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ElSEVIER Surface Science 306 (1994) 427-433

Diffusion on stepped surfaces

II. Step attraction and adsorbate-adsorbatc repulsion
C. Uebing *
Institut fir Festk%perforschung, Forschungszentrum Jiilich, GrnbH, 52425 Jiilich, Germany

R. Gomer
Department of Chemtitry and James Franck Institute, The University of Chicago, Chicago, IL 60637 USA

(Received 2 August 1993; accepted for publication 15 November 1993)

Abstract

Diffusion of adparticles on stepped surfaces has been investigated via Monte Carlo simulations, with step sites
assumed to exert extra binding energy, Jste,. In addition repulsive nearest-neighbor interactions were added, either
JNN = -Jstep, or J,, = - i J,,,,. These interactions were also assumed to be present between nearest-neighbor step
sites and step and nearest-neighbor terrace sites. For both cases J,, largely nullifies trapping by steps and greatly
reduces diffusion anisotropy at all coverages and temperatures. However fairly subtle effects balancing NN repulsion
and step attraction remain and affect the temperature and coverage behavior of diffusion.

1. Introduction diffusion anisotropy, except at low temperature

In paper I El] we presented results of Monte
Carlo simulations for the diffusion of adparticles
on square lattices with evenly spaced steps. In
most of the simulations step sites were assumed
to exert extra binding energy, so that diffusion
from a step site required added activation energy.
A few simulations were also carried out for repul-
sive steps, i.e. those requiring extra energy to be
crossed. In both cases absence of ad-ad interac-
tions was assumed. The results for attractive steps
indicated that at low coverage steps intercepted
atoms in such a way as to lead to very little
where steps were nearly saturated, thereby con-
stituting a barrier for diffusion across them but
not parallel to them. At high coverage this
anisotropy became pronounced at higher temper-
atures. In the present paper we consider the
effect of nearest-neighbor adsorbate-adsorbate
repulsion, assumed to be effective also within
step rows. The results show some initially unex-
pected features, which however can be readily
understood.
2. Method

The procedures used were identical to those

* Corresponding author. described briefly in Ref. Ill and in more detail in

0039-6028/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved

SSDI 0039-6028(93)E0998-A
428 C. Uebing, R. Gomer /Surface Science 306 (1994) 427-433

a previous paper [2]. As in paper I 64 x 64 square

lattices with periodic boundary conditions and
steps every fourth row were used. Step coverages
were determined both in the canonical and grand
canonical ensembles. In the latter case a large
number of runs giving overall 8 as functions of p
and T were found from which values of ester at
fixed 0 could be obtained as function of reduced
temperature.
Simulations were carried out for two cases, (I)
J NN = -Jstep and (II) J,, = - +J,,,,. Here J,,
stands for nearest-neighbor repulsion and Jst,
for step attraction, the positive sign signifying
attraction #l. Temperatures were expressed in Surface Coverage
terms of k,T/I J,, 1 in both cases, even though Fig. 1. Phase diagram for adsorption on a simple square
this changes the scale relative to Jstep. The reason lattice with nearest-neighbor repulsions; T, is the critical
for this convention is that for purely repulsive NN temperature (after Ref. [3]).
interactions the phase diagram, shown in Fig. 1
has a critical temperature given by [3]
scale is identical to that used in paper I, while in
k,T,/I J,, 1 = 0.567 (1) case (II) T is reduced by a factor of 2 relative to
and it seemed worthwhile to relate T to T, in a this.
simple way. Thus for case (I) the temperature

3. Step coverage
#’ The use of the symbol J for interactions is not universal
but has been used by us in previous work [2] and we retain it It will be useful to start with step and terrace
here. populations as function of I J,, I/k,T, shown in

1 B=0.8 1
0.9
0.8
0.7

IJNNI~~ IJNNII~BT
Fig. 2. Row coverage l9, versus 1JNNI/k,T for various Orotalindicated on the figures. (a) J,, = -Jstep. (b) J,, = - ; Jstep. (0)
denotes the step coverage, (0) represents the rows adjacent to steps, and A gives the coverage in the middle of terraces.
 C. Uebing, R. Gomer / Surface Science 306 (1994) 427-433 429

