METALORGANIC CHEMICAL

VAPOR DEPOSITION

Description of the MOCVD equipment

Analysis of the MOCVD growth process
Growth modes in MOCVD

Metalorgenic Chemical Vapor Deposition (MOCVD)

[Metalorganic Vapor Phase Epitaxy (MOVPE),
OMCVD, OMVPE]
One of the premier techniques for epitaxial growth of thin layer
structures (semiconductors, oxides, superconductors)

Introduced around 25 years ago as the most versatile technique for

growing semiconductor films.

Wide application for devices such Lasers, LEDs, solar cells,

photodetectors, HBTs, FETs.

Principle of operation: transport of precursor molecules (group-III

metalorganics + group-V hydrides or alkyls) by a carrier gas (H 2, N2)

onto a heated substrate; surface chemical reactions.

Complex transport phenomena and reactions, complicated models to

determine reactor designs,growth modes and rates.

In-situ diagnostics less common than in MBE.

Description of the MOCVD equipment

R. L. Moon and Y.-M. Houng, in Chemical vapor deposition Principles and applications, edited by M. L. Hitchman and K. F.
Jensen (Academic Press, London, 1993).
G. B. Stringfellow, Organometallic vapor phase epitaxy: theory
and practice (Academic Press, Boston, 1989).

MOCVD Facility, horizontal reactor

Gas handling
Research system (left): AIX 200
1X2 wafer capacity

Reactor

Glove box

Production system (right):

AIX 2600
Up to 5X10 wafer capacity
(AIX 3000)

Schematics of a MOCVD system

Carrier
gas

Material
sources

Gas
handling
system

In-situ
diagnostics

NO electron
beam probes!

Reflectance
Ellipsometry
RAS

Exhaust system

Safety system

Reactor

Gas handling system

The function of gas handling system is mixing and metering of the

gas that will enter the reactor. Timing and composition of the gas
entering the reactor will determine the epilayer structure.

Leak-tight of the gas panel is essential, because the oxygen

contamination will degrade the growing films properties.

Fast switch of valve system is very important for thin film and abrupt
interface structure growth,

Accurate control of flow rate, pressure and temperature can ensure

stability and repeatability.

Carrier gas

Inert carrier gas constitutes about 90 % of the gas phase

stringent purity requirements.

H2 traditionally used, simple to purify by being passed through a

palladium foil heated to 400 C. Problem: H2 is highly explosive in
contact with O2 high safety costs.

Alternative precursor : N2: safer, recently with similar purity, more

effective in cracking precursor molecules (heavier).

High flux fast change of vapor phase composition. Regulation:

mass flow controller

P ~ 5- 800 mbar

Mass flow controllers

Material sources

Volatile precursor molecules transported by the carrier

gas

Growth of III-V semiconductors:

Group III: generally metalorganic molecules (trimethylor triethyl- species)
Group V: generally toxic hydrides (AsH3; PH3
flammable as well); alternative: alkyls (TBAs, TBP).

Hidrides and dopants

Form: gases from high pressure cylinders

Mixed into the carrier gas line
Flow control: valve + mass flow controller (MFC)

Bubblers

Metalorganics
Liquid (or finely divided solid TMIn) contained in a
stainess steel bubbler.

Vapor pressure fixed by constant temperature in a

thermal bath; T -20oC 40oC; T = 1oC.

Controlled H2 flow through the bubbler saturated

H2, N2

stream; composition depends on H2 flow rate

adjustment through MFC

To reactor

P ressure controller (PC) to keep a fixed pressure in the

bubbler and throttles the resulting mixture of H2 and MO

down to the reactor pressure.
PC
MFC
Valve NC
Valve NO

Bubbler

Thermal
bath
To reactor

Metalorganic compounds
Optimal thermal decomposition temperature between 300 and 500C
availability of transported reactant at the substrate surface.

The vapor pressure of the MO source is an important consideration in

MOCVD, since it determines the concentration of source material in
the reactor and the deposition rate. Too low a vapor pressure makes it
difficult to transport the source into the deposition zone and to achieve
reasonable growth rates. Too high a vapor pressure may raise safety
concerns if the compound is toxic.

