surface s c i e n c e

ELSEVIER Surface Science 375 (1997) 129-140

Diffusion on strained surfaces

M . S c h r o e d e r *, D . E . W o l f 1
Theoretische Physik, FB 10, Gerhard-Mercator-Universitat, 47048 Duisburg, Germany
Received 15 October 1996;accepted for publication 23 October 1996

Abstract

The change of diffusion kinetics when elastic fields are present is discussed for diffusion on (001) surfaces of simple cubic, fcc and
bcc lattices. All particles interact pairwise with a Lennard-Jones potential. The simple cubic lattice was stabilized by an anisotropic
prefactor. It is found that genericallycompressivestrain enhances diffusion whereas tensile strain increases the activation barrier. An
approximately linear dependence of the barrier in a wide range of misfits is found. In heteroepitaxy,diffusion on top of large clusters
is inhomogeneous and anisotropic. The kinetics close to edges and centers of islands are remarkably different. In many cases changes
of binding energies are small compared to those of saddle point energies. Thermodynamic arguments (minimization of free energy)
are not appropriate to describe diffusion on strained surfaces in these cases. © 1997 Elsevier Science B.V. All rights reserved.

Keywords: Models of non-equilibrium phenomena; Models of surface kinetics; Semi-empiricalmodels and model calculations; Surface
diffusion; Surface relaxation and reconstruction; Surface stress

I. Introduction can be reached locally at moderate flux, the whole

Growth of high-quality thin films and multilayer
systems has attracted increasing interest during
recent years. Experimentally it is a great challenge
to optimize the growth of both hetero- and homo-
epitaxial layers. The adjustment of growth parame-
ters like temperature, flux, substrate preparation,
growth interruption and heating is, however,
mainly guided by the enormous empirical back-
ground. In addition to the technical relevance for
semiconductor devices, epitaxial growth is also an
interesting field for theoretical research. The depos-
ition flux prevents the system from reaching its
equilibrium morphology. Although equilibrium
* Corresponding author. Fax: +49 203 379 2816;
.'-mail: schroed@comphys.uni-duisburg.de
1 Present address: HLRZ c/o Forschungszentrum J01ich,
D-52425 Jiilich, Germany.
system is generally far away from its minimal
free energy.
Classical rate equation treatments and computer
simulations have been used to understand growth
up to a few monolayers [ 1 - 7 ] . These treatments
took into account the basic microscopic processes
of MBE such as deposition, diffusion, island forma-
tion and growth, but have not considered strain.
Elasticity can influence the surface morphology in
three ways: by interactions between steps a m o n g
themselves or with adatoms [ 8 - 1 3 ] , by modifica-
tion of the sticking probability at edges of islands
[ 1 4 - 1 7 ] and by strain-dependent surface diffusion
constants 1-18-20]. A rich variety of microscopic
and mesoscopic approaches has been used to take
strain into account in the description of growth
and diffusion. H o w strain affects the kinetics of
pair-bonded systems was addressed with con-

