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Lattice gas models and Kinetic Monte Carlo

simulations of epitaxial crystal growth
Theoretische Physik und Astrophysik
& Sonderforschungsbereich 410
Julius-Maximilians-Universität Würzburg
Am Hubland, D-97074 Würzburg, Germany

http://theorie.physik.uni-wuerzburg.de/~biehl
Mathematics and Computing Science
Intelligent Systems
Rijksuniversiteit Groningen, Postbus 800,
NL-9718 DD Groningen, The Netherlands

biehl@cs.rug.nl
Michael Biehl Michael Biehl
Outline
• Motivation
Non-equilibrium growth - Molecular Beam Epitaxy (MBE)
• Theory / modeling / simulation
several levels of theoretical description
• Summary
• Lattice gas and Solid-On-Solid (SOS) models
• Kinetic Monte Carlo simulations
deposition and transient kinetics
thermally activated processes, Arrhenius dynamics
problems and limitations
• Example applications
I) unstable growth, mound formation and coarsening dynamics
II) Atomic Layer Epitaxy (ALE) growth of II-VI(001) systems
Molecular Beam Epitaxy ( MBE )
control parameters:
substrate/adsorbate materials
deposition rate
substrate temperature T
ultra high vacuum
directed deposition of adsorbate
material onto a substrate crystal
production of, for instance, high quality
· layered semiconductor devices
· magnetic thin films
· nano-structures: quantum dots, wires
theoretical challenge
· clear-cut non-equilibrium situation
· interplay: microscopic processes ÷ macroscopic properties
· self-organized phenomena, e.g. dot formation
Mikrostrukturlabor, Würzburg


oven
UHV
T
Theory / modelling of (growing) surfaces
Quantum Mechanics
faithful material specific description
including electronic properties
often: configuration of a few atoms/molecules,
unit cells of periodic structures,
zero temperature treatment
important tool: Density Functional Theory (DFT)
description in terms of electron densities
typical problem:
energy/stability of surface reconstructions,
preferred arrangement of surface atoms
CdTe (001) surface reconstructions
Molecular Dynamics
numerical integration of equations of motion + thermal fluctuations
effective interactions, e.g. classical short range pair potentials
(QM treatment: e.g. Car Parinello method )
© microscopic dynamics of particles
 limited system size and real time ( <<10
-6
s )
example: diffusion on a surface
atomic vibrations ( ~10
-12
s )
with occasional hops to the next local minimum
typical problem:
dissociation of deposited
dimers at the surface,
transient mobility of arriving atoms
Kinetic Monte Carlo (KMC) simulations
stochastic dynamics, consider only significant changes of the configuration
simplifying lattice gas models:
pre-defined lattice of
empty / occupied sites
hops from site to site
Solid-On-Solid (SOS) models:
exclude bulk vacancies, overhangs,
defects, stacking faults, etc.

d+1 dim. crystal represented by
integer array above d-dim. substrate lattice
Deposition of particles, e.g. with flux F = 1 atom / site / s
(incoming momentum, attraction to the surface...)
incorporation processes, examples:
Transient effects upon deposition
knockout-processes
at terrace edges
downhill
funnelling
steering
weakly bound, highly mobile
intermediate states
regular lattice site
p
o
t
e
n
t
i
a
l

e
n
e
r
g
y

distance from the surface
vac.
Arrhenius law: waiting time
T
B
k
Δ
o
e τ τ
+
=
rate
T
B
k
Δ
o
e R
÷
=u
attempt frequency , e.g.
o
u
energy barrier A , e.g. for hopping diffusion
thermally activated processes, simplifying representation:
A
1 12
o
10 ~
÷
s u
after incorporation: mobile adatoms at surface sites
R (a÷b) = u
0
exp[ A / (k
B
T) ]
R (b÷a) = u
0
exp[ ( E
a
-E
b
+ A ) / (k
B
T) ]
a
b
E
b
E
a
A
more general:
transition states and energy barriers A affect „only“
the non-equilibrium dynamics of the system
E
t
t
R (a÷b) exp[ - E
a
/ (k
B
T) ] = R (b÷a) exp[ - E
b
/ (k
B
T) ]

detailed balance condition ÷ stationary P(s) · exp[- E
s
/ (k
B
T) ]
for states of type a,b,...