Figs. 2a and 2b. We recall also that in the ab-

sence of steps the phase diagram, shown in Fig. 1
consists of disordered lattice gas, a region of
c(2 x 2) (with vacancies) extending from 0.4 G 8
Q 0.6 below T, and “lattice fluid” for 8 > 0.6 at
all T. The line separating lattice gas or fluid from
the c(2 x 2) region corresponds to second-order
transitions. Fig. 2 shows that at low and high 8,
8step increases with decreasing T, reaching limit-
ing values at 1JNN I/k,T a 2. OS,,, is in all cases
higher than overall 8, but considerably less than
in the absence of NN repulsions [l], for the
obvious reason that adjacent filled step sites re-
duce step binding energy from J,_ to J,,,r 0 0.2 0.4 0.6 0.8 1
- 1J,, 1 per adatom. This effect is obviously big-
ger for case (I) so that OS,,, in this case is consid- Coverage t9
erably less than in case (II). Concomitantly the
Fig. 3. Mean square fluctuation ((Shr)2)/(N> versus total
population of terrace atoms decreases because of coverage for .I,, = - Jstep (upper panel) and J,, = - $ Jstep
conservation of adpopulation. However, because (lower panel): (0) (J,,j/kBT= 3.44 and (0) IJ,, I/k,T =
of NN repulsion this decrease is more pro- 1.60. The dotted line represents the high temperature limit
nounced for atoms in rows adjacent to steps. (Langmuir gas) ((SAV>/(N> = 1- 0.
For 8 = 0.5 the situation is more complicated.
As T decreases from high values ester, increases at steps. This can be seen also from equilibrium
first but as T approaches T, 8,,,, decreases, even- “snapshots” (not shown) and from plots of
tually approaching overall 8 again. The reason is ((Slv>*)/(ZV) versus t9, shown in Fig. 3. For
that the ~$2 x 2) structure dominates at low tem- both cases (I) and (II) there is a minimum at
peratures and thus imposes itself also on the 8 = 0.5, which becomes very sharp at low T. This