)039-6028/97/$17.00 Copyright © 1997 Elsevier Science B.V. All rights reserved

PII S0039-6028 (96)01250-2
130 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140
tinuous space Monte-Carlo methods [21-23] and
molecular dynamics simulations [24-26], focus-
sing mainly on the resulting layer growth and the
occurrence of dislocations. Rate equations and
lattice Monte-Carlo simulations based on the
Frenkel-Kontorova model [14-16,27,28] were
performed to analyse modifications of the step-
flow growth mode, cluster statistics and three-
dimensional growth in mismatched systems as well
as in harmonic coupled lattices [ 29]. Furthermore,
molecular dynamics simulations were applied to
study diffusion on semiconductor surfaces, both in
homo- and heteroepitaxy [30-33]. Though three
particle potentials stabilizing the diamond struc-
ture were used, some trends observed on the
strained surface could be understood in terms of
pair potentials. Diffusion equations [ 12,13,34-38]
based on classical elasticity theory were mainly
used to address morphological instabilities. In
these treatments elastic interactions between steps
and adatoms, or chemical potentials modified by
the elastic energy density, lead to a diffusion bias.
Effective medium theory, e.g. Refs. [20,39], and
first principle calculations [40] were used to calcu-
late diffusion barriers on metallic singular surfaces
and close to steps, both in homo- and heteroepitax-
ial systems. Since both approaches include
quantum mechanical details which are computa-
tionally expensive, smaller systems were calculated
in which long-range elastic fields are cut off.
Since the surface morphology is determined by
kinetics as well as thermodynamics it is necessary
to calculate the activation barriers from the micro-
scopic diffusion trajectories, i.e. to determine the
binding (B) and saddle point (SP) energies. The
aim of this work is to analyse the influence of
strain on these energies. We focus on free diffusion
of adatoms on inhomogeneously strained surfaces.
Edge diffusion, advacancy diffusion, etc. will be
deferred to a forthcoming publication. We take
care that the crystal lattices considered for the
evaluation of energy barriers are large enough in
all three dimensions so that the results of classical
elasticity theory are reproduced.
In particular we are going to address the
following questions. Is the SP or the binding energy
more sensitive to strain? Only the latter one can
be treated within a chemical potential approach.
What is the energy landscape seen by an adatom
diffusing on top of a large strained island, i.e. how
are kinetics changed compared to the flat sub-
strate? How does the adatom mobility on top of a
three-dimensional island depend on its height?
The outline of this paper is the following.
Section 2 describes the method used to model
diffusion on discrete elastic solids. In Section 3
elastic properties, including classical interactions
of the modelled solids, are presented. In Sections
4 and 5 results for free diffusion on strained surfaces
and islands are given. The subject of Section 6 is
layer dependent activation energies. A conclusion
is given in Section 7.
2. Method
We consider three different crystal structures,
simple cubic (sc), fcc and bcc, in order to distinguish
general from lattice-specific strain effects. The
origin of the strain is unimportant for the phen-
omena. Hence we need not study an adlayer on a
substrate with a lattice mismatch, where the strain
is 6a/a, but can study a single-species model with
strain due to external forces.
We use a slab geometry with one free and one
frozen (001) surface perpendicular to the z direc-
tion, and periodic boundary conditions in the x
and y directions. There may be islands on the free
surface. The strain is imposed by changing the
system size in the x and y directions for a fixed
number of atoms in the x-y plane. With this
constraint all atoms, apart from those in the frozen
layer, are allowed to relax in order to minimize
the total energy, given by the sum of pair potentials
specified below. Relaxation is done by a conjugate
gradient algorithm and is stopped when both an
energy convergence criterion is fullfilled and the
largest force acting in the system is smaller than a
certain upper bound (10 -5 for fcc and bcc, 10 -3
for sc). The value of this bound was chosen to
guarantee that for a pair of atoms the equilibrium
distance is reached within an error of 0.001%.
Activation barriers for diffusion to a neighboring
binding site are now calculated using the conven-
tional minimal energy path saddle-point method
 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140 131

(see e.g. Refs.[33,41]). The relaxed substrate is perfectly justified; the crystal surface breaks rota-
frozen and an adatom is placed on a binding site. tional invariance anyway and the adatom feels the
While this test atom is moved to a neighboring directional bonds sticking out of the surface along
binding site in small steps, the substrate is either the lattice directions.
kept frozen all the time or it is allowed to relax Each atom interacts with its nearest and second-
due to the influence of the adatom, either only nearest neighbors. For barrier calculations the
locally or globally. The adatom is always relaxed third-nearest neighbor is also taken into account.
in the plane perpendicular to the diffusion path.
Of course, global relaxation is the correct pro-
cedure. However, we are going to show that local
relaxation or even a frozen substrate give surpris-
3. Classical elastic interactions
ingly accurate values for the energy barriers. In
the frozen case only the adatom energies need to
It is well known that linear continuum elasticity
be recorded, otherwise one has to measure the
predicts that two one-dimensional defects, such as
total energy of the whole system and small energy
rows of atoms or vacancies, have a repulsive inter-
differences become susceptible to large relative
action of the form E ~ 1Ix 2, where x is the distance
numerical errors.
between them [8-10]. For periodic boundary con-
All atoms interact pairwise with the same poten-
ditions, the interaction also has to take into
tial. For the fcc structure the conventional
account the periodic images of the defects. The
Lennard-Jones (LJ) potential, VLj(r)=4[(tT/r) 1 2 -
leading terms are E.,. A ( x - 2 + (L-X)--2), where L
(a/r)6], is used. The bcc and sc structures are more
is the lateral dimension of the system [42].
subtle as they are not stable for Lennard-Jones
The question arises of whether this interaction
interactions. The slab geometry of a bcc Lennard-
is reproduced by the discrete systems under con-
Jones crystal can be kept metastable by the peri-
sideration here. Fig. 1 shows the results for the fcc
odic boundary conditions in the x and y directions,
crystal, with two rows of vacancies, oriented along
so that an adatom can trace out the diffusion
the [100] directions, on the surface [43]. The
barrier on the flat free surface. However, islands
lateral system size L was a multiple of the lattice
on top of the surface were unstable with respect to
constant of the crystal at temperature T = 0 and
buckling. The reason why we use the Lennard-
pressure p = 0, which we take as the reference state
Jones potential for the bcc crystal, nevertheless, is
the conceptual advantage that the bcc structure
can be viewed as a deformed fcc lattice (as well
known from martensitic transitions). Rescaling the • i , i , r ' i '

