Basic growth concepts

• Supersaturation: If a phase is brought outside its

stability region, then the difference between the chemical
potential of this phase and the chemical potential of a
thermodynamically stable phase is called
supersaturation. Supersaturation is the driving force for
all phase transformations.
• Supersaturation  = g - s , g = chemical potential of
the gas phase, s = chemical potential of the solid phase
• Example: Supersaturation for a gas-liquid or gas-solid
equilibrium is given by
P P is the actual pressure, P0 is the
  kT ln
P0 equilibrium pressure
ELECT 871 02/16/04
 ThermoDyn. of crystal growth I: Nucleation
• In order for the crystal to grow, the crystalline phase must
have lower chemical potential than the phase from which
the crystal is forming
• The surface energy required to create a nucleus with radius
r is 4r2. The energy released due to the formation of a
nucleus of radius r is - 4r3/(3), where  is the molar
density.
4 r 3

• The free energy is then give by G  4r  2
3
• The stability of the nucleolus is achieved at
G 2
0r  Then the free energy barrier is given by
r 
16 3  2
Gb 
3 2
ELECT 871 02/16/04
 Thermodynamics of crystal growth II
• If the nucleus is below the critical size it will dissolve. Gb
is the potential barrier for crystallization

Growth is always
performed in this
region where no new
nucleolus may appear.
The only process that
occur in this region is
the growth of the
existing nuclei.

ELECT 871 02/16/04

 Basic epitaxial growth modes
Frank-van der Merwe (FM)
Epilayers like to adhere to
substrate, more than to each
other
Example: Growth of
GaAs layers by
Liquid phase epitaxy
(LPE)
Volmer-Weber (VW) Stranski-Krastanov (SK)
Epilayers does not like to Epilayers first wet subsrate
adhere to substrate and then balls up
Example: Initial Example: self-
organized quantum
nucleation of GaN
dots of InAs on
buffer layer after the
GaAs substrate
nucleation layer growth
ELECT 871 02/16/04
 Surface and interface energy
Frank-van der Merwe (FM) Volmer-Weber (VW) Stranski-Krastanov (SK)

First,
n < 0
n < n >
0 0 Then,
n > 0

n = FV + FS - SV , where, n refers to nth layer growth

FV = surface energy of film-vapor interface
FS = interfacial energy between film and substrate
SV = substrate surface energy
Note: Difference between FM and SK arises primarily due
to elastic strain associated with the film ELECT 871 02/16/04
Other epitaxial growth modes, summary

Other epitaxial growth modes

Supersaturation vs. misfit percentage

ELECT 871 02/16/04
 Summary
• Total energy minimization occurs in FM mode by lateral (2D)
growth and in SK by 3D growth. VW changes from one to the other.
• SK and VW growth modes are usually observed for vapor phase
epitaxy, and give rise to islands that coalesce later and proceeds by
columnar growth or step flow growth, giving rise to a high density of
dislocations
• 2D growth is possible for lower supersaturation in presence of steps
or defects such as screw dislocations
• Step bunching (common for SiC growth) can occur in presence of
large step density and large supersaturation
• Dislocation mediated growth morphology is extremely common for
GaN where growth is initially columnar, followed by 3D growth and
finally 2D growth. Screw-island growth is also common in MBE
grown GaN on MOCVD grown GaN templates
• Growth by LPE is an example of near-equilibrium growth, others
usually non-equilibrium growth
ELECT 871 02/16/04
 Common growth techniques
• Bulk crystal growth
– Czochralski: Liquid to solid (Si, GaAs)
– Bridgman: Liquid to solid (CdTe, other II-VI compounds)
– Sublimation: Vapor to solid (SiC, GaN?)
• Epitaxial crystal growth
– Liquid phase epitaxy: substrate moves from one melt to another
(Ex: GaAs, GaN)
• Adv: Simple, high quality defect free layers, equilibrium growth
• Disadv: Multiple layers difficult, QW structure possible, poor layer interface
– Chemical vapor deposition (Ex: all compound semiconductors, Si)
• Adv: Very high quality, high throughput
• Disadv: Toxic gases, non-uniform, not as abrupt as MBE
– Molecular beam epitaxy (Ex: all compound semiconductors)
• Adv: Very high quality, no toxic gases, very abrupt
• Disadv: Low throughput, can be unstable from run to run
ELECT 871 02/16/04
 Growth of Nitrides
Epitaxial growth of nitrides play a much more important
role than in other technologies because ….
• Major Problem: Non-availability of native
(or lattice and thermally matched) substrate
• Therefore….
Heteroepitaxy is done: by MBE or MOCVD
Result: Huge density of dislocations to release
strain
So… strategies to reduce dislocations are very
important for III-nitride technology.
ELECT 871 02/16/04
 Substrates for nitride epitaxy: sapphire
Side view
Plan view of
sapphire
(rhombohedral)

r-plane: non-polar GaN

c-plane: polar GaN

Atomic arrangement of GaN

on sapphire (asap = 4.76 Å)
ELECT 871 02/16/04
 Sapphire physical properties

For GaN: a = 3.189 Å, c = 5.185 Å, and a = 5.59, c = 3.17 (10-6/K)

