PART II: MOLECULAR BEAM

EPITAXY
• Description of the MBE equipment
• Reflection High Energy Electron Diffraction
(RHEED)
• Analysis of the MBE growth process
• Surface diffusion in MBE
• MBE growth of III-V binary compounds and
alloys
• MBE growth of lattice-matched and lattice-
mismatched heterostructures
• Doping in III-V materials
 Molecular Beam Epitaxy (MBE)

• Ultra-High-Vacuum (UHV)-based technique for producing high quality

epitaxial structures with monolayer (ML) control.
• Introduced in the early 1970s as a tool for growing high-purity
semiconductor films.
• One of the most widely used techniques for producing epitaxial layers
of metals, insulators and superconductors.
• Research and industrial production applications (Al-containing, high
speed devices).
• Simple principle: atoms or clusters of atoms, produced by heating up
a solid source, migrating in UHV onto a hot substrate surface, where
they can diffuse and eventually incorporate.
• Despite the conceptual simplicity, a great technological effort is
required to produce systems that yield the desired quality in terms of
material purity, uniformity and interface control.
Description of the MBE equipment

• M. A. Herman, H. Sitter, “Molecular Beam Epitaxy, Fundamental

and Current status”, Springer (1996)
• G. Biasiol and L. Sorba, in “Crystal growth of materials for energy
production and energy-saving applications”, R. Fornari, L. Sorba,
Eds. (Edizioni ETS, Pisa, 2001) pp. 66-83 (http://www.tasc-
infm.it/research/amd/file/school.pdf).
 MBE Facility

• Growth, preparation and introduction chambers

• Stainless steel, bake-out up to 200C for extended periods
of time
• Image: Veeco Gen-II High-mobility MBE system at TASC
 Research and production MBE systems

R&D
Riber Compact21 system:
• Vertical reactor
• Up to 1X3” wafer
• 6 to 11 source ports

Production
Riber MBE6000 system:
Up to 4X8” wafers (MBE7000
model)
• 10 large capacity source ports
• Fully motorized wafer handling and
transfer
 Schematics of an MBE system
Pumping
system

Effusion
cells Liquid N2 cryopanels
Substrate
manipulator • around main walls and
source flange
Analysis tools: • thermal isolation among
• RHEED cells
• RGA • prevent re-evaporation
from parts other than the
• Optical ( cells
ellipsometry
, RDS...) • additional pumping

Cell
shutters
 Pumping system

• Minimization of impurities:
R ~ 1ML/sec, n ~ 1022at cm-3, p ~ 10-6Torr
for nimp < 1015 cm-3 ⇒ p < 10-13 Torr
In practice: p ~ 10-11 – 10-12 Torr, mostly H2
• Used pumps: ion, cryo, Ti-sublimation.
 Effusion cells
Thermocouple
Connector

Heat Shielding
Crucible

Power
Connector
Head Assembly Mounting Flange
Filament and Supports
Thermocouple
Principle of operation of the Knudsen cell.
Features of an effusion cell
The most common type of MBE source is the effusion cell. Sources of this type are sometimes called Knudsen
• 6 –or10K-cells,
cells, cell ininareference
source flange
to the evaporation sources used by Knudsen in his studies of molecular
• Co-focused
effusion. However, onto
a “true” Knudsen ⇒
substrate cellflux
has uniformity
a small diameter orifice (<1mm) to maintain high pressure within
the crucible.
• Flux With certain
stability <1% /exceptions,
day ⇒ ∆Tthis practice
< 1ºC @ isT undesirable
~ 1000 ºCin MBE because it limits deposition rates.
Conventional MBE effusion cells are usually fit with a removable, open-faced crucible having a large exit
• Temperature
aperture. The crucibleregulation by high-precision
and source material PID regulators
are heated by radiation from a resistively heated filament. A
• Minimization
thermocouple of flux
is used driftclosed
to allow as material control. ⇒ choice of geometry
is depleted
loop feedback
 Crucibles

 Cylindrical Crucible
+ Good charge capacity
+ Excellent long term flux stability
- Uniformity decreases as charge depletes
- Large shutter flux transients possible
 Conical Crucible
- Reduced charge capacity
- Poor long term flux stability
+ Excellent uniformity
- Large shutter flux transients possible
 SUMO® Crucible
+ Excellent charge capacity
+ Excellent long term flux stability
+ Excellent uniformity
+ Minimal shutter-related flux transients
 Valved cracker
For elements which sublime as molecules (As, P, Sb …)

1. Cracking zone
2. Conductance tube
3. Mounting flange
4. Power and thermocouple connectors
5. Bulk evaporator zone
6. Crucible
7. Back flange
8. Valve positioner

Principle of operation for the Valved Cracker.