Vapor pressures of Metalorganic compounds are calculated in terms of

the expression

Log(p)=B-A/T

Vapor pressure of most common MO compounds

Compound

P at 298 K

Melt point
(oC)

(torr)
(Al(CH3)3)2

TMAl

14.2

2780

10.48

15

Al(C2H5)3

TEAl

0.041

3625

10.78

-52.5

Ga(CH3)3

TMGa

238

1825

8.50

-15.8

Ga(C2H5)3

TEGa

4.79

2530

9.19

-82.5

In(CH3)3

TMIn

1.75

2830

9.74

88

In(C2H5)3

TEIn

0.31

2815

8.94

-32

Zn(C2H5)2

DEZn

8.53

2190

8.28

-28

Mg(C5H5)2

Cp2Mg

0.05

3556

10.56

175

Log(p)=B-A/T

Flow rate of MO sources

Ideal gas equation MO flux QMO

PMO(Tbub) = equilibrium vapor

pressure of the metalorganic

component
V
Tbub = bubbler temperature
PMO Tbub mbar ml / min
Ni
t
QB = carrier gas flux at standard
mol / min
N At
J
l
4
atmosphere
k B Tbub K N A

10

K
mol
Pstandard = standard atmosphere

PB = regulated bubbler pressure

mbar
P
PMO Tbub mbar QB mol / min standard
PB mbar
QMO mol / min
J
8.314 104
Tbub K
K
mol

piV N i k BT

(Rolf Engelhardt, Ph.D. Thesis, TU Berlin,

2000, http://edocs.tu-berlin.de/diss/2000/engelhardt_rolf.pdf)

Partial pressure of MO sources

PMO reactor mbar

Pstandard mbar
PB mbar
mbar
P
Qtot mol / min standard
Preactor mbar

PMO Tbub mbar QB mol / min

PMO-reactor = partial pressure of the metalorganic components in

the reactor
PMO(Tbub) = equilibrium vapor pressure of the metalorganic
component
QB = carrier gas flux
Pstandard = standard atmosphere
PB = regulated bubbler pressure
Qtot = total gas flux
(Rolf Engelhardt, Ph.D. Thesis, TU Berlin,
2000, http://edocs.tu-berlin.de/diss/2000/engelhardt_rolf.pdf)

MOCVD reactors

Different orientations and geometries.

Most common:
Horizontal reactors: gases inserted laterally with

respect to sample standing horizontally on a slowlyrotating (~60RPM) susceptor plate.

Vertical reactors: gases enter from top, sample

mounted horizontally on a fast-rotating (~5001000RPM) susceptor plate.

Horizontal reactors

Primary vendors: AIXTRON

(Germany).

The substrate rests on a graphite

susceptor heated by RF induction or

by IR lamps.

Quartz liner tube, generally

rectangular

Gas flow is horizontal, parallel to the

sample.

Rotation ~ 60RPM for uniformity by

H2 flux below the sample holder.

Horizontal reactors

Advantages
Common reactor high experience.
Uniform epitaxial growth provided the gas velocity is large enough, and
attention is paid to hydrodynamic flow.

Small height above the wafer the effect of natural convection is

minimized.

Quite large gas velocity very rapid changes in the gas phase
composition.

Disadvantages
Uniformity can either be achieved by very high gas flow, ( inefficient
deposition), or by implementing rotation, which is tricky in this type of
design.

Throughput: difficult to scale this design up to accommodate large volume

production.

Planetary reactors

Primary vendors: AIXTRON.

Derived from horizontal reactor.
Material: stainless steel
Very widespread now for production, and
can
achieve
uniformities.

very

good

wafer

Uniformity: rotation of the main disk +

individual satellites.

Up to 5X10 wafer capacity (AIX 3000,

see photo)

Vertical reactors

Primary vendors: Veeco (former Emcore

(USA)).

Gas flow generally normal to the wafer.

Temperature gradients buoyancy

induced convection high residence time

of the gases degradation of
heterostructure compositional abruptness.

Solution: rotation of susceptor at high

angular velocities (centrifugal pumping

action to suppress convection and obtain
more efficient use of precursors.