ELECT 871 02/16/04
 Summary of sapphire as substrate
Growth steps of GaN on sapphire
• The growth of GaN on sapphire
results in the rotation of the crystal
directions by 30° to reduce strain
between the substrate and the
epilayer
• The lattice mismatch with GaN is
13.9%
• The steps for GaN growth includes:
(a) Nitridation and (b) low
temperature buffer layer (usually
AlN) growth
• Growth on c-plane of sapphire gives
c-plane GaN, while growth on r-
plane gives a-plane GaN
• Energy gap of sapphire is > 8eV so
light extraction possible from
substrate side for LEDs
ELECT 871 02/16/04
 Growth of GaN on SiC

(0001) SiC
• For GaN: a = 3.189 Å, c = 5.185 Å, and a = 5.59, c = 3.17 (10-6/K)

No AlN layer: relaxed GaN, With AlN layer: strained GaN

no 2D growth 2D growth of AlN
• AlN nucleation layer used for GaN growth. If not used then
3D growth is possible as relaxed GaN islands are created
GaN
• In situ hydrogen etching makes substrate smooth
structure
• Large step density not good, as it causes stacking mismatch (2H)
boundaries (SMB)
• Usually, Ga-face GaN on Si-face SiC, and N-face on C-face
• Cubic GaN can be grown on 3C SiC due to similar stacking ELECT 871 02/16/04
 Comparison of sapphire and SiC as substrates
• Thermal conductivity of sapphire is much lower than SiC  High
power devices can be fabricated
• Sapphire is much cheaper (> 10 times) compared to SiC. The cost of
devices/ICs can be kept low.
• Growth of GaN on SiC is more lattice matched, so lesser
dislocations expected (not seen very much in practice though!).
Lower dislocations good for device performance.
• Sapphire is always semi-insulating but SiC has to be made semi-
insulating. Semi-insulating substrate is good for high frequency
performance
• Growth on SiC can give rise to stacking mismatch boundary, which
is not a problem for growth on sapphire. SMB is bad for devices.
• Polishing SiC substrates is tougher than sapphire substrates, but they
can be etched in situ using hydrogen inside the chamber. Polishing is
required for good growth.
ELECT 871 02/16/04
 Growth on other substrates
• AlN
– Advantages: Similar lattice structure (no SMB), closely lattice and thermal
matched, higher thermal conductivity, electrically insulating
– Disadvantages: Difficult to grow
• LiGaO2
– Advantages: Very low lattice mismatch (0.9%), polar, easy bulk growth, easy
to etch away
– Disadvantages: Low stabiltiy under MOCVD growth conditions, large
mismatch, poor thermal conductivity
• ZnO
– Advantages: Low lattice mismatch (2%), polar, conductive substrate
– Disadvantages: Low thermal stability, difficult to grow
• Si
– Advantages: High quality, low cost, extrmely smooth surface, thermal
stability, integration with optoelectronc devices
– Disadvantages: Lattice and thermal expansion mismatch, tendency to form
SiN
ELECT 871 02/16/04
 Bulk growth of GaN: direct synthesis
Melting conditions of semiconductors Equilibrium curve for GaN
(without dissociating)

Bulk crystal of GaN,

grown at 10 – 20 Kbar,
and 1400 – 1600 °C 2Ga (melt) + N2 = 2GaN
without seed, along the
10-10 direction).
Squares grids have 1
mm sides
ELECT 871 02/16/04
 Summary of bulk of Nitrides
• Bulk GaN is not possible using standard techniques i.e.
Czochralski or Bridgman method due to extreme melting
conditions (without dissociating)
• Growth of AlN bulk crystals is easiest and those of In is toughest
due to difference in equilibrium partial pressures
• Growth rate of more than 100 m/hr is considered viable for
technological and economical purposes
• The growth processes can be made easier by
– Quasi-bulk growth by Hydride Vapor Phase Epitaxy (HVPE) using a
starting substrate
– By Physical vapor transport of Ga vapors in a sublimation reactor using
GaN powder as the starting material
• Main problems with bulk growth are the introduction of
impurities from the sources. They also need to be polished for
further epitaxy
ELECT 871 02/16/04
 MBE growth system

