ARTICLE IN PRESS

Vacuum 76 (2004) 465–469

STM observation of Ag adatom interactions on the

Si(1 1 1)-(7
7) surface
Pavel Sobot!ık*, Ivan Os$t’a! dal, Pavel Koca! n
! 2,
Department of Electronics and Vacuum Physics, Faculty of Mathematics and Physics, Charles University of Prague, V Hole$sovickach
18000 Praha 8, Czech Republic

Received 24 July 2003; received in revised form 6 May 2004; accepted 6 May 2004

Abstract

STM imaging of Ag atoms adsorbed on the Si(1 1 1)-(7
7) surface is studied. Appearance of a single Ag adatom on
perfect surface is compared with images of adatoms interacting with surface defects and adsorbates. Importance of real-
time observation of surface processes for image interpretation is demonstrated on imaging Ag adatoms at various
situations. Influence of tunnelling conditions (voltage between a tip and surface) on imaging surface objects is studied
and visibility of single Ag adatoms and clusters is discussed.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Scanning tunneling microscopy; Surface diffusion; Adsorption; Silver; Silicon; Adatoms; Surface defects

1. Introduction Si(1 1 1)-(7
7) and data on Ag adsorption on

STM technique represents a powerful tool for
studying surface processes with atomic resolution.
Detailed experimental study of growth processes
and phenomena resulting from interaction be-
tween particular atoms at surfaces, cannot be
performed without UHV STM. Imaging in STM is
a complex problem and interpretation of data may
be rather difficult. We present here an approach
used for studying early stages of heteroepitaxial
growth of Ag on the reconstructed surface
*Corresponding author. Tel.: +420-2-2191-2336; fax: +420-
2-8468-5095.
E-mail address: sobotik@mbox.troja.mff.cuni.cz
(P. Sobot!ık).
0042-207X/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2004.05.008
the surface.
Heteroepitaxy of Ag on the Si(1 1 1)-(7
7)
surface represents one of the often studied
problems due to nonreactivity of Ag with the
reconstructed surface, abrupt interface and negli-
gible interdiffusion of both elements [1]. Recently
reported experimental works on self-organised
growth of arrays of ordered metal islands—
quantum dots—on the Si(1 1 1)-(7
7) surface
[2,3] stimulate need of detailed understanding of
mechanisms controlling the growth.
Initial stages of metal growth on Si(1 1 1)-(7
7)
are significantly influenced by the surface recon-
struction. Large (2.7 nm) triangular half-unit cells
(HUCs) of two different types (faulted—F HUCs—
containing a stacking fault, and unfaulted—U
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466 P. Sobot!ık et al. / Vacuum 76 (2004) 465–469
HUCs) separated by dimer rows and corner holes
[4] form a highly corrugated surface potential for
diffusing metal adatoms. At temperatures when
mixed surface reconstructions are not formed,
HUCs act as traps for deposited metal atoms
which nucleate inside HUCs [5,6] with stronger or
weaker preference for occupying F HUCs. Diffu-
sion processes of non-reactive metals on Si(1 1 1)-
(7
7) were studied in [7,8]. STM data showed
high mobility of Pb and Ag atoms inside HUCs
but low mobility between HUCs. The rate of
thermally activated hopping of single Pb atoms
between HUCs was estimated.
Several STM studies of the growth of Ag on
Si(1 1 1)-(7
7) succeeded in distinguishing the
appearance of single Ag atoms and dimers [9–11]
on the Si surface. We used dynamic observation of
Ag adatom hopping, for calculation of intercell
diffusion parameters. Real-time observations re-
veal some interesting interactions between ada-
toms and the surface and contributed substantially
to interpretation of imaged objects.
2. Experimental
Experiments were performed in a UHV chamber
equipped with the non-commercial STM measur-
ing head of our design. The pressure in the system
did not exceed 5
109 Pa during experiments.
Si(1 1 1) substrates (Sb doped, n-type, resistivity
0.01—0.005 O cm) were used. The (7
7) recon-
structed surface was obtained using a standard
flashing procedure. Ag was deposited from a
tungsten wire evaporator. Samples with very low
coverage used for real-time observations (0.002
ML, which corresponds to one Ag adatom per 8
HUCs, 1 ML=7.54
1014 atoms/cm2) were pre-
pared at room temperature at a rate of 0.0004 ML/
s, measured by a quartz crystal thickness monitor
[11]. The coverage of Ag/Si(1 1 1)-(O3
O3) re-
constructed islands on an annealed (650 K for
10 min.) sample with B0.6 ML of deposited Ag
was measured for calibration of the monitor.
Electrochemically etched tungsten tips were
cleaned by electron bombardment before every
experiment. Samples were resistively heated during
the observation by passing current. Sample tem-
perature was determined with an accuracy of
72 C from the calibrated heating power. Tunnel-
ling conditions during STM measurement were: tip
voltage 1.5 to 2 V, current 0.4 nA. STM images
were acquired with the period Dt ¼ 60 s.
3. Results and discussion
3.1. Adsorption of a single and two Ag atoms in a
HUC
STM imaging of a single Ag adatom in a F
HUC at room temperature (RT) is shown in Fig. 1
(object A1). The Ag adatom appears as a HUC
with highlighted corner adatom positions both in
empty (b) and filled state imaging (a) [9,11] (similar
behaviour has been reported for Pb, Y, Sn
[7,12,13] and can be expected also for other
nonreacting metals). Observed features agree well
with the theoretical predictions of Cho and
Kaxiras [14]. They found that surface potential
inside a HUC is quite shallow, and can be divided
into three areas (basins of attraction) located
around each restatom of the reconstruction. Metal
adatom can migrate easily within each basin and
jump among basins inside a HUC. It results in a
‘‘fuzzy’’ STM image due to relatively low scanning
speed in comparison with hopping rate of metal
adatom inside a HUC at RT.
An image of two Ag atoms adsorbed in a HUC
(object D on Fig. 1, see [9] for more details) shows
an interaction in the centre area of a HUC-dimer.
Fig. 1. Appearance of a single Ag atom (A1) and two Ag atoms
(D) in a HUC.
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P. Sobot!ık et al. / Vacuum 76 (2004) 465–469 467