x and y directions of the fcc crystal of lattice

constant 1 by a factor a v ~ and the z direction by -3.850
a produces a bcc crystal with lattice constant a.
In order to stabilize a simple cubic lattice, an
anisotropic LJ potential, ~ -3.86o
LU

V(r)=
I
0.1+8 x

y2 1 I
o^ i I , i , i ,

"3"87z.0 4.0 6.0 8.0 10.0 12.0

is used. This potential is not rotationally invariant
but for the purpose of simulating a single adatom
on a crystal surface with cubic symmetry this is
x
Fig. 1. Elastic interaction of two rows of vacancies on a (001)
surface of an fcc lattice of size L=25. The line is a fit with the
analytical form of the interaction obtained from continuum
elasticity theory, with the parameter A =0.199 (see text).
132 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140
for the strain. The expected elastic interaction is
nicely reproduced, indicating that already for mod-
erate sizes of the discrete system the continuum
description is applicable. We stress that these inter-
actions, calculated for an elastic halfspace, are only
observable if the thickness of the slab was larger
than its lateral dimension. Otherwise the frozen
first layer gives rise to an additional boundary
condition that cuts off the elastic interaction along
the surface at distances of the order of the slab
width.
The simple cubic system behaves completely
differently. First of all, on an unstrained slab, no
dependence of the energy on x could be observed.
Second, for a strained slab, the total energy did
depend on the distance between the vacancy rows
in a qualitatively similar way as in Fig. 1, although
the energy variations were smaller by about a
factor of 0.01. This result did not depend on the
slab width. In fact, it remained essentially
unchanged even if the two terraces, separated by
the missing rows, were sitting directly on top of
the frozen layer. This shows that the x-dependence
of the energy is not caused by an elastic interaction
mediated by the bulk. Instead, the edges of the
terraces relax. This relaxation must extend over
several lattice constants, so that the energy gain is
largest if neither of the two terraces is too small.
Obviously the relaxation of the terrace edges
does not lead to significant displacements in the
underlying slab and so no observable elastic inter-
actions are mediated. This is peculiar to the aniso-
tropic LJ potential [Eq. (1)]. Calculating the
elastic constants C44 and Cll related to shear
(exz S 0 ) and uniaxial strain (ex~ S 0 ) reveals that
C44 is 80 times smaller than Cll, i.e. the terraces
almost "float" on top of the underlying material
when relaxing laterally. Hence, a two-dimensional
Frenkel-Kontorova model should be a more
appropriate theoretical description than contin-
uum elasticity.
The evaluation of the elastic energies of a unit
cell as a function of the strain not only leads to
the values of the elastic constants but also allows
assessment of the limits of validity of linear elastic-
ity. A harmonic approximation of the energy is
only reasonable up to e~x ~ 0.03 due to the anhar-
monicity of the potential. For shear strain it is
valid up to ex~ ~0.3.
4. Diffusion on homogeneously strained surfaces
In this section the influence of strain on the
diffusion barrier of an adatom on a flat (001)
surface will be discussed. Fig. 2 shows the total
energy of a simple cubic system as function of the
x coordinate of an adatom, which is moved from
one binding site to the next one across the saddle
point along the [100] direction. Different values
of strain are imposed by varying a in the Lennard-
Jones potential. Thus the system's lateral size in
units of the equilibrium lattice constant varies
while the number of atoms in the x - y plane
remains fixed.
For tensile strain (upper curves in Fig. 2) the
barrier is increased. Compressive strain (lower
curves) decreases the barrier. This is mainly due to
a change of the saddle-point energy, whereas the
binding energies are shifted only very little. In
systems with pair potentials this is a general trend.
Suppose that only nearest-neighbor interactions
have to be taken into account and that the mini-
-0.8
c-
ILl -1.1
-1.2
o.o 1.0
Position
Fig. 2. Diffusion barrier of a homogeneously strained (001)
surface of a simple cubic lattice. Middle two curves: unstrained