Fig. 4. Normalized tracer diffusion coefficients versus I J,, I/k,T for 0 indicated on the figures. (a) JNN = --Jo_. (b) J,, = - $
Jstep’ (0) D */Do;(+I 0:/D’; (X ) Of/D”. Do is the chemical diffusion coefficient for the non-interacting system without steps.
430 C. Uebing, R. Gomer / Surface Science 306 (1994) 427-433
behavior is typical of repulsive interactions, as
shown by Fig. 6 of Ref. [2]. The reason is that
((Shrj2)/(N> is proportional to the compress-
ibility of the adlayer [2], which becomes very
small in the c(2 x 2) region of the phase diagram,
because of the very high stability of this structure.
As already mentioned, this extends from 0 = 0.4
to 0.6, precisely where the dip in ((Shrl*)/(N)
begins and ends. Since the structure is most nearly
perfect at 0 = 0.5 this is also the coverage where
the minimum is seen. It is interesting that step
attraction in excess of NN repulsion attenuates
this minimum somewhat.
4. Tracer and jump diffusion coefficients
We present next results for these quantities,
D* and Dj respectively, defined in Refs. [1,2].
Figs. 4a and 4b show D*/D” versus 1J,, I/k,T
for cases (I) and (II) for 8 = 0.2, 0.5, and 0.8. Dj
(not shown) is virtually identical to D* and both
will be discussed together. Two general facts stand
out: there is very little diffusion anisotropy, and
except at 8 = 0.8 relatively little temperature de-
pendence. In order to understand these results
we note that the presence of NN repulsion serves
to make steps less of a trap for diffusing atoms,
first because two adjacent filled step sites reduce
the extra diffusion activation energy to - 1.I,, 1
for case (I) and to 0 in case (II); NN neighbors in
rows adjacent to steps have the same effect. Thus
steps act as traps mainly under conditions where
they are largely empty, and then reduce
anisotropy, just as in the case of J,, = 0 by
affecting equally the perpendicular and parallel
random walk components of atoms. At high step
coverage there will again be very little anisotropy
but for the opposite reason: steps now do not
constitute very much of a barrier. We should also
note that for repulsive NN interactions and J,,,,
= 0 negative activation energies and values of
D*/D’ > 1 were found in Ref. [2], because J,,
< 0 facilitates jumps relative to the non-inter-
acting case represented by Do.
We are now able to discuss the results in
detail. Starting with 8 = 0.2 we note that for case
(I) the effect of J,, dominates at all T so that
negative activation energies result. For case (II)
where repulsion is weaker J,, dominates only at
lower T. A small positive activation energy occurs
at high T where step population is quite small.
For high coverage, typified by the 8 = 0.8 results
steps are so highly populated as to constitute very
little energy barrier. Since the overall coverage is
already high they also do not affect diffusion
markedly via jump availability. For cases (I) and
(II) the numerical D*/D” values are virtually
identical to those for JsteP= 0, shown in Fig. 7 of
Ref. [2]. For case (I) there is virtually no
anisotropy; for case (II) diffusion across steps is
slightly more difficult than diffusion parallel to
them, for the obvious reason that the latter can
occur with no step crossing at all. For 8 = 0.5 the
situation is more complex. At high T the step
population is in both cases 8,,,, > 0.5 so that
steps are largely neutralized, both because of
vacant sites in them and because diffusion from
step sites is made easier by the fact that an atom
entering a step row can leave it easily because of
NN repulsion. Thus at high TJ,, dominates and
E * is negative, i.e. D*/D’ increases as T de-
creases. However below T, the c(2 X 2) structure
dominates. It was found previously [2] that even
for repulsive NN interactions only, a positive
activation energy, i.e. decreasing D*/D” with
decreasing T occurred below T, because diffu-
sion requires breaking of the very stable c(2 x 2)
structure. Since we have seen that the latter even
controls step population it is not surprising that it
dominates diffusion as well.
5. Activation energies of D*
Fig. 5 shows activation energies, E * relative to
the non-interacting case as function of coverage
for case (I) in units of J,,. Values are shown for
the high temperature regimes and also for
J,,/kBT = 2, i.e. below T,. The results for case
(II) (not shown) are very similar, indicating that
E * is dominated by J,, rather than by J_,. The
nearly linear relationship at high T is similar to
that found for NN repulsion only without steps at
high T [2]. The positive peaks at 0 = 0.5 corre-
spond, as already pointed out to the need of
 C. Uebing, R. Gorner / Surface Science 306 (1994) 427-433 431

4 0 0.2 0.4 0.6 0.8 1

Covemge 0
Fig. 5. Normalized activation energies for tracer diffusion
tE, = E * - I?‘)/[ J,, 1versus total coverage etotal for J,, =
- Jaw (0) En,,= EAI for IJNNI/kBT-+O; (+) EAI for
I~,,I/ka~=2;and(x) EA,, forJ,,,,/k$‘=S.
1 2

disrupting the c(2 x 2) structure. It shouId ako be lJN~llk~T

noted that E * shows very little anisotropy, for Fig. 7. timparison of D, /Do (thin symbols, dotted line) and
the reasons already mentioned. D,, /Do (thick symbols, solid line) Btotal= 0.2. (0) l&/D”,
D,/D’; t+) D,, /Do- DKGl/D’; (~1 D,,,,‘D”,
D~q /Do. JNN= - Jstetep.
6. Chemical diffiwion coefficient
El1 and labeled D,,, and DFI respectively as
Figs. 6a and 6b show the chemical diffusion function of 1J,, j/k,T for 8 = 0.2, 0.5, and 0.8.
coefficients obtained by the fluctuation method Comparison of these-results with D Ko, the diffu-

b 1000
100
10
1

10

0 1 2

1JNNtlrcBT iJNNjlkBT
Fig. 6. Normalized chemical diffusion coefficients obtained with the fluctuation method, D,, versus )JNN l/k&f for8 indicated
on
the figures. (a) JNN = -J_; (b) JNN = - 1 Jstep: (of D,/D’; (+> D, I/Do; (X) DpII/Do. D, obtained from a square probe,
D FL and D,,, from the slit probe.
432 C. Uebing, R. Gomer / Surface Science 306 (1994) 427-433

