Surface Science 606 (2012) 17491754

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Surface Science
journal homepage: www.elsevier.com/locate/susc

Adsorption behavior of iron phthalocyanine at the initial stage on Cu(100) surface

R.A. Rehman a, b, Weidong Dou a, c, Huiqin Qian a, Hongying Mao a, Frederik Floether d, Hanjie Zhang a,,
Haiyang Li a, Pimo He a, Shining Bao a
a
Physics Department, Zhejiang University, Hangzhou, 310027, China
b
Physics Department, Forman Christian College University, Lahore-54600, Pakistan
c
Department of Physics, Shaoxing University, Shaoxing, 312000, China
d
Homerton College, University of Cambridge, UK

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption behavior of iron phthalocyanine (FePc) on the Cu(100) surface at the initial stage has been
Received 24 March 2012 investigated by combining scanning tunneling microscopy (STM) and density functional theory (DFT) calcu-
Accepted 18 July 2012 lations. At low coverage, FePc molecules deposited on the sample surface at room temperature tend to adsorb
Available online 27 July 2012
dispersedly with their molecular planes parallel to the crystallographic directions of the substrate. Another
interesting STM observation
h ifor the sub-monolayer coverage is that the molecular axes of FePc are aligned
Keywords:
Iron phthalocyanine
along [037] (as well as 037 ) azimuth. At the monolayer coverage and elevated temperature, two types of
Copper ordered structures are observed. The FePc adsorption sites for the experimentally observed two distinct or-
Thin lm structures dered domains have been revealed through DFT calculations. With further increasing the coverage, molecular
STM clusters are formed particularly near the step edges.
DFT 2012 Elsevier B.V. All rights reserved.

1. Introduction
Because of the broad eld of applications, metal phthalocyanine
(MPc) molecules and their derivatives have increasingly attracted
the interest of researchers during recent decades. Phthalocyanines
are extensively used as pigments, dyes, and models of biologically im-
portant species such as porphyrins, hemoglobin, and chlorophyll.
They can serve as the active elements in chemical sensors; mainly
for re detection and pollution monitoring [1,2], and are of great in-
terests for use in thin lm transistors [3,4], organic electronic devices
[5], and solar cells [6].
However, the structure and properties of the adsorbate layer on
metal surfaces are largely determined by the competition between
inter-molecular interactions and moleculesurface interactions [79].
In order to obtain a better understanding of the adsorption geometry
and structure of MPc thin lms, a variety of experimental investigations
have been carried out by using multi-probing techniques such as scan-
ning tunneling microscopy (STM) [7,8], photoemission spectroscopy
(PES) [10,11] and low-energy electron diffraction (LEED) [12]. For ex-
ample, Lippel et al. studied CuPc molecules on Cu(100) [13] and H. J.
Gao et al. investigated the adsorption of FePc on Au(111) [14,15].
Their results demonstrate that the contrast in STM image depends on
Corresponding author.
E-mail address: zhj_fox@zjuem.zju.edu.cn (H. Zhang).
the central metal atom because the degree of d-orbital occupation
varies between atoms.
The rst reported STM images of FePc molecules deposited on
Au(111) were revealed by Hipps et al. [16,17]. In their report, each
FePc molecule is distinguished as a four-lobed cross structure with a
protrusion at the center, which is in agreement with the FePc's chem-
ical structure and which ultimately enhances tunneling through the
half-lled dz2 orbital of Fe 2+ ion. Another recent study demonstrates
the signicant inuence of the Ag(111) substrate on the structure of
the adsorbed FePc molecules [18]. In a previous paper, the adsorption
of FePc on Cu(100) surface was studied by STM [19]. However, these
studies mainly focused on monolayer structure. In order to shed light
on and control over the growth of molecular lms, sub-monolayer,
monolayer and multilayers have to be studied as well.
The results show the deposition of FePc as a molecular cluster. The
Cu(100) surface is particularly attractive in the study of the adsorption
of organic molecules because the chemistry of the surface encourages
molecules to lie at so as to optimize the metalmolecule interactions.
The interest about iron phthalocyanine is motivated by its peculiar pla-
nar shape, as a suitable candidate for the above listed applications. In
this paper we show our investigations of sub-monolayer, monolayer
and multilayer FePc deposited on Cu(100) surface by using STM at
room temperature 300 K (RT), since the adsorption at the initial stage
is very important for the further growth of the organic molecules on
metal surface. In addition, the density functional theory (DFT) studies
are carried out to investigate the metalmolecule interactions. The