system. Upper two curves: tensile strain Exx=Err=0.05. Lower
two curves: compressive strain Exx=Err= --0.05. Energies are
shown for global relaxation (filled symbols) as well as for a
frozen slab (open symbols). For local relaxation close to the
adatom only, the curves lie slightly above those for global
relaxation (within half the symbolsize).Energyis given in units
of the energy parameter of the LJ potential and the zero of the
energy scale is arbitrary in this plot.
 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140
mum of the pair potential is at a distance to. The
adatom will have this distance to all its nearest
neighbors at the binding site. Applying a compres-
sive strain the adatom will therefore move a little
away from the surface, while for tensile strain it
will get closer to it, always trying to keep the
preferred distance r0 to all its nearest neighbors.
Hence the binding energy will not change as long
as only nearest-neighbor interactions are taken
into account and the strain is sufficiently weak.
Thus the diffusion barrier is mainly determined by
the strain dependence of the saddle-point energy,
where the interaction with next-nearest neighbors
is stronger than at the binding site. This is in
contrast to recent effective medium calculations
for A g ( l l l ) [20], which indicate that in that case
many body contributions to the energy are strong.
In addition, the decrease of the barrier for com-
pressive, and its increase for tensile, strain is a
general principle (cf. Ref. [20]). It can be under-
stood easily by considering the limits of large
strains. For large compressive strain the substrate
can be viewed as a continuous film. There are no
more discrete binding sites in this limit and, hence,
diffusion barriers vanish. In the other limit, for
large tensile strains, the substrate consists of iso-
lated atoms. Diffusion is equivalent to breaking a
pair of atoms and building a new pair. Hence the
diffusion barrier is equal to the pair-binding energy.
Fig. 3 shows that the diffusion barrier AE
depends approximately linearly on strain, as also
observed in Ref. [20]. This is also a general result.
//
i i i
~)~ 0.50
C-
(I)
t- 0.40
o values of the strain. However, this is not true for
.>
D 0.30
0 results from a comparison between the extra strain
<
0.20 ' ~ , ' , ' ,
-0.10 -0.05 0.00 0.05
Strain
Fig. 3. Activationbarrier versus strain for diffusionon a (001)
surface of a simple cubic crystal. A linear dependenceis given
between strain and activationbarrier for up to 8°,/ostrain.
133
This can be seen most easily by expanding
A E = [ ~ V((I+
"~'sP)=
~-, --'ad~(SP)',
+ 1/2 ~ V((l+O(r,(SP) - r ~(SP))) 1
t,J
- [(SP)~(B)] (2)
to first order in the strain tensor =e [10]. The
summation indices label the atoms in the slab, and
rad is the position of the adatom. All atomic
positions in the fully relaxed system depend on
whether the adatom is at the saddle point or at
the binding site. If one ignores the extra strain due
to the presence of the adatom, as will be justified
below, r!sP)=r! B), SO that the second term in Eq.
(2) cancels with the corresponding one in the
second half of the formula. Then the expansion is
simply
(SP)- m.~
(B))e.~ ,
AE = const. + (muv (3)
where
muv = ~ O~V(ri-- r,d)(ri)~ (4)
i
denotes the force dipole tensor of the adatom, to
be taken at the saddle point or the binding site,
respectively. As we argued above, the binding
energy changes much less than the saddle point
energy, [m(m[<<[m(SP)[, so that the first order of the
expansion does not vanish. This explains why in
general the diffusion barrier depends linearly on
the strain.
The barriers obtained by global relaxation (filled
symbols in Fig. 2) [44] are only slightly smaller
than the ones for diffusion on a frozen surface
(open symbols). Energy changes due to adatom-
induced displacements can be ignored for moderate
strains below 0.01 or above 0.09. This estimate
induced by the adatom and the original strain ¢ of
0.10 the slab. The elastic contribution to the diffusion
barrier is correctly estimated from a calculation
with a frozen substrate as long as the extra strain
close to the adatom is much smaller than e. For
large values of ¢ the extra strain is large because
134 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140