The source material is loaded into the large capacity crucible and heated. A
needle valve in the conductance tube regulates the amount of evaporant that
enters the growth chamber. Cracking zone temperature is controlled so as to
produce beams of either cracked (e.g., As2) or uncracked material (e.g., As4).
 Dopant sublimation sources

“SUSI” Si sublimation source from Omicron

• Sublimation from a Si wafer
• Suitable for doping and thin Si layers
• High crystal quality and purity
• Low growth rates
 Evaporation flux

The flux J at the substrate a distance d (cm) from the tip of the cell and on its
axis can be calculated, assuming that the evaporant is in equilibrium with its
vapor at pressure p (Torr) (cosine law of effusion, see lecture 1):

h e a tin g b lo c k
s u b s tr a te

J
p (T ) A  at 
J = 1.12 × 10 22
 cm 2 s 
d 2 MT
A d
log P = + B log T − C
T
A
M: molecular weight in amu
T: source temperature in K
p
A: source area in cm2 M
T
 Vapor pressure chart

As4 Ga

Al

TAs4 < Tsubstr < TGa,Al ⇒ As re-evaporation ⇒ growth in As4 overpressure

 Numerical Application:

Estimation of the GaAs growth rate r

Typical values:
T (Ga cell) =1000oC=1273oK ⇒ P ~ 10-3 Torr

p (T ) A  at 
J = 1.12 ×10 22
2  2 
d = 10cm, A = 3.14cm 2
, M = 70
d MT  cm s 
at
J = 1.18 ×1015
cm 2 s
r = JΩ 0 , Ω 0 (GaAs) = 2.27 ×10 − 23 cm3
r = 2.67 Å/s = 0.96 µm / h
 Cell shutters

• Function: flux triggering

• Materials: Ta – Mo
• Mechanical or pneumatic actuators
• Operation (~50ms) much faster
than ML deposition time (~1s)
• Designed for more than 1 million
cycles
• Not outgassing from cell heating
• Minimization of heat shield ⇒ no
flux transients
• Computer control for reproducibility
 Substrate manipulator

• Continuous azimuthal rotation ⇒ uniformity

• Heater behind sample (Ta, W, C):
temperature uniformity, small outgassing
• Beam flux monitor (BFM) opposite to sample
for flux calibration
• Temperatures up to >1000C
 Wafer holders

• Mo- or Ta- made holders

• Bonding: In (Ga), or In-free
(clamped)
• Quick and easy transfer

Image: In-free, 3-inch sample

holder fitting a quarter of a 2-inch
wafer
 Residual Gas Analyzer

• Filament: Atoms and molecules are ionized in a signal ion source following electron
impact.
Electrons are emitted from the hot filaments.
• Quadrupole: Ions with a specific mass-to-charge ratio are filtered by applying a
combination of DC and RF voltages to each quadrupole.
• Faraday Cup: Mass filtered ions are collected by the Faraday cup detectors.
• Functions: leak detection, measure of the system cleanliness (quality of bake and
pumping, impurities from outgassing...), studies of growth mechanisms
Reflection High Energy Electron
Diffraction (RHEED)

• M. A. Herman, H. Sitter, “Molecular Beam Epitaxy, Fundamental

and Current status”, Springer (1996)
• G. Biasiol and L. Sorba, in “Crystal growth of materials for energy
production and energy-saving applications”, R. Fornari, L. Sorba,
Eds. (Edizioni ETS, Pisa, 2001) pp. 66-83 (http://www.tasc-
infm.it/research/amd/file/school.pdf).
 Reflection High Energy Electron Diffraction
Si(001) RHEED patterns
sputter-cleaned surface

