Filament life=60-70 hr
Tfilament = 3000K Jc= 14.2 A/cm2 = 440000 A/cm2.steradian Filament life= 1 hr
)(SEM

Normal filament temperature
2650 2900K
2650-2900
K
100X150m emission area
FEG
LaB6
)(SEM

LaB6

LaB6

1680C A/cm2
.

1600 C A/cm2
5X105A/cm2 .Steradian
75 KV Steradian
) ( A/cm2.Ster.
)(SEM

LaB6

106 torr

.

.

1700
1700-2100K
2100 K
LaB6
(
)

.
2.5 .
)(SEM

)(FEG

.

.
)(SEM

)(FEG
.

) (
.

)(SEM

)(FEG

106 A/cm2 )

1m 1.75 A/cm2 ( 23 KV

5X109A/cm
A/ 2 .Steradian
S
di

LaB6 . 1010 torr

.
.

.
(SEM)

Pi
Primary
electron
l t
beam
b
~ 10 nm: SE
~ 1-2 m: BSE
~ 2-5 m: XX-ray/CL
Interaction volume
)(SEM

) (Pixel ) (Pixel

::

P= 100m/M
M
.

Pixel
e

M = 100,000 P = 0.001 m = 1 nm
)(SEM

.

Pixel

Pixel
.
LaB6 FEG

Pixel

)(SEM

d0

d1 = d0.(v1/u1).WD/u2
WD= Working Distance
d1=0
u1
v1
u2
WD
d1
)(SEM

pixel
Primary electron beam

) (p
~ 1-2 m: BSE
~ 2-5 m: XX-ray/CL
Inte
eraction volu
ume
~ 10 nm: SE
)(SEM

ds=2.Cs. 3
dd=22 . (0.612
(0 612 / n. Sin
) Si
d1 = d0.(v1/u1).WD/u2
d=(d12+ds2+dd2)1/2
d d1=0 ) (
dmin=K. 3/4.Cs1/4
K
)(SEM

dmin=K. 3/4.Cs1/4

(=0.0086 nm) 20KV
SEM

Cs=20mm =5.1x10-3 rad 0.3
dmin=2.3
=2 3 nm

) Pease (Nixon
3/8
9 I .T
d = d min 7.92 10
+ 1
j

)

T

I
( j ) (100-200 A.
(SEM)

Electron Sources differ:
Resolution
L kV performance
Low
f
Lifetime
Ease of maintenance
Cost
(SEM)
(FEG)
W
resolution at 3.5nm
30kV
l
low
kV
+
performance
lifetime
2
weeks
time to
1
stabilise
minute
costs
low
LaB6
FEG
2.5nm
2nm
++
++++
1
year
2 hours
2
years
1 day
high
highest
(SEM)

Vacuum
Tungsten
configuration
LaB6
LaB6
configuration
IGP
IGP
valve
XL
XL
ODP or
TMP
rotary
t
FEG
configuration
IGP
valve
XL
ODP
rotary
ODP
rotary
)(SEM

Column optics control

d0 : gun cross
cross--over
diameter

.

1-beam diameter

2-beam current

3-convergence angle
condenser lens
d1: demagnified
d
ifi d
cross--over
cross
1
aperture
objective lens
Final probe size
(SEM)
Astigmatism
disc of least confusion

magnified point source
)(SEM
Astigmatism
(SEM)
Astigmatism
corrected
over focus
under focus
no orientation
90
(SEM)

Filament Saturation
emission
n curre
ent
Saturation point
False peak
f
filament
current
)(SEM
Depth of field
.

focal plane

0.612.
=h
) n.Sin( ).tg (
)(SEM
Depth of field
.

focal plane

(SEM)

L/I=
Magnification
l
SEM
Scanning System
Resulted Image
Image recording
(SEM)
Scintillator-type
Scintillator
type Backscattered
detector (Robinson)
P-scintillator
Robinson detector
With Phosphor Scintillator
through light guide to
Photomultiplier tube
specimen
i
Aluminum
High image quality.