the elastic constants of the crystal become very All energies and barriers are plotted versus a
small. If one is interested in differences of diffusion since the value of the strain depends on the choice
barriers for different strains, instead of the value of the reference state (bcc or fcc), c = l - a / a r o f ,
of a barrier itself, Fig. 2 shows that a calculation where O'ref is the value for the reference state. In
with a frozen substrate is almost as good as the any case the distance between atoms in units of
correct fully relaxed one because the error one the equilibrium lattice constant decreases for
makes is almost the same for the different strains. increasing a, as explained above. Therefore, the
This justifies the approximation made in Eq. (2). activation barrier for diffusion decreases mono-
On bcc or fcc (001) surfaces the trend is the toneously with a, as expected according to the
same in a wide range of strain (Fig. 4). By varying general arguments above. As for the simple cubic
tr in the Lennard-Jones potential the solid can lattice, a linear dependence between strain e and
be shifted from a bcc crystal (trb~=0.793) to barrier is given in a good approximation around
an fcc type (af~=0.899), although the former is O'bcc and O'fc e.
unstable without periodic boundary conditions For the fcc crystal the binding energy of an
(ground state energy per particle Eb~c= adatom depends only weakly on strain, in
-- 12.708 > -- 13.442 = Erc¢). agreement with the general argument above.
However, the bcc crystal obviously violates this
rule (Fig. 4b)" Here the strain dependence of the
2.5 ' i , i , i ,
diffusion barrier is mainly due to the binding
energy. This exception from the rule can easily be
2.0 ~
== understood. In the bcc crystal the atom sitting in
o
the second layer directly under the adatom is so
._~ 1.5
close that its contribution to the binding energy is
1.0 about three times larger (E~b~=0.187) than for the
fcc crystal (Eft=0.062). For larger tensile strain
0.5 i I I this atom gets closer and closer to the adatom and
(a) at a=0.725 would be as close as the nearest
-2.00 r i i neighbors. The simple argument above fails
because a next-nearest neighbor gives a non-
negligible contribution.
--3.00 (
We increased the number of neighbors taken
into account when the energy of the adatom is
•
f-
--4.00 [] [] binding energy calculated. For the values of a considered there is
LU no qualitative difference to the data shown.
Quantitative changes are about A E / E ~ 8 % for
--5.00 both the saddle-point and the binding energies.