• Cells ⊥ substrate ⇒
RHEED // substrate

• Control of the
crystallographic structure perfect surface
of the growing epitaxial
surface

• Pattern for 2D surface:

series of // lines

high density of steps

rough surface
 Surface sensitivity of RHEED

12.247
[ Å]
Ek = 5-40KeV
λ=
λ = 0.17-0.06Å EK
Θ = 1-3o d(penetration) = λesin θ
λe ≈ 10ML ⇒ d = 0.5ML ⇒ Surface sensitivity
 Diffraction: 3D vs 2D

3D 2D
(1st layer of perfectly flat surface)

G ⇒ // ∞ rods
a=5.65Å ⇒ G=2π/a=1.1 Å-1
∆K = G Ek=5KeV ⇒ k∝1/λ=36.5Å-1
⇒ k >> G
 Ideal RHEED Pattern
Ewald sphere
Projected image
on screen

Sample

• Perfect 2D
crystalline surface Ideal pattern: series of
Intersection of Ewald
points on a half circle (for
• Perfectly monochromatic, sphere with G vectors
each nth-order Laue zone)
collimated beam
 Diffraction in real case

Thermal vibrations, lattice imperfections

⇒ finite thickness of reciprocal lattice rods
Divergence and dispersion of e-beam
⇒ finite thickness of Ewald sphere

⇓
Diffraction spots ⇒ streaks with modulated intensity even for 2D surfaces
 Non-ideal Surfaces

• Ideal surface ⇒ circular arrays of

(elongated) spots Ideal surface
• Amorphous layers ⇒ no diffraction
pattern, diffuse background
• Polycrystallyne – textured surface
Polycrystal
⇒ diffuse rings (Debye-Sherrer
construction)
• 3D surface ⇒ electrons transmitted
through surface asperities and Rough surface
scattered in different directions ⇒
spotty RHEED pattern
 Non-ideal Surfaces: Example
RHEED SEM

De-oxidized GaAs substrate

+ 15nm epitaxial GaAs

Lateral, periodic
intensity modulation!

+ 1µm epitaxial GaAs

A. Y. Cho, J. Cryst. Growth 201/202 (1999), 1

 GaAs (001): (2x4) RHEED Pattern

2x ([110] direction ) 4x ([-110] direction)

Reciprocal space
 GaAs (2x4) Reconstruction

Original model:
GaAs(001) (2x4) unit cell: 3 As
dimers along [-110] + 1 dimer
vacancy ⇒ surface energy
reduction

Top As layer
Top Ga layer
2nd As layer

Direct space
 GaAs (2x4) Reconstruction

Top As layer
Top Ga layer
2nd As layer

Further studies (total energy

calculation, STM: 4 phases with As
coverage 0.25 → 0.75 and different
dimer distribution.

Right: STM of GaAs(001)-β2(2X4)

V. P. LaBella et al., Phys. Rev. Lett. 83, 2989

(1999)
 GaAs surface phase diagram

• As-stable (2X4): 4 phases with As coverage 0.25 → 0.75

• Lower T, higher As4/Ga: As-rich c(4X4) with additional As
dimers
• Higher T, lower As4/Ga: Ga-stable (4X2), Ga dimers
along [110]
• Even higher T, lower
As4/Ga: Ga droplets
• Other reconstructions
exist, maybe as
interference between
domains
 Growth dynamics: RHEED Oscillations

RHEED maximum spot intensity indicate # of deposited atomic layers = #

completion of growing layers of maxima
⇒ layer-by-layer control of the growing
growth rate = 1ML / τ
crystal surface
 GaAs Growth

shutters open
shutters closed
GaAs

RHEED intensity (Arb. Units)

AlAs

0 10 20 30 40 50
Tim e (s)

Shutter closed:
Oscillation dumping: statistical
GaAs: 2D rearrangement of
distribution of growth front → constant
mobile Ga adatoms ⇒ intensity
surface roughness.
recovery
Persistence of RHEED oscillations ⇔
AlAs: low surface mobility of Al
layer-by-layer epitaxial quality
adatoms ⇒ no recovery
Analysis of the MBE growth process