The image forming speed is fast
enough to produce a direct
i
TV
image, however it strongly limits
the mobility of the specimen, in
particular when tilting.
(SEM)

(BSE)
Base plate Semiconductor
Solid state detector

+++++++++++++
----------------------
Silicon dead layer

Surface electrode
Backscattered electrons
A+B Compositional contrast
(0.1 mean atomic number resolution)
A B Topographical information
A-B
A or B
The image
i
forming
f
i speed is
i
not fast enough to produce a
direct
d
ect TV
V image,
age,
but good image quality may
be obtained at slow scan rates.
)(SEM

)(SEM

)(BSE
a:
b
b:
BSE detector
60 degree
(SEM)

(BSE)
Phase B
mean atomic number -
-
y
g p
p
preferred orientation
crystallographic
(channeling)
surface inclination -
internal magnetic field -
Phase A
The image forming speed is not fast enough to produce a direct TV image,
but good image quality may be obtained at slow scan rates.
)(SEM

)(SE
final
lens
SE33
SE
SE11
SE
SE22
SE
specime
n
Everhart Detector
(SEM)
Detector parameters
Pole piece
Collection angle
Detector
ttake
takek -off
ff
angle
Specimen
(SEM)

(SE)
Surface roughness has

also
l an influence
i fl
on
the TOA
Could lead to false
conclusion
)(SEM

Beam energy

small-scale
small
scale surface topography

surface inclination
mean atomic number
crystallographic orientation
(SEM)

Pi
Primary
electron
l t
beam
b
~ 10 nm: SE
~ 1-2 m: BSE
~ 2-5 m: XX-ray/CL
Interaction volume
)(SEM

SE
BSE
frequ
uency
Auger
EPE
2 kV
electron energy
50 eV
(SEM)

=nSE/nB
=Secondary electron coefficient

nSE=Number
Number of secondary electron
nB=Number of electrons put in the specimen by the beam
Secondary electron coefficient increases as the beam energy decreases
Below 5KV the effect becomes apparent, because the penetration depth
Is so small that a significant portion of the generated Secondary
electrons can escape from the surface.
(SEM)

IIn this
thi conditions
diti
Secondary
S
d
electron
l t
coefficient
ffi i t may exceeds
d unity.
it
So no charge built-up from an access of electrons occurs at the
specimenss surface
specimen
surface.
So non-conducting specimens can be examined at low voltages
without need for conducting
g coating.
g
The no-charge beam energy lies at around 2-3 KV for most materials
and may be increased when tilting the specimen.
1
E1 <1kV
beam energy
E2 >1.5kV
(SEM)

Tilt effect
When the beam hits perpendicularly to the specimen only a a small
volume may contribute to the secondary electron signal.
At an inclined surface secondary electrons escape from a much
larger volume and the Secondary electron coefficient may increase.
Electron beam
primary electron beam
SE
SE
R0
inclined surface
Horizontal
surface
)(SEM

15 kV
5 kV
25 kV
)(SEM

Iron
Silver
Carbon
)(SEM

0 degree tilt
70 degree tilt
30 degree
g
tilt
)(SEM

+300 V
SESEdetector
B
C
(SEM)

Magnetic Contrast
primary electron beam
SE
SE
alternatively magnetized domains
(SEM)

(SE)
Light guide
Faraday cage
(-150 - +300 V)
Phosphorous
screen (Al(Al-coated) Scintillator
S i till t
(10 kV)
Photomultiplier
glass target
Electrons are transformed into light by Scintillator

Scintillator.
Light is transformed electrical signal in the Photomultiplier tube.
This transformation is fast enough to make a TV image on the screen.
(SEM)

(SE)
A positive bias of 10 KV is applied to the thin aluminum layer,

so the low energy secondary electrons are accelerated to carry
Sufficient energy to produce light in the Scintillator.
Secondary electron detector receives a combination of
secondary electrons or back scattered electrons.
(SEM)

(SE)
A separate bi
bias voltage
l
between
b
-150V
150V to +300V
300V can bbe applied
li d to the
h
Faraday cage, which is insulated from the Scintillator bias.
When applying a negative bias all secondary electrons are rejected and only
back scattered electrons can enter the detector.
In normal operations, a positive bias is employed to attract secondary electrons
that
h do
d not travell directly
di l by
b line-of-sight
li
f i h to the
h detector.
d
)(SEM
)(SEM

Sample
p Preparation
p
)(SEM

Sample Preparation
)(SEM

Sample Preparation

Out gassing

.

)

(

.
)(SEM

Sample Preparation
(SEM)

Electrical Charging
Coating
Fast scans
Lower voltages
Smaller spot
p
(SEM)

Electrical Charging
Coating properties
Good conduction
Chemical inertness
Good secondary electron emission
Small grain size
Easy to produce thin films
Not many materials have all these properties
(SEM)

Electrical Charging
Common Coats
Gold
Gold/Palladium
Ch
Chromium
i
Carbon
(SEM)

Electrical Charging
Coating Methods
Vacuum evaporation
(Simpler, non continuous for complicated shape samples)
S tt i
Sputtering
(Dislodging atoms from a metal cathode using gas plasma, more uniform)
Both methods can damage delicate specimens and creating artefacts
1.
Thermal
damage
2.
Surface
etching
3.
Decoration of the specimen
Evaporation involves radiant heat (reduction by increasing the distance)
Sputtering raises the surface Temp. by hit the electrons on the surfaces
(SEM)