O i i i
-6"00.72 0.82 0.92 1.02 5. Diffusion on inhomogeneously strained surfaces
(7
(b)
In this section we investigate the adatom diffu-
Fig. 4. (a) Activation energy for diffusion on homogeneously sion on an island of atomic height on top of the
strained bcc/fcc (001) surfaces. The trend of increasing/ strained slab considered so far. As the island edges
decreasing barrier for tensile/compressivestrain is similar to relax, the strain along the surface is no longer
the simple cubic system. (b) For the bcc crystal the main shift constant but inhomogeneous. We show that bind-
is due to changes of binding energies that are affected by
changes of crystal plane distances according to the Poisson ing and saddle-point energies then also depend on
ratio. Mainly saddle-point energies are changed in the fcc position. Diffusion close to the edge is different
system. from that near the center of the island. This can
 M. Schroeder, D.E. Wolf~Surface Science375 (1997) 129-140
be understood qualitatively by applying our previ-
ous results for homogeneously strained layers
locally, which is not so surprising as the main
energy contributions, proportional to the strain of
the slab, had a local origin, whereas the long-range
terms were much weaker (order 10 - 6 , cf. Fig. 2).
Whereas the changes of binding and saddle-
point energies can be predicted by our previous
results, as will be shown below, their inhomo-
geneity has new kinetic implications, which will be
discussed now. In general, binding as well as
saddle-point energies will depend on position but
have completely different physical consequences.
In order to illustrate this, we compare the two
limiting cases illustrated in Fig. 5. Either only the
saddle-point or only the binding energy depends
on position, in such a way that the respective
activation barriers are locally the same.
In the first case (Fig. 5a) diffusion currents on
the surface are given by Fick's law, whereas in the
second (Fig. 5b) there is an additional drift towards
lower binding energies. This can be easily derived
by evaluating the current Jm from site m to the
adjacent site n,
jmn=a(pmWm~n--pnWn~m),
where a2pmis the probability of finding an adatom
at sitem and Wm_.n=Vexp~--pt mn -- E~))
"°'E(SP)
denotes the transition rate from site m to n.
Assuming that the attempt frequency v does not
depend on position, and expanding Jm to first
Position
Fig. 5. The limiting scenarios of diffusion barrier changes. (a)
Only the saddle-point energies change. (b) Only the binding
energies change.
135
order in the difference of adatom density and
binding energy, one obtains
u(B) ~(B.)
Pm - - Pn Pm -[- Pn ~ m - - L~(n)
jmn ~'~JDmn - - "~ ~ n n - - , (6)
a 2 a
where Dmn=a2x/Wm~nWn_.mand #m=flD~ are
the local adatom diffusion constant and mobility,
respectively. The first term in Eq. (6) is Fick's law,
the second the drift term. Hence the two cases
shown in Fig. 5, although having the same activa-
tion barriers for diffusion, imply quite different
kinetics. Inhomogeneous activation barriers, for
example, lead to inhomogeneous nucleation of
islands and inhomogeneous binding energies
induce a drift. Only the strain dependence of the
energy at the binding sites has been dealt with in
most of the previous publications (see e.g. Refs.
[12,13,17,34-38]). It should be stressed, however,
that a strain dependence of the activation barriers
also has morphological consequences.
Fig. 6 shows the energy landscape for diffusion
on an island in the simple cubic system both for
7% tensile and 6% compressive strain. AE changes
by 28% (21%) for compressive (tensile) strain from
the center to the edge. The shape of the landscape
(5)
can be understood by referring to Fig. 3. In both
cases the island edge is able to relax. The lattice
constant at edges is closer to the one of the
unstrained system. Close to the center the surface
is still highly strained. The lattice constant there is
close to the one imposed by the substrate. As a
consequence of this inhomogeneous relaxation,
diffusion is faster in the middle of the island for
compressive strain (negative misfit) compared to
the island edge. This leads to a reduction of the
nucleation rate of islands at the center and because
of the increased diffusion length adatoms try more
often to escape from the terrace. This slows down
their accumulation and hence the nucleation of
new islands. Tensile strain (positive misfit), how-
ever, slows diffusion down in the middle of the
island. Therefore adatoms can escape from the
terrace less easily and the nucleation probability
of an island on top of the island is enhanced. For
the cubic lattice essentially only the SP energies
vary across the island. Hence, no significant drift
current arises, which could spoil the simple argu-
ment by transporting adatoms towards the island
136 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140

i i i

-0.80

t-
-1.00
LU

- 1.20

-1.40 I i I
200.0 205.0 210.0 215.0 220.0
Position

Fig. 6. Diffusion on top of a simple cubic island for tensile (solid line) and compressive strain (dashed line). Diffusion is faster in the
center (close to the edge) of the island for compressive (tensile) strain.

edge or center and thereby also decreasing or
increasing the nucleation rate.
The fcc system shows a similar behavior though
the effect is less pronounced than for the sc system,
since AE changes from the center to the edge only
by about 13% (Fig. 7). The reason is the stronger
coupling to the underlying crystal layers, which
hinders the relaxation of the island edges.
Although both systems are completely different
with respect to coordination numbers and elastic
properties, there is a remarkable agreement in the
trends observed for free diffusion on their strained
surfaces. In the fcc system again predominantly
the SP energies are shifted by strain.
On the bcc (001) surface an island is unstable
against a vertical corrugation, indicating that the
bcc structure is unstable for Lennard-Jones sys-
compared with the above data, since the vertical
corrugation affects all energetic shifts. However,
depending on the sign of strain, barriers are shifted
in agreement with the fcc and sc systems to higher
or lower values.
We stress that the energy landscapes of Figs. 6,
7 and 8 are due to the inhomogeneous strain. They
are hardly affected (comparable to the line width)
when elastic step-adatom interactions are switched
off. This was checked by calculating the barriers
on a frozen island, similar to Section 4. Classical
elastic interactions can be neglected for strong
enough lattice mismatch.
6. Layer-dependent diffusion barriers

jJl/i/!/iji
tems. Nevertheless, barrier calculations were per- If an island on top of a strained slab is several
formed (Fig. 8). The results cannot easily be atomic layers high, the relaxation at its edges is