3.2. Adsorption in non-perfect HUCS voltage of 1.8 V). It can be interpreted by (i)
missing the corner adatom (creates a very reactive
Interaction of an Ag adatom with a surface position); (ii) replacement of the corner adatom by
defect in a HUC is presented in Fig. 2. Sequence of other atom (less probable); (iii) reaction of the
images (taken at substrate temperature elevated to corner adatom with other adsorbed atom or
310 K) shows that an object X located in a HUC molecule (probably oxygen [15] or hydrogen
corner is an Ag adatom. After hopping out of the [16]). Fig. 3a (the defect is in U HUC) shows an
HUC, the atom reacts with another Ag atom in the attractive interaction—the Ag adatom is localised
adjacent HUC and forms an Ag dimer (object D in at the defect position. The interaction on Fig. 3b
the 4th frame in the sequence). The image reveals (the defect is in F HUC) has a repulsive
that the left HUC contains some kind of defect (in character—the Ag adatom hops within an intact
a position of the corner Si adatom of the surface part of the HUC. It cannot be concluded if the
reconstruction), which captured the Ag atom. The defects are of different types or the various
dimer decays and an Ag atom jumps back into the interactions indicate just difference between U
previous adsorption position after 2 min (5th and F HUCs.
frame). The defect position occupied by the Ag
adatom also influences imaging of the single Ag
adatom (and probably behaviour as well) in the
adjacent perfect HUC (object A2).
The 1st and 2nd frame of Fig. 2 show a situation
when an Ag adatom jumps into the defected HUC
already occupied by an Ag atom (object X changes
to Y). The two Ag atoms do not create dimer in a
usual form, it seems that one of the adatoms is still
captured at the defect position and the second
migrates within remaining HUC area (Y). The
HUC imaging is similar as in the case of
adsorption of a single Ag atom in a HUC (object
A1 in Fig. 1).
Different interactions of the Ag adatom, appar-
ently with the same kind of defect, are shown in Fig. 3. (a) Ag adatom in a perturbed HUC. The atom is
localized at a defect position. (b) Escape of Ag adatom from a
Fig. 3. In both cases the defect imaging is similar— perturbed HUC. Ag adatom is localized in non-perturbed part
not visible Si corner adatom in a HUC (missing of the HUC contrary to the situation in the case (a). Tip voltage
tunnelling current around this position at a tip was 1.5 V (a) and –1.8 V (b), tunnelling current 0.4 nA.