Electrical Charging
Shorter but alternating coating times
Higher
Hi
h resolutions
l ti
image
i
also
l individual
i di id l grains
i off material
t i l within
ithi coating.
ti
This structure detracts from true structure of the sample (Decoration)
Th thickness
The
hi k
off the
h coating
i iis also
l worth
h consideration.
id
i
A thick coat is most effective at conducting the charge
But
May obscure very fine surface details.
Thickness chosen depends on the severity of the charging and the highest
desired magnification
(SEM)

Mounting media
Aluminium
Carbon
Copper
mounting adhesives
Double--sided tape
Double
Metallic tapes
Wax or oil based mounting media
(SEM)

Electrical Charging
Mounting media
1 Aluminum
1Al i
stub
b
Good conductivity, low cost and easy shaping
Flat, 30, 45 and 60 degree
Usage:
Secondary imaging
Back scattered imaging
Cathodoluminescense imaging
EDS analysis
(SEM)

Electrical Charging
Mounting media
2- Carbon
For
particles or powders which need X-ray analysis
But only contain elements above carbon in the periodic table
Carbon shows low atomic contrast in the backscattered mode
(Carbon atomic contrast appears black in backscattered mode)
Usage:
(SEM)

Electrical Charging
Mounting media
3- Copper
A cup like shape cooled in liquid nitrogen
For polymeric or biological samples
Usage:
Secondary imaging
Cathodoluminescense imaging
EDS analysis
(SEM)
Mounting Adhesives
1 Liquid
1Li id or semii liquid
li id
Make a conductive connection between substrate and specimen surface
Adhesive must withstand the vacuum without outgassing continuously
More common solvents:
Toluene, Xylene, Benzene, Dichloro-ethylene, Amil-acetate, Acetone,
Alcohol, Pentane, Ketone and Water
Al solvents
Also
l t in
i the
th adhesive
dh i may
prolong
outgassing
Affect the sample material
Detrimental to health
2- Double-sided tape (Copper or Carbon)

3- Metallic tapes
Preparation Techniques
Fracture Study
1-Metals
Fracture,, machining,
g, shock (immersing
(
g in liquid
q
nitrogen)
g )
2-Non-Metals
Plastics: immersion in liquid nitrogen)

Ceramics: Normally not so willing to fracture even at low
temperatures (hard
(h d iimpact iis normally
ll necessary))
Organic materials: (food stuffs, plant and animal tissue &
semi-solids like fats or oils) More care is necessary, damage
due to the ice forming at low temperatures, a special system
is needed (Cryo-system by a pre-cooling and then complete
immersion in liquid nitrogen.
Sections
1-Hard samples
Metals: diamond (wheel, saw or paste), Electro polishing, Ion

beam etching
Rocks: diamond (wheel, saw or paste)
Glass: carborandum powder ending with diamond paste
11-Soft
Soft samples
Mounting
S l l blade
Scalpel
bl d
Dispersions
Wet dispersions
P l
Polymers,
paint
i t pigments,
i
t biological
bi l i l cultures
lt
Dilution for homogenizing, then pipeting or atomizing on a
substrate and/or conductive coating
Dry dispersions
Non metallic Powders must have at least some well conducting
Non-metallic
particles (sputter coating with care to prevent thermal
damage) sticky carbon disk
damage),
Live Materials
Insects
R
Removing
i off th
the ffatt tto preventt th
the explosion
l i within
ithi th
the SEM
chamber
Immersingg in to ethyl-alcohol
y
for at least 1 or 2 weeks to
dissolve the fats. Then wash with fresh ethyl-alcohol.
Coat and mount with carbon and follow with Au or Au/Pd coat.
For a presentational exercise, use a fly which has been dried out
in a spider web only for 1 or 2 days.
days
Live Materials
Plants
Pl
t
Cryogenic treatment can be effective for 15 minutes, using 1KV
with no coating. After that the structure collapse.
y g and Cryogenic
y g
treatment are generally
g
y effective for live
Drying
materials
)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

H13

)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

Over modify
Al Si
Al-Si

Al-Si
)(SEM

Al Si
Al-Si

Al-Si
)(SEM
Al-Si
Al
Fe
Si
Mn
)(SEM

)(SEM

)(SEM

Al-Si
)(SEM

Energy Dispersive Spectroscopy
Epicurus Democritus

.

. )( Atom .

.

.

.

:

Anaximander
.

.
Prout :

(
)

The Mathematical principles of natural

.

philosophy
hil
h

.
.

interaction.
.

. .
.

.

.