--2.6

==
tu --3.6

--4.6 i

255.0 260.0 265.0 270.0 275.0

Position

Fig. 7. Diffusion on strained fcc (001) islands. Dashed top curve: compressive strain. Lower curve, energies shifted by - 1: tensile strain.
 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140
-,
-3.00
-4.00
(1)
(-
klJ
-5.00
-6"0013.5
Fig. 8. Diffusionon a strained bcc (001) island, ___3% strain. The vertical corrugation, indicating that the bcc structure is unstable
for LJ interactions, causes a modulated energy landscape. For tensile strain barriers increase (dashed line).
height dependent. In continuum elasticity this can
be modelled by the strain field in the island for a
strain boundary condition on one side (correspond-
ing to the uppermost complete layer of the slab)
and free boundary conditions (stress equal to zero)
on all other sides. Above a certain height, propor-
tional to the lateral size of the island, the height
dependence of the displacement fields becomes
negligible; the strain tensor approaches a constant.
Correspondingly, the diffusion barriers depend on
the height of the island.
This should not be confused with recent experi-
ments [18] and first principle calculations [19]
which showed that activation energies depend on
the thickness of a heteroepitaxial film. In contrast
to our island, the film was not limited by edges
[19] or the film thickness was much smaller than
the lateral extent [18].
For both simple cubic and fcc systems com-
pressed islands of varying thickness were set up on
a frozen substrate to analyse height-dependent
barriers in our model. They had the shape of a
square cylinder. Fig. 9 shows that lateral displace-
ments, measured at the edges, in a certain layer
depend on the lateral size L of the islands.
All curves can be fitted with an exponential
~ exp(-z/~), where the characteristic length ~ is
proportional to the lateral island size (Fig. 9c), as
expected. This is analogous to the well-known
result of continuum elasticity theory, where
the displacement field of an infinite half-space,
subject to a periodic force distribution with wave
length L on its surface, decays with an
exponential exp(--z/L) into the bulk. Because of
the approximately linear relation between the
137
I i , ..
i i i
523.5 533.5 543.5
Position
diffusion barriers and the strain, the activation
barrier, measured, for example, at the center of the
island, approaches its value for the stress-free
surface exponentially with increasing height of the
island, with the same characteristic length
(Fig. 10).
7. Conclusion
We analysed the effects of strain on surface
diffusion barriers for (001) surfaces of three
different crystal structures: simple cubic, bcc and
fcc. In all cases diffusion is slowed down for tensile
and enhanced for compressive strain. We claim
that in purely pair-bonded systems this is always
the case, irrespective of coordination numbers, i.e.
of surface geometry. This is in agreement with
more refined calculations and experiments [ 18-20]
for special systems. For strains up to + 5 % the
relation between activation barrier and strain is
linear to a very good approximation.
The similarity of the results for all three crystal
structures might seem surprising in view of their
very different elastic bulk properties, as discussed
in Section 3 and reflected in the different mediation
of elastic interactions between surface defects. The
reason is that activation barriers for surface diffu-
sion are mostly influenced by the lattice distortion
in the neighborhood of the adatom, whereas elastic
interactions mediated by the bulk are only small
corrections. Also, for moderate physical values of
strain it is found that displacements imposed on
the bulk by the adatom force distribution can be
138 M. Schroeder, D.E. Wolf/Surface Science 375 (1997) 129-140

i , i

0.0

c
-0.2
E
o
^^AAAA^A^AAAAA

"1o
-- 0.4 ~ .××x×xxx

t~
_.1
, ',',',-i-I-
--0.6

--0.8
0.0 10.0 20.0 30.0 40.0
Height
(a)
i

-0.20

e-
Q
E
--0.40

"o

0 i I

--0.60 13 23 33
L

i
-,0.80
0.0 10.0 20.0
Height
(b) (c)

Fig. 9. Lateral displacements at the island edge of an fcc (001) island as a function of island height. Different symbols correspond to
different lateral sizes L of the island, as specified in (c). All curves were fitted with an exponential ~ exp(-z/~). (a) Same as as (b)
for simple cubic island. (c) The characteristic length ~ is proportional to L. Upper line: fcc. Lower line: simple cubic.