Simulated streamlines in a vertical spinning cylinder

reactor for MOCVD of GaAs from TMGa, AsH3, H2. Gases
enter at 600K through the top plane and react at the flat top
surface of the spinning inside cylinder. The rotation rate is
1000rpm and the deposition surface temperature is 900K
(http://www.cs.sandia.gov/CRF/MPSalsa/ )

Vertical reactors

Features

Advantages

All stainless construction

MBE vacuum technology
Safety (no glass)
Electrical resistance heating
Gate valve, and antechamber for
minimizing O2/H2O contamination.
High precursor utilization efficiency
Scaling to very large wafers/ multiple wafers.
Multiple wafer capacity:
Up to 3 x 8", 5 x 6", 12 x 4", and 20 x 3"

Disadvantages:
Very high speed rotation, up to 1200 rpm.
Possible memory effects.

Exhaust system

Pump and pressure controller

Low pressure growth: mechanic pump and pressure controller

control of growth pressure. The pump should be designed to handle

large gas load (rotary pump).

Waste gas treatment system

The treatment of exhaust gas is a matter of safety concern.
GaAs and InP: toxic materials like AsH3 and PH3. The exhaust gases
still contain some not reacted AsH3 and PH3, Normally, the toxic gas
need to be removed by using chemical scrubber.
For GaN system, it is not a problem.

AIXTOX system

Safety issues
Concerns:
Flammable gases (H2)
Toxic gases (AsH3, PH3)
Safety measures:
Lab underpressurization.
Design of hydrides cylinders.
Extensive gas monitoring systems placed in different

locations, able to detect the presence of gas as small as parts

per billion.
Alarms located in different parts of the buildings + beeper calls
to operators.
Immediate shut down of the system to a failsafe condition in
case of leakages and other severe failures.

Alternatives: use of alternate gases

N2 carrier
TBAs, TBP (toxic but liquid low vaopr pressure)

Analysis of the MOCVD growth

process

MBE versus MOCVD growth rate

MBE
Tcell Pv(T)

Ballistic
transport

Sticking
coefficient = 1

MOCVD
Flow rate
f (total flow F, total
pressure P, vapor pressure Pv)

r = r (F, P, Pv,
mass transport,
reaction kinetics)

Diffusive mass
transport

Chemical
reaction kinetics

r = r (T)

Growth steps in (MO)CVD

1. At
Flow
reactant
(precursors)
reactor
3.
theofsame
time:
chemicaltoreactions
tube,
either by:

homogeneous,
heterogeneous
Mixingdeposit)
in gas handling
manifold,
(parasitic
reduction
of
then concentration,
enter the reactorshift in alloy
reactant
Separate until
the reactor
(no
composition,
reduced
growth
rate,
premature
sideroughening.
reactions)
epitaxial
surface
4.
decomposed)
precursor
2. (Partially
In the reactor:
establishment
of gas
diffusion
to the surface
layers governing
transport
of reaction
mass, to
energy
and
momentum:
entry effects
form
the
desired
material.
and possibly achievement
5. Simultaneous
desorptionofofsteadyreaction
state condition.
products
(hydrocarbons), surface
diffusion of material to lattice sites.

R. L. Moon and Y.-M. Houng, in Chemical vapor

deposition - Principles and applications, edited by M.
L. Hitchman and K. F. Jensen (Academic Press,
London, 1993).

Reactive-flow conservation equations

(Crosslight Procom Users manual)

The state of the gas phase in a reactor can be completely described

by the continuum mass density , the individual chemical species
number density ni, the momentum density v, and the energy density
E. The basic partial differential conservation equations are:
total mass (continuity equation)
individual species (precursors,
intermediate species)
momentum (Navier-Stokes equation)
energy (heat conduction equation)
Total energy density

Chemical production rate of species i

Number density of species i

Heat flux

Fluid velocity

Radiative heat flux

Number of chemical species present

Diffusion velocity of species i

Pressure tensor

Fluid mass density

Simplified model of (MO)CVD reaction kinetics

Simplified deposition process of a film, starting from a molecule AB in

the gas phase

(L. Vescan, in Handbook of thin film process technology, edited by

D. A. Glocker and S. I. Shah (Institute of Physics Publishing, Bristol, 1995), p. B1.4:1)

AB(g) A(s) + B(g)

J1: molecular flux from the gas phase to the substrate surface,

J2: consumption flux of AB corresponding to the surface reaction:

J1 hG (CG CS)
J 2 k SCS

(~supersaturation)

with
hG = gas diffusion rate constant,
CG = gas-phase concentration of AB,
CS = surface concentration of AB,
kS = heterogeneous rate constant

J1

J2

Simplified model of (MO)CVD reaction kinetics

Steady-state conditions:

CG
J1 J 2 J 1
k S hG1
Growth rate r = J0 (with 0 = unit volume of the crystal)

r mole fraction of the species AB in the gas phase, and determined by

the smaller of the rate constants hG, kS.