RHEED techniques for growth study

ELECT 871 02/16/04

 General MBE growth features
• Advantages
– Precise layer by layer growth process
– Excellent in-situ growth rate monitoring possible
– Very abrupt (one atomic layer) growth possible
– Can replicate starting layers in excellent manner
• Disadvantages
– Growth occurs far from equilibrium and is not
thermodynamically favorable
– Growth temperature lower and so film quality is not as good

– Slower growth rate than MOCVD; difficult design for multiple

wafers

ELECT 871 02/16/04

 MBE growth of III-Nitrides
• Precursors for III: Solid sources of Ga, Al, In; V: NH3 or N plasma
(RF source (13.56 MHz.) or ECR source (2.45 GHz.) used for N-
source activation)
• Difficult to find a good nitrogen source as N2 or NH3 does not
dissociate at lower temperature
• Growth temperature usually in the range of 800 – 850 °C. Higher
temperature causes lower growth rate as growth is governed by
kinetics, i.e. both forward and reverse reactions are taking place
simultaneously at , but at different rates.
• Higher V/III ratio increases the growth rate as it prevents GaN
dissociation by providing enough vapor pressure of nitrogen
• The low temperature nucleation layer must be AlN to obtain Ga-
face polarity. GaN nucleation layer gives N-face polarity

ELECT 871 02/16/04

 MBE growth of Nitrides: Kinetics and
Thermodynamics
• Energy for forward reaction
Kinetic barrier lowered by catalyst
– energy from the vapor of group III
atoms Kinetic barrier ~1.3 eV
– rf or ECR plasma source for group V
activation GaN (s)
– The growth temperature
G = 1.9 eV
• Energy for backward reaction 2Ga (l) + N2 (g) (@ 800 °C and
– The growth temperature 10-6 Torr)

• The growth temperature is limited Thermodynamic barrier

by
– the rate of supply of activated N- Thermodynamic barrier does
species and not change with reaction path
– the kinetic barrier for GaN and catalysis
decomposition
GaN growth by MBE proceeds via competition of the forward
and reverse reactions, where the reverse reaction is suppressed
ELECT 871 02/16/04
MOCVD growth system

ELECT 871 02/16/04

 General MOCVD growth features
• Advantages
– Faster growth than MBE, can be a few microns per
hour; multi-wafer capability easily achievable
– Higher temperature growth; growth process is
thermodynamically favorable
– Quality of layers usually better than MBE
• Disadvantages
– Difficult to monitor growth rate exactly (no Rheed
possible due to higher pressure)
– Not as abrupt a process as MBE due to gas flow
issues and memory effects
– Toxic gases are to be handled
ELECT 871 02/16/04
 MOCVD growth of III-nitrides
• Precursors for III: TMGa, TMAl, TMIn; for V: NH3,
Hydrogen carrier gas; 25-760 Torr pressure
• Growth of GaN is carried out at 1000 – 1100 °C, which
is much higher than the MBE growth temperature
• Growth on both SiC and sapphire substrates have been
optimized and used regularly
• If SiC is used as substrate, it can be etched in-situ to get
very smooth surface showing step flow
• Growth always results in Ga-face polarity irrespective of
the nucleation layer used
• Problem of hydrogen passivation of p-type dopants, since
hydrogen is used as the carrier gas
ELECT 871 02/16/04
 Basics of MOCVD growth of Nitrides

Best growth zone

Growth rate
Diffusion controlled

Temperature

• Important growth parameters: growth temperature T and V/III ratio

• T too high: desorption, nitrogen vacancies. T too low: impurities incorporation,
adatoms low surface mobility, structure defects; Usually temperature ~1050 °C
• V/III ratio too high: III-atoms low surface mobility, structure defects. Too low:
decompose, nitrogen vacancies, auto background doping
ELECT 871 02/16/04
 MOCVD growth of Nitrides on sapphire
• A two-step growth method is
followed with the growth of a
low temperature AlN layer
• Before any growth the sapphire
surface is nitridated to reduce
defect density by causing
changes in surface energy
• The low temperature layer can
be either GaN, AlN or even
AlGaN
• In MOCVD growth (unlike
growth by MBE), the polarity of
the GaN film is always Ga-face