neglected as far as activation barriers are
concerned.
In the fcc system, and even more so for the sc
crystal, it is mainly the shift of the saddle-point
energy which is responsible for the strain depen-
dence of the activation barrier. We argued that
nearest-neighbor pair potentials do not contribute
to the strain dependence of the binding energy.
Therefore, if the next-nearest-neighbor interaction
has a sufficiently weak strain dependence, the
binding energy will be essentially constant.
However, on the bcc (001) surface this is not the
case, as a next-nearest neighbor gives an important
strain-dependent contribution to the binding
energy.
Diffusion barriers on top of islands, which could
be several layers high, were analysed. Because of
the height-dependent strain relaxation the barriers
approach the value of the unstrained surface expo-
nentially for increasing island height. This is in
agreement with continuum elasticity theory.
Generically, diffusion on top of islands is aniso-
tropic and inhomogeneous. Since island edges are
able to relax more effectively, the activation barrier
 M. Schroeder, D.E. Wolf/Surface Science 375 (1997) 129-140
1.20
o
t-
O
< 1.15
J .-
, ,
1. 1 0
-0.0 10.0 20.0
Layer index
(a)
Fig. 10. Layer-dependent barriers for diffusion on (a) fcc and (b) simple cubic (001) islands. The barriers were calculated at the
island centers.
changes across the island, which is clearly seen for
the stable fcc and simple cubic lattices. For tensile
strain, diffusion is enhanced near the edges com-
pared to the center of the island; for compressive
strain it is slowed down. This has to be distin-
guished from inhomogeneities of the energies at
binding sites, which vary only very little in our
systems. Such a variation is responsible for a drift
of adatoms towards stronger binding sites. We
conclude that in the fcc and sc lattices we studied
the dominant kinetic effect of strain is due to the
modification of the saddle-point energies. This
feature cannot be captured by a strain-dependent
chemical potential; instead, it corresponds to a
strain-dependent surface diffusion constant.
According to Lau and Kohn I-9] the chemical
potential of an adatom, i.e. its binding energy, is
roughly changed by an amount of 0.1 eV by elastic
interactions with another adatom two lattice con-
stants apart (metallic surface). In all of our systems
we saw mainly saddle-point changes that were at
least of that order of magnitude for reasonable
strains of e ~ ___0.05. However, the changes were
not due to adatom-induced displacements, i.e. elas-
tic interactions. Whereas shifts of saddle-point
energies are certainly pronounced in purely pair-
bonded systems it was demonstrated that (i) both
139
0.38
~J
i/
0.36
0¢,,.
0
g 0.34
0.32
0.30 i i i
, 0.0 10.0 20.0 30.0 40.0
30.0 40.0 Layer index
(b)
SP and B energies might be affected by strain and
(ii) the induced shifts can be as large as those
induced by classical elastic interactions.
The inhomogeneous kinetics on an island can
be traced back to position-dependent strain relax-
ation. One gets the correct qualitative picture by
applying the energy-strain relations obtained for
the diffusion on uniformly strained surfaces locally.
This also works in more complicated geometries.
We have checked that one gets the correct physical
answer, e.g. for detachment barriers, from steps. It
is generally believed that detachment barriers are
always reduced for strained layers. The argument
is based on the correct idea that the binding energy
of an adatom at the island edge is reduced because
attachment increases the island size and thereby
the strain energy per atom stored in the island.
However, we find that the strain dependence of
the saddle points may overcompensate this effect
so that the detachment barrier may increase or
decrease depending on the sign of the strain 1-45].
Although in this paper we have emphasized
some elementary properties, which can be argued
to be typical for diffusion on many strained sur-
faces, we stress that, in general, aspects of strain
have to be analysed in a case-by-case manner,
especially when more complicated situations like
140 M. Schroeder, D.E. Wolf~ Surface Science 375 (1997) 129-140
detachment, attachment and diffusion along or
across edges are concerned.
Acknowledgements
We thank Pavel Smilauer, Jacques Villain and
Andy Zangwill for illuminating discussions. This
work was supported by Deutsche Forschungs-
gemeinschaft through SFB 166.
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[42] One-dimensional defects are modelled by rows of vacen-
cies, i.e. as two stripes of different width. Hence, an
island-island edge interaction +In(r), depending on the
sign of the steps, is not observable; repulsive and
attractive contributions add up to zero.
[43] Following elasticity theory for the isotropic solid the
prefactor A is given by A ~ [(1--~2)/nY]Lm2, where ~ is
the Poisson ratio and Y is Young's modulus. We
estimated m ~ l [9,12] and calculated 4=0.42 and Y=
71, which gives A~0.1.
[44] Global relaxation requires us to ignore the force acting
in parallel to the diffusion direction, otherwise the whole
crystal would move, i.e. the adatom would be relaxed
into a binding site again. We used a frozen bottom layer
to prevent the whole system from moving.
[45] M. Schroeder and D.E. Wolf, in preparation.