.
plank
.
" " .

) J.J.Thomson & G.p.Thomson, The conduction of Electricity
( Through
Th
hG
Gases V
V.1.2.
1 2 1928,
1928 voll II.1933
II 1933

)( .
.
Thomson Millikan
.
.

) (probe

.

.

. .
BOHR

.

.
) (

.

)
( ) (Quanta.

((.
)
.
Packets of energy

.
) ( .
6X1019 .
= h.

.

Philosophical
Phil
hi l

) (Louis De Broglie .

.
.

.

. .
.

= h/m.v

10E-15
3.6E30 3E8
3 6E30
3.6E-63
) (

6.6E-63 .

.

6E7 .
1E-7 .
) (Lave X

(Debye
D b &S
Schere
) h

.
.

.

.
.
.

.

(
)
= h/m.v

:
(

)

.
:

.

" ) ( Stationary states .

.
=h.
.

.
)

( ) (Quanta.
BOHRs Theory
.

)
.(....
(

= h.
.

(

)

h
=
m.v

.

:
((e, m, c, h
))h,

-

-
.
.
.

.
.

.

) (

n

-
) .(
. .

l

-
:(erg.sec
0(n-1), (n-2), (n-3),
n=1l=0
1 l 0
n=2l=0,1
n=3l=0,1,2
.

.

) (2=n

) (

.

.

.

)

(

))

(.
)

(

.

.
.

-
.
/ erg.sec

- m
L (L-1),
L,
(L 1) (L-2),
(L 2) ,0
0
) (m

.

.

.
E2 - E1 ( = X)X-ray radiation

J .
|J= |l+ s
J

:
x= 2j+1

.

= l
1
1 J = 0

x 2J+1
x=2J+1

x=2J+1
J= |l+ s|,
|s
|J== |l+ s
(2j+1
)2j 1
)
(
)(erg.sec
)
1, J = 0
1
)s (erg.sec
l = 1,
1
)l (erg.sec
1s
1/2
-1/2, +1/2
2s
1/2
-1/2,, +1/2
2p1/2
1/2
-1/2
2p3/2
3/2
+1/2
3s
1/2
-1/2, +1/2
3p1/2
1/2
-1/2
3p3/2
3/2
+1/2
3d3/2
3/2
-1/2
3d5/2
5/2
+1/2
n
1
2
1
2
.

.

.
E2 - E1 ( = X)X-ray radiation

. .

.

.

- )(Bremsstrahlung
- )(

L
L
K
K

) (L
K

) (K
.
) (M
K

) (K
.
)

) (M ) (L
L .

) p (
P S P
K K
K1
K2
1S
2S 2P
)(SEM

(SEM)

Si(Li) crystal : Li drifted zone to p
prevent leakage
g current
cooling is needed
Bias voltage over crystal to
create charge free zone
Crystal produces electron /
hole pairs
FET (field
(fi ld effect
ff t transistor)
t
i t ):
noise reduction by cooling
(SEM)

Electron / hole pair created for
every 3.8 eV incoming X-ray
Ca Ka X-rayy ((3.80 KeV)) will
produce 1000 e/h pairs
Electrons (charge) are counted
No accurate counting process :
peak broadening
(SEM)

Detector must be protected:

1- Windowless system
2- Beryllium Window
3- Polymer window
3
(SEM)

Continuum radiation = Brems- strahlung or background radiation

Observed fall out at low energies due to X-ray absorption enroute to the detector
B k
Background
d need
d tto b
be removed
d ffor quantification
tifi ti
(SEM)

Ch
Characteristic
t i ti lines
li
superimposed
i
d upon the
th background
b k
d
(SEM)

Continuous background : non-linearity, decreasing peak height towards high energies
Never compare peak heights
(SEM)

Typical spectrum of Ti K
radiation
di ti
K radiation normally
doublet (for elements
with a Z higher than K)
K-lines : Gaussian shape
Ratio between Ka and Kb :
about 5 : 1
(SEM)

Typical spectra of Sb L
radiation
Multiple-lines
Often not Gaussian,
Gaussian tailing
towards high energy side
(depending on element)
)(SEM

(SEM)

All X-ray lines of all elements visible with 30kV beam

Max. visible K-line = Mo (42)
Mo Ka = 17.44 KeV
Mo Kab = 20.00 KeV
overvoltage = 1.5
Elements > 42 : use L-lines or M-lines
(SEM)

CrK
MnK
K lines are unique for each element

However, possibility of overlay by different types of rays (CrK, MnK)
)(SEM

CrK
MnK
K
Si Detector resolution ~ 135 ev Deconvolution
(SEM)