in absence of deposition and desorption:
system approaches thermal equilibrium
an example: Ehrlich-Schwoebel instability
AE
S
AE
+
AE
|
diffusion bias: adatoms attach to
upper terraces preferentially
uphill current favors mound formation
additional Schwoebel barrier
hinders inter-layer diffusion
non-equilibrium, kinetic effect:
additional barrier AE
S
is irrelevant for
equilibrium properties of the system
÷ implicitly used simplifications and assumptions
deep (local) minima, infrequent events
exclude, e.g., double or multiple jumps:
transition state theory:
correct treatment takes into account entropies / free energies
constant prefactor (attempt frequency)
- temperature independent
- state independent
disregard actual shape of the
energy landscape
a
b
t
u
o
(a÷b) = u
o
(b÷a)
?
consistent with discretized state space
and concept of detailed balance
frozen crystal :
e.g. single, mobile particle in a static environment, neglect
concerted rearrangements of the entire crystal / neighborhood
desorption
islands
diffusion
nucleation
deposition
downward diffusion
edge diffusion
some microscopic processes on the growing surface
+more: incorporation, knockout
attachment to edges / islands
detachment processes, ...
Kinetic Monte Carlo Simulation (rejection free)
· perform the selected event
(evaluate physical real time step)
· initial configuration of the (SOS) system
· catalogue of all relevant processes i=1,2,...n
and corresponding Arrhenius rates
R
1
R
2
R
3
R
n
... rates ...
· pick one of the possible events randomly
with probability p
i
· R
i

0
1
r
a
n
d
o
m

n
u
m
b
e
r


· update the catalogue of possible processes
and associated energy barriers and rates
R
3
exchange processes / concerted moves
e.g. exchange vs. hopping diffusion
dimer and island mobility
material specific input ?
direct / indirect experimental measurement
calculations/estimates: first principles
semi-empirical potentials
quantitative match of simulations and experiments
complete catalogue of events ?
potentially relevant processes:
Problems and limitations
lattice gas / SOS description:
defects, dislocations ?
hetero-epitaxial growth ?
strain and other mismatch effects ?
material specific simulations
realistic lattices or off-lattice simulations
interaction potentials, realistic energy barriers
particularities of materials / material classes
Applications:

abstract models, further simplifications
basic questions
example: (universal?) dynamical scaling behavior
I) Unstable growth: slope selection and coarsening
model features / simplifications
SOS lattice (e.g. simple cubic) neglect overhangs, defects
÷
knock-out process upon deposition momentum of incoming particles
÷
irreversible attachment
immobile islands
forbidden downward diffusion
high barriers (large enough flux)
÷
limited diffusion length for
terrace / step edge diffusion
effective representation of
nucleation events
single particle picture
÷
l
sed
:

characteristic length of step edge diffusion

• initial mound formation
due to Schwoebel effect
• coarsening process
merging of mounds driven by
- deposition noise
and/or - step edge diffusion
• saturation state
finite system size ÷ single mound
example: slow step edge diffusion (associated length l
sed
=1 lattice const. )
16 ML 256 ML
4096 ML
• selection of a stable slope:
compensating particle currents
upward (Schwoebel)
downward

(knockout)
dynamic scaling behavior time t · <h> (film thickness)
surface width
~mound height
w =
t
|
for t< t
x
w
sat
· L
o
for t> t
x
growth exponent
roughness exponent
saturation time t
x
· L
z
dynamic exponent z= o/ |
system
sizes
L =