Limiting cases:
r kS C G 0
r hG C G 0

surface kinetics control

mass transport control

Interpretation in terms of supersaturation

Driving force: supersaturation (chemical potential difference between gas

phase and solid) out-of-equilibrium process; equilibrium at the vaporsolid interface

The relative importance of surface kinetics and mass transport can be

interpreted as a function of the chemical potential dependence on the

reaction coordinate. If most of the chemical potential drop occurs in the
boundary layer (red line), the growth is controlled by mass transport; if it
occurs at the interface (green line), the growth is kinetically limited

Chemical potential

Input gas
phase

Boundary
layer

Interface

Mass
transport

Reaction coordinate

Solid

Reaction
kinetics
R. L. Moon and Y.-M. Houng, in Chemical vapor
deposition - Principles and applications, edited by M.
L. Hitchman and K. F. Jensen (Academic Press,
London, 1993).

Mass transport

Fundamental and very complex aspect in reactor design

Factors influencing gas flow in a reactor:
temperature
concentration and momentum gradients
gravity ( convection)
homogeneous, heterogeneous chemical reactions ( parasitic nucleation)
Simplified (2 regions) picture in a horizontal reactor:
Upper region: turbulence or vorticity good mixing and heat transfer
Close to the susceptor: region of laminar flow (boundary or stagnant layer)
molecular diffusional
transport to the hot
substrate, where the
transverse velocity is zero.

Mass transport

Assuming a gas velocity U = U in the bulk gas

phase, and U = 0 at the growth surface

calculation of boundary layer width ( D. W. Kisker and T. F. Kuech, in Handbook of crystal growth,
edited by D. T. J. Hurle (Elsevier Science, Amsterdam, 1994), Vol. 3, p. 93)

~ (PU)-1/2, where P is the total reactor pressure.

If the molecular transport in the boundary layer proceeds by diffusion alone, the rate
constant hG can be written as

D where D ~ P-1 is the diffusion coefficient

hG

mass-transport-limited growth rate

where CG ~ pAB = AB partial pressure

r ~ p AB

U
P

growth rate is practically independent of the growth temperature, and

depends linearly on the species partial pressure.

Reaction kinetics

Two kinds of thermally-activated reactions

Reactions in the gas phase (homogeneous reactions)
Reactions at the surface (heterogeneous reactions)
Forward and reverse rates are characterized by rate constants that
can be expressed in an Arrhenius form:
k = A exp (-E/kBT),
where E is the activation energy for the process.

Surface kinetics are poorly known processes, in which a number of

sub-processes can be identified. Among them:
adsorption of reactant species,
heterogeneous decomposition reactions,
surface migration,
incorporation and desorption of products.

Reaction kinetics

In the most simplified picture, the chemistry of heterogeneous

reactions can be modeled by taking into account only adsorption and

desorption:
k ads

AB(g) + A + B(g)
k des

where is a vacant surface site,

A is an adsorbed state,
kads and kdes are the adsorption and desorption rate constants

Assumptions: no interaction between absorbed species; equivalence

among all the adsorption sites.

G. B. Stringfellow, Organometallic vapor phase epitaxy: theory

and practice (Academic Press, Boston, 1989).

Reaction kinetics

Steady state (adsorption rate = desorption rate):

k ads
A*

adsorption coefficient K
k des * AB( g ) 1 p AB
with = fraction of occupied lattice sites

Kp AB
assumes the form of a Langmuir isotherm:
1 Kp AB

G. B. Stringfellow, Organometallic vapor phase epitaxy: theory

and practice (Academic Press, Boston, 1989).

Reaction kinetics
MOCVD of binary compound semiconductors: two molecules AB and
CD are transported to the surface, and are adsorbed on cation and
anion sites, respectively.