ELECT 871 02/16/04

 Hetero-epitaxial growth: MBE vs. MOCVD
kT 5 104
Mean free path   ~ (m), at 1000 °C
1.414 P P
where  is the collision cross-section
Ultra-high vacuum: 10-5~10-11Torr Hydrogen atmosphere, 25-760 Torr
Long mean-free path (> chamber length) III: Metalorganics such as TMGa,
III: Solid source, V: NH3 or N plasma TMAl, TMIn, V: NH3

MBE: reactions occur only at the substrate, MOCVD: parasitic

reactions can occur before the reactant species reach the substrate.
MBE growth, unlike MOCVD growth, is not thermodynamically
favorable and is governed by Kinetics ELECT 871 02/16/04
 Growth of ternaries and quaternaries
• InGaN should be grown at lower temperature than GaN and at
higher V/III ratio due to lower dissociation temperature and higher
nitrogen partial pressure
• AlGaN should be grown at higher temperature than GaN and at
lower V/III ratio due to higher dissociation temperature and lower
nitrogen partial pressure
• Growth of quaternaries InGaN GaN AlGaN
(InGaAlN) are difficult
T Low High Higher
due to the conflicting
740 oC 1050 oC 1100 oC
growth conditions of
AlN and GaN. Usually P 200-400 40-100 30-50
max. In incorporation is torr torr torr
possible only up to ~5% V/III >5000 1000-2000 <=1000

ELECT 871 02/16/04

 Various problems associated with mismatches
Substrate Property Consequence
1. Lattice (a-lattice constant) 1. All problems typically associated
mismatch with high dislocation density
2. Vertical (c-lattice constant 2. Anti-phase boundaries, inversion
mismatch) domain boundaries
3. Coefficient of thermal expansion 3. Thermally induced stress, cracks in
mismatch epitaxial films
4. Low thermal conductivity 4. Poor heat conduction; unsuitability
for high power devices
5. Different chemical composition of 5. Contamination, interface states, poor
the epitaxial film wetting of surface during growth
6. Non-polar surface 6. Mixed polarity; inversion domains

ELECT 871 02/16/04

 Strain and critical thickness
aepi x   asub
Lattice mismatch f m ( x) 
aepi x 
asub  aepi x 
In-plane strain  ( x)   f m x  
aepi x 
aepi x   a sub
Strain relaxation r x  
aepi,0 x   a sub
aepi,0(x) = measured lattice constant, aepi,0(x) =
relaxed lattice constant, asub(x) = substrate
lattice constant
Calculation of the critical thickness is
very difficult experimentally as it
depends on many different factors such
as in-plane strain, burgers vector of
dislocations, growth methodologies etc.
ELECT 871 02/16/04
 Formation of dislocations
• Dislocation are formed in the epitaxial layers due to
– Transfer of defects/dislocations already present in the substrate:
Happens when substrate has high density of defects (example:
when SiC used as a substrate)
– Misfit dislocation: When dislocations are caused by a
difference in the lattice constant of the epitaxial layer and the
substrate
– Imperfections resulting from island coalescence
• Main types of dislocation in GaN
– Threading edge dislocation
– Threading screw dislocation
– Mixed screw-edge dislocations
ELECT 871 02/16/04
 Dislocation types
• Pure edge
dislocation: b
= 1/3[11-20]
• Pure screw
dislocation: b
= [0001]
• Mixed screw-
edge
dislocation: b
= 1/3[11-23]
(a), (b): full core and
open core edge
dislocation. (c) Ga-
terminated full core,
and (d) open core
screw dislocation
ELECT 871 02/16/04
 Dislocations line structure in GaN film
 1 1  r0
    2 R2

 R2 R1  r r
R1
b 2
r0  2
8 
b = magnitude of Burgers vector,  = shear
modulus,  = specific surface free energy, r0
R1 and R2 inner and outer radii of curvature

• Whenever dislocation reach the surface it ends in a pit

(this makes possible for AFM to record dislocations)
• Screw dislocations have higher radii of surface pit than
edge dislocations due to higher burger’s vector
ELECT 871 02/16/04
 Dislocation characterization by AFM
2 nm
/div

0.50
nm/
Div

(a)
0.0 1.0 2.0 m
(b)