80
100
125
140
256
512

w

/

L

scaling plot, data collapse

o=1 (slope selection)
z=4
|=1/4

relatively slow
coarsening

The role of step edge diffusion (sed)
for the morphology and coarsening dynamics
64ML
fast sed
(l
sed
~ L)
o ~ 1.00
| ~ 0.45
sed driven
coarsening
128ML
slow sed
(l
sed
~ 1)
o ~ 1.00
| ~ 0.25
noise assisted
coarsening
128ML
absent sed
o ~ 0.70 < 1
| ~ 0.20
absence of
slope selection,
rough surface
additional
corner barrier
hindered sed,
noise assisted
coarsening
128ML
significant step edge diffusion
characteristic exponents:
o = 1, | ~ 1/3, z ~ 3
for 1 << l
sed
<< L


|
l
sed
universality: observed in various types of lattices
simple cubic (001), body centered cubic (001)
simple hexagonal (001), hcp (001)

contradicts continuum model predictions:
| ~ 0.24

for cubic lattices
| ~ 1/3 for all other lattices
Siegert, 1998
Moldovan, Golubovic, 2000
Ahr, Kinne, Schinzer
anisotropic
binding structure:
] [ 0 1 1
] [110
x
y
example system: II-VI (001) semiconductor surfaces
· zincblende lattice, (001) orientation:
alternating layers (square lattices) of, e.g., Cd / Te
SOS representation, four sub-lattices
· surface reconstructions observed:
- c(2x2), (2x1) vacancy structures Cd-terminated
- (2x1) dimerization Te-terminated
II) Competing surface reconstructions in non-equilibrium
CdTe (001)
properties of Cd-terminated surfaces
maximum coverage 50 %
two competing vacancy structures: checkerboard or missing rows
simultaneous occupation
of NN sites in y-direction,
i.e. [1-10], is forbidden
(extremely unfavorable)
Te
Cd
x empty
electron counting rule, DFT
[Neureiter et al., 2000]
small difference in surface energies
favors checkerboard c(2x2)-order at low temperatures
e.g. DFT: AE~ 0.008 eV per site in CdTe [Gundel, private comm.]
0.03 eV ZnSe
Te at the surface
isotropic N.N. interaction
additional Te dimerization
motivation: coverage 3/2 observed under flux of excess Te
allows for Te deposition on a perfect c(2x2) Cd surface
beyond SOS
weakly bound, highly mobile Te-atoms ( Te* ) on the surface, e.g.
at a Cd-site (Te-trimers)
bound to a single Cd (neutralizes repulsion)
temporary position
time consuming explicit treatment / mean field like Te
*
reservoir
Kinetic Monte Carlo simulations
Arrhenius rates for elementary processes v = v
o
e
–A/ (kT)
v
o
= 10
12
/s
choice of parameters: qualitative features, plausibility arguments
semi-quantitative comparison,
prospective first principle results
Atomic Layer Epitaxy (ALE)
alternating pulses (1s)
of Cd and Te
flux: 5ML/s
dead time: 0.1s
Cd Te Cd Te
reconstructions ÷ self-limitation of the growth rate at high temperature
experiment [Faschinger, Sitter]
simulation [M. Ahr, T. Volkmann]
overcome at lower T due to presence of highly mobile, weakly bound Te* :
Summary
• Motivation
Non-equilibrium growth - Molecular Beam Epitaxy (MBE)
• Theory / modeling / simulation
several levels of theoretical description
following talks: continuum descriptions, multi-scale approach,...
• Lattice gas and Solid-On-Solid (SOS) models
• Kinetic Monte Carlo simulations
deposition and transient kinetics
thermally activated processes, Arrhenius dynamics
problems and limitations
• Example applications
I) unstable growth, mound formation and coarsening dynamics
II) Atomic Layer Epitaxy (ALE) growth of II-VI(001) systems
Outlook (Wednesday)

application of KMC method in off-lattice models
treatment of
- hetero-epitaxy, mismatched lattices
- formation of dislocations
- strain-induced island growth
- surface alloys of immiscible materials