Deconvolution
X-ray energy M < L < K
Barium : K -lines
lines normally not visible because of insufficient primary
beam energy (max 30keV)
)(SEM

(d . sin
) i (
)(SEM

X
X-ray
Atomic planes
Light
Mirror
)(SEM

)(SEM

(d . sin
) i (
)(SEM

Brag law
n. = 2.d . sin
2d.sin=1/100
First & 50th rays
)(SEM

Brag law
n. = 2.d . sin
)(SEM

Brag law

Fe
n. = 2.d . sin
)(SEM

Rolands Circle
(SEM)

Detector
Detector resolution
Detection limit
Energy range
spectrum
Element range
Photon efficiency
Beam current
WDS
Crystal (diffraction)
~ 10 eV
0.01 wt%
one line
EDS
Si(Li) semi-cond.
~ 135 eV
0.1 - 0.2 wt%
complete
Z > 5 (B)
small
high
Z > 5 (B)
high
low
(SEM)

EDS
WDS
Example
p of EDS and WDS : Overlap
p of Pb Ma ((2.342 KeV)) and S Ka
(2.307 KeV) difference = 35 eV
(SEM)

Quantitative analysis is normally carried out by comparing the Kratios
ti (comparing
(
i sample
l picks
i k with
ith pure element
l
t picks)
i k)
However
In more complex specimens the concentration is not simply calculated
from the K-ratio by
y comparision,
p
but is a function of the K-ration
corrected for Z, A and F
Z A F method
(SEM)

Signals generated in the SEM
Backscattered electrons
Secondary
d
electrons
l
Auger electrons
X-ray quanta
Photons
Heat
(Specimen current)
Cathodoluminoscence
(SEM)

Signals generated in the SEM

Auger electrons
)(SEM

Operation of the Analytical Microscope

Fixed
D = intersection distance
E = elevation angle
A = azimuth angle
Variable
W = working distance
S = scale setting
M = sample tilt
Calculated
T = take-off
t k ff angle
l

Hi h TOA
Higher
WD < ID
TOA < EA
WD
ID
More photon
Minimizing
g of absorption
p
path distance
WD > ID
TOA > EA
WD < ID
TOA < EA
Tilt > 0
TOA
Elevation
angle
WD
WD
ID
ID

Take-off angle - Absorption
X-ray generation in sample :
absorption from photon by each
depth
Variation of the absorption
against taketake-off angle
Minimum taketake-off angle = 30
30
Tilt will
ill increase
i
the
th taketake
t k -off
ff
angle

Take-off angle - field of view
L
Low
TOA
Optimum
p
TOA
and field of view
High TOA
Low field of view

Take-off angle - Solid angle
WD
WD
Solid angle
WD
Solid
S
lid angle
l
TOA=cte
TOA
Operation
p
of the Analytical
y
Microscope
p

Over voltage
Incoming electron must be higher
in energy than the critical
excitation energy of the element
Fe Ka = 6.398 KeV
Fe Kab (Ec) = 7.11
needed voltage = 20 25
Optimum : 2 - 5 x the energy of
the emission line
X-ray
y Generation
Fluorescence yield (Z effect)
X-ray
X
ray fluorescence yield:
probability of a photon being
emitted
Fractions of ionisation >
results
in X-rayy
Emitted X-ray ejects an electron
from one of the outer shells and is
itself absorbed.
Yield higher for K - than
for Llines
li
Yield larger for high Z
X-ray
y Generation
The atomic number factor or Z factor, corrects for the
difference between X-rays that are generated in the
sample compared to those generated in the standard
It arises because of differences in the backscatter
coefficient and the electron stopping power between
unknown and standard
X-ray
y Generation
Fe
C
25 KV
X-ray
y Generation
For higher Z there is less penetration of beam in the
specimen (less Z effect)
It can be eliminated by using a standard similar in
composition to the unknown sample
Z effect can be minimized by using a high over voltage
(however this approach will increase the absorption effect
X-ray
y Generation
Absorption (A effect)
X-ray
X
ray absorption : stopped
enroute to the detector
Absorption by material
and detector window
Absorption depending on
the Take-off
Take off angle
X-ray
y Generation
Fe Ka X-ray line
6.398 keV
Fe abs energy
7.111 keV
To eject an electron : amount of