Fig. 2. Image sequence showing interactions of adsorbed Ag adatoms. The 3rd—5th frames of the sequence reveals that the object
marked as X is a single Ag atom captured in a HUC with the defect. The Ag adatom is captured in one corner of the HUC, but it can
hop out of the HUC and form a dimer (D) with Ag adatom in the adjacent HUC. 1st—3rd frames show the interaction of two adatoms
in the HUC with the defect. One Ag atom is captured in the corner with defect, the second Ag atom migrates within the remaining part
of the HUC. Resulting image (Y shown in the 2nd frame) is very similar to the imaging of the single adatom in nonperturbed HUC.
Tip voltage –1.8 V, tunnelling current 0.4 nA.
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An interaction of the Ag atom with other types
of surface object in a U HUC is shown in Fig. 4.
The object could be probably an extra Si atom or
cluster (see [17]) or an oxygen molecule [15]. Ag
adatom is localised immediately after jumping into
a HUC adjacent to the non-perfect one. We did
not observe release of the captured Ag adatom
from its position (substrate temperature 310 K).
This interaction seems to be much stronger in
comparison with previous cases.
3.3. Dependence of imaging on tunnelling voltage
Fig. 5 illustrates how different structures on the
surface can be imaged and resolved in STM. The
images of the same surface area of a sample with
Fig. 4. Localization of Ag adatom in a HUC with an extra Si
atom (or cluster) or oxygen molecule. Tip voltage –1.8 V,
tunneling current 0.4 nA.
Fig. 5. Bias-dependent imaging of Ag atoms and clusters. Ag atoms and clusters are almost invisible at particular tip biases. Tip
voltages are indicated in images, tunnelling current was 0.4 nA.
Ag clusters were taken at different values of tip
bias in the range from 2.2 to +2.8 V.
The images represent some kind of tunnelling
spectroscopy. We can observe that a single Ag
adatom (A1) is not visible at low negative voltages.
The occupied HUC seems to be empty. The
negative tip voltage (at imaging in empty states)
should be higher than 1 V for observation of
single Ag atoms. This behaviour of single ad-
sorbed atom is very similar to the previously
observed phenomena for Y atoms on the Si(1 1 1)-
(7
7) surface [12]. Also larger Ag clusters are not
almost visible at low negative voltages and
corresponding HUCs appear featureless. It corre-
sponds well with the STS results published in [5],
where authors reported a reduction of the density
of states upon adsorption of the Ag for energies
from 0.5 to 1 eV around Fermi level.
We can also observe objects which appear as
dark corner adatoms at particular voltages and
simultaneously as bright spots at different voltage
(marked by circle). It means that apparently
missing corner adatom of the reconstruction could
be in fact the image of an adsorbed atom or
molecule (for example oxygen, hydrogen or other
molecules contained in a background spectrum of
an UHV experimental system).
The image taken at +400 mV shows Ag clusters
surrounded by the darker areas in adjacent
HUCs. It could reflect a possible influence of the
larger Ag islands on the electron states in the
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P. Sobot!ık et al. / Vacuum 76 (2004) 465–469
neighbouring HUCs. We believe that surface
imaging at different voltages can resolve clusters
of different size and different materials on the
surface.
4. Conclusions
We presented basic interactions observed at
studying adsorption of Ag atoms on the Si(1 1 1)-
(7
7) surface by means of STM. Different
imaging of the Ag adatom in a HUC was shown
in dependence on an interaction with various
defects in the HUC.
We also studied STM imaging of Ag adsorbate
at different tip voltages. The best conditions to
image Ag on the surface are at negative tip voltage
higher than 2 V. We have demonstrated that
direct, real-time observation of the same area and
imaging it at different voltages can considerably
help to identify observed features especially in
comparison with single STM images. Imaging of
the hopping silver adatom can help to resolve
interaction of a single atom with the defects,
imaging at different voltages can resolve images of
different clusters, defects and adatoms on the
surface.
Acknowledgements
This work was supported by the Grant Agency
of Czech Republic—projects 202/01/0928 and 202/
03/0792, and by the Ministry of Education, Youth
469
and Sports of the Czech Republic—research
program MSM113200002.
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