D ko is good in all cases for JNN/kGBT d 1.2 but

below these temperatures all components of D,
fall signifi~a~~y below D,. At B = OS (not
shown) there is good agreement between I), and
D xo for cases (I) and (II) over the entire temper-
ature range probed. At 0 = 0.8 (Fig. 8) there is
good agreement for case (I) for all components
over the entire range. This is also true for case
(II) except for DrL at J,,/k,T a 1.2 where
D r I is smaller than D, I . The reason for this
deviation may have to do with the breakdown of
the fluctuation method under conditions where
steps are trapping, for small probes as discussed
in Ref. 111.
One other point is worth noting. We have
E &(j already seen that the temperature dependences
a, 1 2
of D* and Dj are relatively small. Fig. 9 indi-
e lJNNI fkBy
cates that the temperature
((&V)*>/(N)
dependence
is considerably larger and corre-
of

Fig. 8. Comparison of &/Do (thin symbols, dotted line) and sponds to positive activation energy, consistent
DK,/DO (thick symbols, solid line) for 61total = 0.8. (0) also with the results of Fig. 3 of Ref. 121. The
D,/D’, D, /Do; (+) DFI /Do. D,, ,. /Do; (XI reason for this is that
DF,,& DKG,,/D'. JNN = - Jste,.
C(Shr)2)/(N) = k,T((%‘~)K (2)
where K is the compressibili~ of the adlayer.
sion coefficient obtained by combining r>ij and When repulsive NN interactions dominate K will
((~~)2)/(~), as discussed in Refs. [1,2f is shown increase with increasing T. Since
in Fig. 7 for case (I) and 0 = 0.2. Results for case
D = [tN)/(sN)2)]Dj (3)
(II) are very similar. Agreement between D, and

0 1 2 3 4

IJNNV~BT IJNNI PBT

Fig. 9. Mean square fluctuations ((SN)2>/( N > versus fJ,, Ik,T for different total coverages 8,,! as indicated: (a) JNN = -Jstep.
(b)J,N=-iJ * step.
 C. Web&, R. Gotner /Surface Science 306 (1994) 427-433
the temperature dependence of [((Slv>2)/
(N)]-’ dominates that D, accounting for nega-
tive activation energies of D (relative to Do> over
the whole temperature range studied.
7. Conclusion
The simulations presented here indicate that
NN repulsions affect diffusion on stepped sur-
faces drastically if such repulsions also exist within
step rows, since they then tend to decrease trap-
ping by steps. The compensation is of course
greatest for the somewhat artificial example of
equal step attraction and NN repulsion, but is
still quite appreciable when step attraction ex-
ceeds NN repulsion by a factor of 2. We have not
treated the case of NN repulsions on terraces but
no NN repulsion within step rows. For this latter
case one may also envision either repulsion be-
tween step and adjacent terrace adsorbed atoms,
or no such interaction. In the latter case the
effect of steps would be essentially that found in
Ref. [l], namely strong anisotropy at high cover-
age and at low T at all coverages. For the first
433
two sub-cases the situation would lie between
that reported here and encountered in Ref. [l].
We have also ignored the possibility of attrac-
tion by the bottom edges of steps (ledges) and
weaker binding at the terrace outer edges, as well
as the various possibilities of different activation
energies along these directions (i.e. parallel to
steps) as discussed in section 1 of Ref. [l]. We
hope to address some of these situations in future
simulations.
8. Acknowledgments
This work was supported in part by NSF Grant
CHE9222051. We have also benefited from the
Materials Research Laboratory of the NSF at the
University of Chicago.
9. References
111C. Uebing and R. Gomer, Surf. Sci. 306 (1994) 419.
(21 C. Uebing and R. Gamer, J. Chem. Phys. 95 (1991) 7626.
[3f K. Binder and D.P. Landau, Phys. Rev. B 21 (1980) 1941.