energy needed (overvoltage)
Discrete and specific energy
required to excite electron =
- absorption edge energy
-critical
critical excitation energy
- ionisation energy
Always slightly higher than
X-ray
emission line
Fe Ka X-ray line = 6.398 keV
Fe abs energy = 7.111 keV
X-ray
y Generation
Accelerating Voltage= normally 1.5-20 times of characteristic ray
X-ray
y Generation
Quantitative analysis - Background subtraction
X-ray
y Generation
Mass absorption coefficient
function of atomic number
(Z) and energy (E)
Sharp discontinuity :
absorption edge
Energy of incident X-ray
drops
p below Kab : no
energy to eject K-electron
Absorption continues to Lab
to Mab
X-ray Generation
Fluorescence (F effect)
Consequence of absorption is
X
X-ray
fl
fluorescence
or
secondary fluorescence
Generated X-ray in sample can
eject an another electron
Ni-Fe alloy:
shaded area indicates X-rayy of
sufficient energy to excite Fe
K X-rayy
X-ray Generation
Z A F Method
C bi d effects
Combined
ff t results
lt iin an overall
ll correction
ti
known as ZAF
X-ray Generation
Z A F Method
Characteristic radiation :
complex system
Background radiation :
remove for quantification
Non-linearity
X-ray fluorescence yield (Z effect)
X-ray absorption (A effect) : absorption edges
X-ray fluorescence (F effect)
Quantitative analysis - Matrix correction

Sample steel, 25kV
25kV
Element
K-ratio
WT%
Cr K
Mn K
Fe K
Ni K
0.1927
0.0099
0.7167
0.0735
0.995
0.979
0.999
1.018
0.986
0.996
0.957
0.839
1.203
1.010
1.012
1.000
16
16..33
1.00
74
74..08
8.61
Cr to high : total ZAF correction

0.995 x 0.986 x 1.203 = 1.18
Correct Cr contents = (0
(0.1927
1927//1.18
18)x
)x 100 % = 16.
16.33
Quantitative analysis - Matrix correction

Standardless analysis of steel
25kV
Standardless analysis of steel

15kV
X-ray Measurement - Resolution

Peak broadening by electrical noise
and statistical errors
Natural peak of Mn Ka = 2.3 eV
O i i l Mn
Original
M Ka
K off 2.3
2 3 eV
V wide
id and
d
1000 cts high
Degraded to a Mn Ka peak of 150 eV
wide : 15 cts high
Small peak due to broadening (1.5 %
from the original
g
peak)
p
)

FWHM=Full Width at Half Maximum:
Resolving power of the detector based
on Mn Ka line
Today's detectors
130 - 135 eV (Mn Ka)

Resolution depending on energy
Decreases approximately 3- 4 eV
per element
Al K FWHM = 95 eV
Cu K FWHM = 150 eV
Resolution depending on count
rate (and temperature)
p
Never compare peak heights
Operation
p
of the Analytical
y
Microscope
p
Calibration
Al FWHM 95 eV
Cu FWHM 150 eV
Operation
p
of the Analytical
y
Microscope
p
Calibration
X-ray peaks must be located
accuratelyy on the energy
gy axis
Therefore calibration needed
Automatic s/w procedure :
zero and gain adjustments
U ttwo elements
Use
l
t : Al and
dC
Cu
Calibrate using a countrate
as under normal operations
p
countrate :
Optimum
dead time 25 - 35 %
Operation
p
of the Analytical
y
Microscope
p
Calibration
Calibration of amplification times
Slow ampl.time is used for
quantification:
good resolution (130
g
(
- 138 eV)
V)
Fast ampl.time
ampl time used for
mapping poor resolution
(145 - 180 eV)
Calibration every 2 - 4 weeks
(if temperature is constant)
Qualitative analysis - Spectral artefacts
Peak overlap
Sum peaks
Dead time
E
Escape
peaks
k
Peak distortion
Absorption edge
Rough surface
Poor counting statistics
Non-linearity detector
Window absorption
Stray radiation
Ch i
Charging
Warming of the detector
S-FEG (semi-inlens
system)
y
)
Low vacuum analysis :
skirt
Quantitative analysis - Background subtraction
Qualitative analysis - Spectral artefacts

Identification of all possible peaks
Auto or Manual Peak ID
Do not trust system :

it is not 100% reliable
Be aware of :
- spectral artefacts
- skirt effects (low vacuum systems)
Qualitative analysis Peak ID
Identification of an element
Place cursor exact on the top of the peak (expand scale)
L and M line can show shift due to poor separation of a/ line

First check main lines such as L or M lines
Check the other lines of the same element
Heavy elements will produce K and L radiation
Q lit ti analysis
Qualitative
l i Peak
P k ID
Pb M - lines and Pb L - lines (note the shift of the Pb M lines)
Q lit ti analysis
Qualitative
l i Peak
P k ID
Pb M - lines and Pb L - lines (note the shift of the Pb M lines)
Q lit ti analysis
Qualitative
l i Peak
P k ID
Zr L - lines and Zr K - lines (note the shift of the Zr L lines)
Q lit ti analysis
Qualitative
l i Peak
P k ID
Zr L - lines and Zr K - lines (note the shift of the Zr L lines)
Spectral artefacts - Peak overlap