• M. A. Herman, H. Sitter, “Molecular Beam Epitaxy, Fundamental

and Current status”, Springer (1996).
• G. Biasiol and L. Sorba, in “Crystal growth of materials for energy
production and energy-saving applications”, R. Fornari, L. Sorba,
Eds. (Edizioni ETS, Pisa, 2001) pp. 66-83 (http://www.tasc-
infm.it/research/amd/file/school.pdf).
 Three-phases model

heating block substrate

• Gas phase (molecular beam crystallization zone
substrate
generation + vapor mixing zones): vapor elements
mixing zone
complete lack of order, no
homogeneous reactions (ballistic molecular beam
transport). generation zone

• Crystalline phase (substrate,

epilayer): complete short- and
long-range order.
• Near-surface transition layer
(substrate crystallization zone):
area where all processes leading
to epitaxy occur (heterogeneous
reactions on hot surface). Layer
geometry and processes strongly
dependent on growth conditions.
 Atomic-scale mechanisms of epitaxial growth
chemisorption
physisorption
Adsorption (physi-chemisorbtion)
of the costituent atoms or tet rameric
molecule
molecules impinging on the
substrate surface
Ea Edp distance to the
Edc substrate surface

p
o
ra
c
lte
in
physisorbed precursor
state
• Surface diffusion rc chemisorbed state

• Thermal desorption rp
• Formation of two-dimensional
clusters
• Incorporation at steps
• b
Step diffusion
• Incorporation at kinks
f
All steps (a-f) strongly dependent c e
a a
on kinetics (T, r, V/III ratio, crystal d
orientation...)
Surface diffusion in MBE
step-flow growth 2D nucleation–surface diffusion: RHEED analysis

High T ⇒ λ > λ 0

λ0 Critical T:
Tc ≈ 590C ⇒
λ ≈ λ0
nucleation of 2D islands

Low T ⇒ λ < λ 0

λ0

Neave et al, APL 47 (1985) 100

 Growth modes: GaAs homoepitaxy
T=520°C 550°C 600°C

a) b) c)
650°C 700°C 750°C

d) e) f)
Transition from 2D island nucleation to step flow growth (MOCVD). 5X5
µm2 post-growth AFM scans, heigth scale 2-5nm
 Growth modes: Si homoepitaxy

In-vivo STM of Si (001) homoepitaxy; 0.3X0.3 µm2 scans

B. Voigtländer et al., Phys Rev. Lett. 78, 2164 (1997)
http://www.kfa-juelich.de/video/voigtlaender/

T = 450C
T = 550C
island nucleation growth
Step-flow growth
 Determination of diffusion coefficient

Exactly: τ = τnuc
• λ = λ(T, r, V/III)
Assumption: τ = 1/r
• Einstein relation: λ2 = 2Dτ (upper limit)
• D = diffusion coefficient, τ =
characteristic time for diffusion
• ⇒ D = λ2 / (2τ), D = D0 exp (-ED / kT)
• ED = activation energy for Ga surface
diffusion
• Experiment: measurement of Tc(r) at
fixed misorientation (λ(Tc) = l)
• Arrhenius plot ⇒
ED = 1.3±0.1eV
D0 = 0.85 X 10-5 cm2 s-1
Neave et al, APL 47 (1985) 100
 Surface diffusion: a more rigorous
Assumptions: approach
• Vicinal surface with uniform step separation λ0
• Rough step edge ⇒ negligible step diffusion ⇒ 1D problem
• JAs >> JGa ⇒ As disregarded except for reaction at step edge

dns d 2 ns ns
Basic diffusion equation (steady-state) = Ds + J − =0
dt dy 2
τs

ns = adatom surface concentration

Ds = surface diffusion coefficient
J = flux from Knudsen cell
τs = re-evaporation (residence) time
λs = sqrt (Dsτs) = re-evaporation
diffusion length
T. Nishinaga, in “Handbook of crystal growth”, vol.3,
p.666, ed. By D.T.J. Hurle, 1994 Elsevier Science B.V.
 Solution of diffusion equation
⇒ Surface concentration :
cosh ( y / λs )
ns ( y ) = Jτ s + ( nstep − Jτ s )
cosh ( λ0 / 2λs )
2 
 2y  
2
Jλ0
= nstep + 1 −    (for λs >> λ0 (typical for MBE)
8Ds   λ0  
 

