Lattice gas models and Kinetic Monte Carlo

simulations of epitaxial crystal growth

Theoretische Physik und Astrophysik
& Sonderforschungsbereich 410
Julius-Maximilians-Universitt Wrzburg
Am Hubland, D-97074 Wrzburg, 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, Wrzburg


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

o
e
+
=
rate
T
B
k

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 (ab) = u
0
exp[ A / (k
B
T) ]
R (ba) = 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 (ab) exp[ - E
a
/ (k
B
T) ] = R (ba) 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
(ab) = u
o
(ba)
?
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