EDS poor resolution :
result peak overlap
Difference at least 60 eV to
separate lines
Poor result : use standards
Classical example:
Pb Ma
- S Ka
2.345 KeV - 2.307 KeV
diff
difference
= 38 eV
V
Qualitative analysis - Deconvolution
Deconvolution = peak strip

method
Requires well calibrated system
Check
Ch k d
deconvolution
l ti ffor
overlapping elements
Check other lines
Spectral artefacts - Sum peaks

Sum peaks due to pulse pile-up
pile up effects
Two X-rays are entering detector at the same time
S
Sum
off th
the energies
i iis seen as one energy
Sum peaks depending on (high) count rates and chosen
amplification time
pure elements : combinations p
possible
Not onlyy p
Prevent sum peaks by keeping count rate in balance

with the chosen Ampl.Time
Spectral artefacts - Dead time

Dead time = system is busy with pulse shaping
Dead time = relationship of input and output count rate
p
g on amplification
p
time
Dead time depending
Reasonable dead time 25 - 35 %
High dead time : system is slow
Result : sum peaks and peak broadening
Use live-seconds (corrected for dead time)

Sum peak Cr Ka = 2 x 5.411 = 10.822 KeV

Glass with SUTW : sum peak of O and Si ( 0.52 + 1.74 = 2.26 KeV)
Spectral artefacts - Escape peaks

Escape peak : result of losing Si K energy in the Si-dead layer of
th crystal
the
t l
Si K line = 1.74 KeV
Remaining energy is original energy minus Si K energy
Difficult to identify
Intensity of the escape peak belongs to the main peak
S/ can correctt ffor escape peaks
S/w
k

Escape peak of Cr Ka = 5.411 - 1.740 = 3.671 KeV
Spectral artefacts - Absorption edge

Every X-ray line has an
absorption
p
edge
g
Sometimes clearly visible
In many cases underneath peak
Absorption edge may influence
th b
the
background
k
d modelling
d lli
Absorption edge of the detector
can be seen (like C, Si)
p discontinuity
y
Not a sharp
Spectral artefacts - Absorption edge
Spectral artefacts - overview

Artificial spectrum of Fe, showing background shape, escape and sum
peaks and the absorption edge
Spectral artefacts - Peak distortion

Peak distortion = peak has no Gaussian
shape
h
Distortion due to :
- Incomplete charge collection
g
at low
- Increased background
energy side
- Absorption edge
- Influence of the L-L line
Peak broadening due to high count rate

Topology
Surface roughness has also an
influence on the TOA
Could lead to false
conclusion
Example
Matrix : Fe
Inclusion : BaSO4
BaSO4
Absorption of O by matrix
Result on detector :
Ba and S
Spectral artefacts - Rough surface
Practical aspects - Particle analysis
Mass effect
Absorption effect
Particle analysis - Mass effect

Mass effect best visible
with
ith high
hi h energy line
li
Difference in excitation
volume between particle
and bulk material
Small particles 1 - 5
micron : only
yq
qualitative
analysis
Particle analysis - Absorption effect

Absorption effect best visible
with low energy line
Difference
ff
in absorption path
between particle and flat
b lk material
bulk
i l
Small particles 1 - 5 micron :
only qualitative analysis
Practical aspects - Thin film analysis

Thin film analysis is also very difficult
Two kind of analysis :
1.unsupported thin film
2.thin film on substrate
Single layer or multi-layer
Unsupported thin film : NO absorption and fluorescence
effect
ZAF correction can not be used in case of unsupported
film
Thin film on substrate : change in interaction volume due
t diff
to
differentt compositions
iti
off the
th layers
l
ZAF correction is not correct due to (multi) layers
Practical aspects - Thin film analysis
unsupported thin film
Multi
Multi--layers on substrate
Spectral artefacts - Poor counting statistics

Low count rate results in noisy spectrum = poor statistics
Noisy spectrum will introduce PEAK ID errors
System will identify noise (Auto ID)
Solution
Long acquisition time
disadvantage : limited number of specimens
High count rate in combination with appropriate ampl
ampl. Time
disadvantage :
poor peak separation
Find the ideal combination for your own samples
Spectral artefacts - Non-linearity
Non-linearity of detector below 1 KeV

Results in peak shift of the light elements
Peak shift depending on used material ( B or BN or TiB2)
Check system and if necessary correct
Old detector : LEAP series
New detector : Sapphire series
Spectral artefacts - Window absorption