Close to step edges, adatoms reach the step and incorporate before re-
evaporation ⇒ lower density
 Boundary condition at step edge

nstep given by balance of incorporation flow at the step and

surface diffusion flow
Incorporation flow (⇔ step supersaturation):

 λ0  nstep Dstep
Js  = ∇µ step Nernst-Einstein relation
 2 k BT
nstep − ne
=a
τ step
Js = surface lateral flux
nstep = concentration at step edge
ne = equilibrium concentration
Dstep = a2/ τstep = step diff. coeff.
a = lattice constant
τstep = adatom relaxation time to enter
τstep depends on activation
the step energy to enter the step and on kink
density
 Boundary condition at step edge

nstep given by balance of incorporation flow at the step and

surface diffusion flow
Surface diffusion flow

 λ0   dn s 
J s   = − Ds   λ
 2  dy  y= 0
2
 n step  λ0
=  J − 
 2
 τs 

(for λs >> λ0)

 Supersaturation ratio at step edge

n step − ne  n step  λ0
a =  J − 
 2
τ step  τs 

−1
nstep ne  λ0τ step   λ0τ step ne 
α step = =  1 +   J + 
ne τ s  2 aτ s    2 aτ s τs 
ne pe
where =
τs 2πmkT

pe = equilibrium pressure of growth atom with the surface

m = mass of growth atom
 Step edge activity
−1
nstep n  λ τ   λ0τ step n 
α step = =  e 1 + 0 step   J + e 
ne τ s  2 aτ s    2 aτ s τs 
• J, λ0 decreased • J, λ0 increased
(small Ga flux to the step) (high Ga flux to the step)
• Temperature increased • Temperature decreased
(τstep decreased) (τstep increased)

Step edge very active to accept Negligible incorporation of Ga

Ga atoms, nstep → ne atoms at steps, nstep → n∞
 Critical supersaturation for 2D nucleation

 Ωπhσ 2 
Nucleation theory: α c = exp  2
 ( 65 − ln I c )( kT ) 

Where
Ω = atomic (cell) volume
h = step height
σ = free energy of 2D nucleus side surface
Ic = nucleation rate
 2D nucleation vs. step flow

 Jλ20 
At the middle of the terrace α max =   + 1 (for nstep = ne )
 8Ds ne 
αmax > αc ⇒ 2D nucleation αmax < αc ⇒ step flow

ns ( y ) Jλ 2   2 y 2 
α ( y) = = 1+ 0
1 −   
nstep 8 Ds nstep   λ0  
 2D nucleation vs. step flow

 Jλ20 
At the middle of the terrace α max =   + 1 (for nstep = ne )
 8Ds ne 
Applications: GaAs (001): larger flux, smaller miscut
⇓
larger αmax
⇓
Higher Tc for 2D nucleation
MBE growth of III-V binary compounds
and alloys
 Modulated molecular beam techniques

• Experimental technique: Modulated-Beam Mass Spectrometry

(MBMS)
• Applications: studies of growth process chemistry in GaAs MBE on
(001) surfaces
• Basic method: evaporation of neutral atoms beam onto substrate;
detection of desorbing flux with RGA mass spectrometer
• Problem: discrimination beteen background and desorbing species
• Solution: modulation of incident beam or desorbing flux.

• C. T. Foxon and B. A. Joice, Surf. Sci. 50 (1975) 434, Surf. Sci. 64 (1977) 293
• C. T. Foxon, in “Handbook of crystal growth”, vol.3, p.156, ed. By D.T.J. Hurle, 1994
Elsevier Science B.V
 Binary III-V compounds

• Group III (Al, Ga, In): monomers, low vapor pressure at

typical substrate growth temperatures ⇒ sticking
coefficient = 1 (no desorption or re-evaportation) ⇒
group-III flux determines growth rate.