1. 40 Morphologies of
Height AlGaN/GaN
(nm) 1.00
heterostructure
0.60 on (a) SiC and
0.0 1.0 2.0 (b) sapphire
Distance (m)
ELECT 871 02/16/04
 Points to note about dislocations
• Step heights in nitride epitaxial films are ~2.6 Å (about
half the unit cell height of 5.185 Å)
• Dislocations chains are formed around coalescing islands
formed during the initial part of the growth
• Density of dislocations in epitaxial films grown on either
sapphire or SiC is ~109 -1010 cm-2
• Screw and mixed edge-screw dislocations can terminate
steps (usually two) as they both have a vertical component
of the burgers vector
• Screw and mixed-screw dislocations usually terminate in
larger pits than edge dislocations due to larger burgers
vector (pit-radius is proportional to the square of the
burgers vector magnitude)
ELECT 871 02/16/04
 An estimate of density of acceptor states
with dislocations
• Dislocation dangling bond
density = (2/5.210-8) cm-1 =
3.85 107 cm-1
• The density (per unit area) of
dislocation induced states for 2
micron thick epitaxial layer =
3.85 107 cm-1  1010 cm-2 (2 
10-4 cm) = 7.7 1013 cm-2
• Assuming just 10% of the states
capture electrons there are 7.7 A full-core edge dislocation
1012 cm-2 electrons lost has 2 dangling bonds (1Ga
• Since the dislocations states are and 1 N atom along the
so close in real space they will be dislocation line) in a per unit
energy band in the reciprocal lattice spacing along c-axis
space along the c-axis
ELECT 871 02/16/04
 Detrimental effects of dislocations I
Leakage through dislocation Recombination of electrons
states in a schottky contact and holes via dislocation states
EF, metal

qVG
(VG -ve)
Dislocation
EF, semi states form a
band in
reciprocal Recombination process via defect
space states usually does not emit light.
Even if it does, it will not be at
 Conduction through the dislocations states the band-edge energy
when they form bands
 Tunneling assisted by the dislocation states.
 Dislocation induced leakage forms a major
component of gate leakage current in HFETs
ELECT 871 02/16/04
 Detrimental effects of dislocations II
Band diagram around a Charged dislocation
charged dislocation -- line
--
e --
-- Electrons get
-- scattered by
--
-- charged
-- dislocations

Mobility vs. sheet charge in

AlGaN/GaN heterostructures for
different dislocation densities

If the Fermi level is above the dislocation

induced acceptor states in the forbidden
gap, then they will capture electrons and
get charged. The bands will look like a
cone around dislocation in 3D
ELECT 871 02/16/04
 Detrimental effects of dislocations: Summary
• Dislocations cause leakage current in schottky contacts by
acting as electrical short (electrons move from state to state)
• Dislocations get charged by capturing electrons. Effect….
– Reduction in sheet charge at the interface
– Reduction of electron mobility
• Dislocation states act as non- radiative recombination center
for electrons and holes and reduce the luminescence
efficiency for opto-electronic devices
• Dislocations also cause lifetime and reliability problems in
devices due to over-heating
Solution to the problems created by dislocation ……..
Get rid of them!
ELECT 871 02/16/04
Major techniques to reduce dislocations
• Bulk growth
– By direct synthesis
– By sublimation
• Exotic substrates
– Si
– ZnO
– Lithium niobate
– Lithium gallate
• Lateral epitaxial overgrowth
• Pendio-epitaxial growth
• Quasi-bulk growth by HVPE on sapphire

ELECT 871 02/16/04

 Reduction of dislocations: LEO growth
3.
1.
2.

• One of the most commonly used Cross-sectional TEM

techniques to reduce dislocation density image of LEO GaN
in nitride films
• Advantage: Simple fabrication
procedure, can be easily implemented
• Disadvantage: Dislocation density only
reduced in selected areas. The stripes
free of dislocation not very suitable for
large scale device fabrication
ELECT 871 02/16/04
Reduction of dislocations: Pendioepitaxy
Cross-sectional image of a GaN film grown
by Pendiepitaxy

Advantage: Reduces dislocations in GaN over

the entire area unlike LEO
Disadvantage: Requires lithographic patterning
and RIE etching step. This may result in stress
in the GaN film. Also, the material has lower
mechanical strength.
ELECT 871 02/16/04
 Quasi-bulk GaN: Hydride Vapor Phase Epitaxy
Ga (melt) + HCl = GaCl + ½ H2

GaCl + NH3 = GaN + HCl + H2

GaN + HCl = GaCl + ½ N2 + ½ H2

“Hydride (not halide)” because of the use

of NH3. If NCl3 is used then it becomes
“Halide”

• Usually requires MOCVD templates

or LEO substrates (not easy to grow
smooth layers just by itself)
• Usual growth rates few tens of
microns per hour resulting in smooth
low dislocation films
• Low cost technique
ELECT 871 02/16/04