Detector separated by window
Different types :
- Be window
- UTW (ultra thin window)
- SUTW (super utw)
- Windowless (ECON)
(S)UTW and windowless systems needs
an electron trap
Collimator has built-in electron trap
Spectral artefacts - Window transmission

Comparison of window material X-ray transmission
Type
ECON
SUTW
UTW
Be
100 %
25 %
12 %
0%
100 %
85 %
42 %
0%
100 %
42 %
20 %
0%
100 %
60 %
30 %
0%
100 %
70 %
35 %
5%
Spectral artefacts - Window transmission
Spectral artefacts - Window absorption

Window performance comparison (Alibite sample = mineral)
Spectral artefacts - Stray radiation

Detector has a large solid angle
Many X-rays from surrounding
material are captured
Use collimator (pin-hole type)
Limits field of view (solid angle)
Working range 8 - 12 mm
El t
Electron
trap
t
needed
d d tto preventt
BSEs from entering crystal
Spectral artefacts - Charging

Non-conducting materials will charge at high kV
After coating specimen will still charge (not visible)
Due to charging the incoming electron is decelerated
Charging is recognised at the end of the spectrum
For ZAF quantification model the acc. voltage is required
EDAX program is not sensitive to small effects
No charging effects at low voltage
Low voltage analysis limits the excitation energy
No charging effects in a Low Vacuum SEM
Spectral artefacts - Charging
Low vacuum microanalysis

y

Low vacuum SEM : charge is eliminated by a gas (air or N2)
g kV possible,
p
, no limitation of excitation energies
g
High
Two major problems :
- beam damage
- beam spread (skirt effect)
Beam damage : because of high kV heating of sample
p
:
Beam spread
- Electron are scattered due to gas collision
- X-ray
X ray generation outside the probe spot
- X-ray information upto 500 micron from central spot (=skirt)
Mineral Jadeite
Large
g sample
p in
homogeneous matrix
Instrument : LV-SEM
High-vacuum spectrum - Jadeite 25kV
Low-vacuum spectrum (0.4 mbar) - Jadeite 25kV
Low-vacuum spectrum (0.8 mbar) - Jadeite 25kV
)(SEM

)(SEM

15 kV
5 kV
25 kV
)(SEM

Iron
Silver
Carbon
(SEM)

0 degree tilt
70 degree tilt
30 degree tilt
)(SEM

( Map
( ( Map
- ) (Mapping -
)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

)(SEM

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)(Scanning Electron Microscopy

Bias on Wehnelt cap

Bias on Wehnelt cap

Bias on Wehnelt cap

Optimum bias voltage

High bias voltage

If negative field gradient is weak ib increases d0 increases is not optimum

The current density in the electron beam at

Maximum value for by Langmuir Eq.

Jc= 1.75 (A/cm2) at 2700K

Bias on Wehnelt cap

Typical values for EPMA and SEM

Increasing of E0 is limited (normally 30 40 KV)

LaB6 . 1010 torr

Primary electron beam

Electron Sources differ:

Column optics control

disc of least confusion

High image quality.

Solid state detector

Silicon dead layer

Surface roughness has

=Secondary electron coefficient

primary electron beam

alternatively magnetized domains

Electrons are transformed into light by Scintillator

A positive bias of 10 KV is applied to the thin aluminum layer,

Not many materials have all these properties

Affect the sample material

2- Double-sided tape (Copper or Carbon)

Plastics: immersion in liquid nitrogen)

Metals: diamond (wheel, saw or paste), Electro polishing, Ion

The Mathematical principles of natural

" ) ( Stationary states .

Detector must be protected:

Continuum radiation = Brems- strahlung or background radiation

Continuous background : non-linearity, decreasing peak height towards high energies

Never compare peak heights

All X-ray lines of all elements visible with 30kV beam

K lines are unique for each element

Si Detector resolution ~ 135 ev Deconvolution

Operation of the Analytical Microscope

Operation of the Analytical Microscope

Operation of the Analytical Microscope

Operation of the Analytical Microscope

Operation of the Analytical Microscope

Operation of the Analytical Microscope

To eject an electron : amount of

Accelerating Voltage= normally 1.5-20 times of characteristic ray

Quantitative analysis - Background subtraction

Quantitative analysis - Matrix correction

Cr to high : total ZAF correction

Quantitative analysis - Matrix correction

Standardless analysis of steel

X-ray Measurement - Resolution

X-ray Measurement - Resolution

X-ray Measurement - Resolution

Never compare peak heights

Qualitative analysis - Spectral artefacts

Quantitative analysis - Background subtraction

Qualitative analysis - Spectral artefacts

Do not trust system :

Qualitative analysis Peak ID

L and M line can show shift due to poor separation of a/ line