• Group V (P, As, Sb): dimers-tetramers, high vapor

pressure ⇒ sticking coefficient < 1 ⇒ need for
overpressure to maintain stoichiometry.
 As2 growth kinetics

• Supplied by GaAs or As cracker

source
• Adsorbed as mobile precursor
(physisorption)
• No Ga:
• Fast desorption as As2 or
As4 (low T)
• With Ga:
• Dissociative chemisorption
(1st order reaction)
• Sticking coefficient ∝ Ga
flux (max = 1)
• Desorption of excess As ⇒
stoichiometry
 As4 growth kinetics

• No Ga: fast desorption

• With Ga:
• 2nd order reaction
between pairs of As4
on Ga sites ⇒ 4
incorporated As atoms
+ 1 desorbed As4
• Max. sticking
coefficient = 0.5
• Second-order
dependence of As4
desorption rate on
adsorption rate
• Similar behavior for other
III-V compounds or alloys
 Simulation of GaAs (001)-(2X4) growth
P. Kratzer and M. Scheffler, Phys. Rev. Lett. 88, 036102

• Kinetic Monte Carlo (kMC) simulations, rates derived from density-functional

theory (DFT) ⇒ chemical bonding on atomic level and surface morphology at
the large length and time scales characteristic for growth.
• GaAs (001)-(2X4) growth from Ga and As2; topmost As dimerized along
[-110] unless Ga atom in between
• > 30 processes with rate laws Γi=Γ0exp (-Ei/kT); activation energies Ei by
DFT
• Surface mobility: Ga, As2 (no As)
• Ga flux: 0.1ML/s
• Ga diffusion: anisotropic, 10 hopping processes
• Ga incorporation for strongly bound configurations ⇒ stop diffusion
• As2 incorporated as dimer (no dissociation) on sites with 3-4 bonds to Ga
• As2 desorption: 3 events with different rates depending on environment
• Simulation results
 AxB1-x-V alloys

• Standard temperatures: sticking coefficient = 1 ⇒ growth

rate r = rA + rB, composition x = rA/(rA+rB)
• High temperatures:
• Transition from group-V stable surface (i.e. (2X4) in
GaAs) to metal-rich surface ⇒ high group-V flux to
keep surface stoichiometry.
• Desorption of more volatile group-III element (In > Ga
> Al) ⇒ deviations from ideal r and x
• Surface segregation of more volatile group-III element

C. T. Foxon, in “Handbook of crystal growth”, vol.3, p.156, ed. By D.T.J. Hurle, 1994
Elsevier Science B.V
 III-AxB1-x alloys

• More complicated situation, no easy relation between x

(vapor) and x (solid):

• Difference in adsorption efficiency

• Difference in vapor pressure (P > As > Sb) (at low T
preferential incorporation of low vapor pressure dimer
or tetramer)
• Mutual interference of the sticking coefficients

C. T. Foxon, in “Handbook of crystal growth”, vol.3, p.156, ed. By D.T.J. Hurle, 1994
Elsevier Science B.V
 MBE growth of lattice-matched and
lattice-mismatched heterostructures
 GaAs/AlxGa1-xAs heterostructures

shutters open
shutters closed
G aAs

RHEED intensity (Arb. Units)

• Lattice-matched system for 0 < x < 1
AlAs

• Interface atomic structure influences optical and

electronic properties of HS, QW and 2DEG-based
devices 0 10 20 30
Tim e (s)
40 50

• λGa >> λAl ⇒ intrinsic asymmetry between morphology of

“normal” (AlGaAs-on-GaAs) and “inverted” (GaAs-on-
AlGaAs) interfaces
• High reactivity of Al ⇒ segregation of impurities towards
the inverted interface
 Growth interruptions: effects on the optical
properties of GaAs/AlGaAs QWs
M. Tanaka, H. Sakaki, J. Cryst. Growth 81, 153 (1987)