For this noncompetitive process, the growth rate of the bimolecular

reaction is proportional to the anion and cation surface coverages
(Langmuir-Hinshelwood isotherm):

r k AB CD AB CD

k AB CD K AB p AB K CD pCD
1 K AB p AB 1 K CD pCD

III-V semiconductors:

tipically V/III ratio ~ 100 AB << 1; CD 1

r K pAB,
with K a typical rate constant for the process, temperaturedependent.

growth rate depends only on temperature and on the group-III

precursor partial pressure, and not on the group-V one.

Reaction kinetics for GaAs

Overall reactions:

TMGa + AsH3:

AsH3 + Ga (CH3)3 GaAs + 3CH4

TEGa + AsH3:

AsH3 + Ga (C2H5)3 GaAs + 3C2H4 + 3H2

Lower activation energies for

decomposition for TEGa than
for TMGa ~200K lower
temperature for 50%
decomposition.
(Markus Pristovsek, Ph.D. Thesis, TU Berlin,
2001, http://edocs.tuberlin.de/diss/2000/pristovsek_markus.pdf)

Reaction kinetics for GaAs

Overall reactions:

TMGa + AsH3:

AsH3 + Ga (CH3)3 GaAs + 3CH4

TEGa + AsH3:

AsH3 + Ga (C2H5)3 GaAs + 3C2H4 + 3H2

TMGa decomposition is strongly
enhanced at the onset of the
AsH3 de-composition.
This is most likely due to
hydrogen radicals produced by
AsH3 decomposition.
(Markus Pristovsek, Ph.D. Thesis, TU Berlin,
2001, http://edocs.tuberlin.de/diss/2000/pristovsek_markus.pdf)

Reaction kinetics for GaAs

Proposed mechanisms (TMGa +

AsH3):
Complex series of decomposition
steps in the gas phase and on the
surface, each with its own
characteristic reaction constant and
activation energy.
K. F. Jensen, Adv. Chem. Ser. 245, 397 (1995)

Growth modes in MOCVD

Growth mode: studies on GaAs from TMGa and AsH3

Effect of substrate temperature
Studies for atmospheric pressure (AP = 10 5Pa = 1000mbar) and for low pressure (LP =
104Pa = 100mbar), and different surface orientations.

Three regimes:
Low T: kinetically limited growth strong T dependence, low P dependence (r K
pTMGa), with K dependent on T.

Mid T: mass transport-limited

High T: increasingly low growth

rates, probably due to homogeneous

reactions in the gas phase, causing
a depletion of reactants, or surface
re-evaporation.

material loss mass transport

850

750 700 650 600 570

510

kinetics
T (C)

r (m/h)

growth r does not depend

appreciably on T and surface
orientation, but increases with
decreasing P (r pTMGa P-1/2 ).

G. B. Stringfellow, Organometallic vapor phase epitaxy: theory

and practice (Academic Press, Boston, 1989).

1/T (10/K)

Growth mode: studies on GaAs from TMGa and AsH3

Effect of reactor pressure

Studies for T = 650C and V/III ratio 100

Two regimes:
P > 100mbar, growth is limited by mass transport, and r ~ P-1/2
After a transition region, at P < 20mbar, the growth rate becomes
independent on P, and growth becomes kinetically limited.
surface kinetics

p-1/2

r
(m/h)

p0

mass transport

G. B. Stringfellow, Organometallic vapor phase epitaxy: theory

and practice (Academic Press, Boston, 1989).

P (10 2 Pa)

Growth mode: studies on GaAs from TMGa and AsH3

Effect of TMGa partial pressure

Studies for different T and substrate orientations

Three regimes:
T = 700oC: r pTMGa at all TMGa pressures and
substrate orientations (mass transport
limited)
T = 500oC: r saturates for high TMGa
pressures and depends on orientation
(kinetically limited). Evidence for (orientationdependent) incomplete AsH3 decomposition
(with TMGa completely pyrolized).
T = 1000oC: decreased growth rate: gasphase reactions ( reduction of gas-phase
nutrients) and surface desorption (
orientation dependence)
R. L. Moon and Y.-M. Houng, in Chemical vapor deposition - Principles
and applications, edited by M. L. Hitchman and K. F. Jensen (Academic
Press, London, 1993).

500C
700C
1000C