Growth x = 0.33 x=1

interruption
A
above-below

B An exciton is a bound state of an electron and a hole in an insulator (or

semiconductor), or in other words, a Coulomb correlated electron/hole pair.
above It is an elementary excitation, or a quasiparticle of a solid.
λ(roughness) << λ
A vivid picture of exciton formation is as follows: a photon enters a
(exciton); λ
C semiconductor, exciting an electron from the valence band into the
(roughness) >> λ
conduction band, leaving a hole behind, to which it is attracted by the
below (exciton) ⇒ sharp
Coulomb force. The exciton results from the binding of the electron with its
PL and
hole ⇒ the exciton has slightly less energy than the unbound electron
D hole. The wavefunction of the bound state is hydrogenic. However, the
binding energy is much smaller and the size much bigger than aλ(roughness)
hydrogen ≈λ
none of the ⇒ broad
(exciton)
atom because of the effects of screening and the effective mass
constituents in the material. PL
 Impurity segregation in AlGaAs

• High reactivity of Al atoms (with

respect to Ga).
•⇒ higher incorporation of
impurities, with segregation to the
surface.
• ⇒ inverted interface is more
contaminated than normal one.
• Left: SIMS profiles of O impurities
in an AlxGa1-xAs multilayer, where
1. O concentration is higher for
higher x.
S.Naritsuka et al., J. Cryst.
2. O segregates at interfaces Growth 254, 310 (2003)
where lower x material is
grown on higher x one.
Lattice-mismatched heterostructures

• Needed to expand flexibility in

materials choice (e.g., InxGa1-
xAs/GaAs)

• Misfit:
fi = (asi-aoi)/aoi

i = x,y (growth plane)

a = lattice constant
s = substrate
o = overlayer
• fx,y (InAs/GaAs) ≈ 7%
 Growth mode for small lattice mismatch

Eε > ED
Relaxation through dislocations

Layer thickness
Eε = ED
Eε < ED
Pseudomorphic growth

ED Eε

Energy

Separate bulk layers of Epitaxy of thin layer of B on substrate A:

materials A and B, with pseudomorphic (strained) growth for Eε
a(B) > a(A) (increasing) < ED (constant),
dislocations for E > E .
 Dislocations

Edge dislocation: line defect that occurs when there is a missing row
of atoms. The crystal arrangement is perfect on the top and on the
bottom. The defect is the row of atoms missing from region b. This
mistake runs in a line that is perpendicular to the page and places a
strain on region a.
 Critical thickness and dislocations

• Thin epilayer grown on substrate with

different lattice parameter
strain Eε • Energetics:
dislocations • Strain: increases with thickness
ED • Dislocations: thickness independent
• Energetic trade-off between
ita
nG
R
N
Y
E
ru
e
p

fo pseudomorphic and dislocated epilayers:

LATTICE MISFIT
• beyond a critical lattice misfit f0 the
adjustement of the two lattices by
dislocations is energetically more
favorable than by strain
Eε
• for thicknesses exceeding the critical
ED thickness h0 dislocations are
energetically more favorable than strain
ita
nG
R
N
Y
E
ru
e
p

ho
LAYER THICKNESS H. Luth, “Surfaces and Interfaces of Solid
Materials”, 3° ed., Springer, Berlin, 1995
 Critical thickness: energetic calculations
• Minimization of energy for the epitaxial system
• Critical thickness in units of as as a function of f, for
the introduction of 60o misfit dislocations on (111)
glide planes in a (001) interface
M. A. Herman, H. Sitter, “Molecular Beam Epitaxy, Fundamental and Current
status”, Springer (1996)
 Strained epitaxy: experiment

• Existence of kinetic barriers ⇒

critical thicknesses much larger
than predicted by energetic
balance.
• Methods to increase t0:
• Reduction of surface diffusion GaAs
(Low T, Ga-stabilized surfaces
(InGaAs on GaAs),
surfactants)
• Gradual lattice
accommodation (graded buffer
layers (BL))
Image: TEM cross section of a metamorphic In0.75Ga0.25As/
In0.75Al0.25As QW grown dislocation-free on a GaAs (001) substrate (f
~ 5%) by insertion of a ~1µm-thick InxAl1-xAs step-graded BL
(F. Capotondi et al., Thin Solid Films 484, 400 (2005).))
 Strained growth: Onset of 3D growth (S-K)

• Very large mismatch: strain

relaxation energetically more
favorable by 3D islanding, rather
than dislocations.
• Right: critical thicknesses as a
function of x in InxGa1-
xAs/In.53Ga.47As for the onset of 3D
tc TRM
growth (t3D) and misfit dislocations
(tc), at T = 525C. Transition from
dislocations to 3D occurs (TRM) at x
~ .75, i.e., f = 1.7% (M. Gendry et al.,
Appl. Phys. Lett. 60, 2249 (1992))
t3D

M. A. Herman, H. Sitter, “Molecular Beam Epitaxy,

Fundamental and Current status”, Springer (1996); original
data from M. Gendry et al., Appl. Phys. Lett. 60, 2249
 Doping in III-V materials

• C. T. Foxon, in “Handbook of crystal growth”, vol.3, p.156, ed. By

D.T.J. Hurle, 1994 Elsevier Science B.V
• G. Biasiol and L. Sorba, in “Crystal growth of materials for energy
production and energy-saving applications”, R. Fornari, L. Sorba,
Eds. (Edizioni ETS, Pisa, 2001) pp. 66-83 (http://www.tasc-
infm.it/research/amd/file/school.pdf).
 Doping in III-V materials

Top: free-carrier densities in

• Group-IV
Doping necessary
atomsforamphoteric:
carrier transport in electronic
donors or optoelectronic
(if incorporated
Si-doped
devices
on group-III
{311}A and (100)
• sites)
Dopingor byacceptors (on group-V
group II (p-type), IV (p- orsites)
n- type)
GaAs andatVI300
atoms
K as (n-type)
a function of
Compositional
• C: acceptor, but very low vapour
• Group II the pressure,
V4 /III ratio.⇒Dotted
dependence very high of SiTNSi(>.
line:
2000C) donor activation
• II-b atoms (Zn, Cd): too high vapour pressure at usual growth
• Ge: amphoteric
temperatures ⇒ not behavior
used in difficult
MBE to control Phase
Bottom: energy
diagram in (V4 /III
•• Sn: too high
II-a atoms (Besurface segregation
in particular): the universal ratio – T) for Al
choice the xGa 1-xAs
conduction
K.Kohler ettype
al.,
of JCG 127, 720
(N. (1993).
Chand et al., PRB
• Si: universal n-type SIMS
dopant profiles
in (Ga,In,Al)As Si-δ
of
• Group-VI atoms uncommon (surface segregation, re-evaporation)
Sidoped
doped
(001) {311}A
30, 4481 (1984)
GaAs.
GaAs grown at different
– n up to ~10 cm before compensation (substitution
19 -3 Dot sizeT ∝ activationon As
(A.
P. Mills et al., JAP 88, 4056 (2000)
efficiency.
sites, Si-vacancy complexes, Si clusters…)
– Diffusivity towards the surface at doping
(N. Sakamoto levels
et al., APL 67,higher than
1444 (1995)
about 2X1018 cm-3 ⇒ problem in sharp doping profiles
– Donor ionization energy increases in AlGaAs ⇒ reduced
doping efficiency
– GaAs(311)A surfaces : n- to p-type transition depending on T
and III/V ratio ⇒ can be used as p-type dopant
 Modulation doping and the two-dimensional
electron gas

Electrical conduction (otherwise semi-insulating)

BUT
Bulk doping
Introduction of impurities ⇒ source of scattering,
limitation of mobility at low temperatures

Temperature dependence of mobility in

n-type GaAs. The dashed curves are the
corresponding calculated contributions
from various mechanisms.
P. Y. Yu and M. Cardona, Fundamentals of
Semiconductors (Springer-Verlag, Berlin, 1996).
 Modulation doping and the two-dimensional
electron gas
Solution: spatial separation between doping layer and conducting
channel
modulation doping
(δ doping)

GaAs GaAs GaAs

substrate epilayer AlGaAs cap Increase of 
mobility
e- +
Energy

conduction band

EF
2 DEG

H. Störmer, Surf. Sci.132 (1983) 519

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