0039-6028/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.susc.2012.07.021
1750 R.A. Rehman et al. / Surface Science 606 (2012) 17491754
systematic study shows the specic adsorption site at the initial growth
stage as well as the molecular structure of the developing thin lm.
2. Experimental and calculation details
The experiments were performed with a multitechnique surface
analysis system (Omicron instrument for surface science) with a
base pressure better than 2.0 10 10 mbar. The system is described
in detail elsewhere [20]. In brief, it consists of a fast-loading chamber,
a preparation chamber, an analysis chamber, and a scanning tunnel-
ing microscopy (STM) chamber. The system is also equipped with a
resistive-heating Ta boat FePc evaporator, a low-energy electron dif-
fraction (LEED), ultra-violet and x-ray photoelectron spectroscopies
(UPS/XPS). All the STM images were recorded in the constant current
mode with chemically etched tungsten tips at 300 K, and all given
voltages are referred to the sample.
Before depositing FePc, a clean 1 1-Cu(100) surface was obtained
by standard Ar+ sputtering and annealing procedures. This resulted in
a clean and very at target surface with terraces larger than 100 nm.
The cleanness of the surface was checked by LEED, STM and XPS
measurements. Prior to the sample preparation, FePc (Aldrich, 90%)
was heated overnight just below the deposition temperature for
purication. Molecules were then thermally evaporated at 540 K onto
the Cu(100) surface held at RT with a deposition rate of 0.1 ML/min.
The measure of the extent of the adsorption of FePc was determined
via quartz thin lm monitor, which was calibrated by subsequent
in-situ XPS and STM measurements. Here 1 ML is dened as the amount
of FePc molecules that fully cover the substrate in the at adsorption
model.
In order to verify the adsorption structure from the experimental
STM images and to inspect the details of the adsorption mechanism,
Density functional theory (DFT) calculations were performed by
using DMol 3 (e.g. density functional for molecules and 3D periodic
solids) [21,22] code within the generalized gradient approximation
(GGA) [23]. For computational details, the PerdewWang (PW91)
[24] functional and the DFT semicore pseudopotential were used to
describe electronelectron and electronion interactions, respective-
ly. The MonkhorstPack scheme [25] was used to sample the Brillouin
zone. Concerning accuracy, the wave function and electron density
a b
c [001]
Fig. 1. a) STM images (40 nm 40 nm) of 0.2 ML of FePc molecules on Cu(100) surface at RT, V= 3.20 V, I = 0.08 nA; b) STM image (50 nm 50 nm) of 0.6 ML of FePc mole-
cules on Cu(100) surface at RT, V= -3.08 V, I= 0.05 nA, two black arrows indicate the [001] and [011] directions of the Cu(100) substrate; c) schematic model illustrating the ad-
sorption of an isolated FePc molecule on Cu(100) surface (top view); d) a proposed structural model of an isolated FePc molecule on Cu(100) surface (side view).
were expanded by DND (double numeric plus d-function) basis sets
and a nite basis set cutoff radius of 4.0 was used to improve the
computational performance. The Cu(100) surface was modeled by a
slab with four layers of Cu atoms and a vacuum region of 20 . During
the process of structural optimization, all atoms except for the bottom
two Cu layers were fully relaxed. The convergence criteria for the geo-
metrical optimizations were set as 2.0 10 5 Hartree for the energy,
4.0 10 3 Hartree/ for the energy gradient, and 5.0 10 3 for the
ionic step displacement.
3. Results and discussions
Fig. 1a shows the STM image recorded after depositing 0.2 ML of
FePc molecules on Cu(100) surface held at room temperature (RT in
the following). Neither compact aggregations nor ordered structures
are observable which on one hand indicates an insignicant surface
diffusion and on the other weak inter-molecular interactions.
The structure of 0.6 ML FePc deposited on the Cu(100) surface is
presented in Fig. 1b. No discernable intense surface modication,
e.g. molecular fragmentation is observed. In both the cases, we see
the fourlobed bright shapes which are the characteristic features of
FePc molecules; dispersedly adsorbed on the low index copper sur-
face. From the molecular shape and the analysis of the protrusions'
size, we can immediately recognize that FePc molecules are adsorbed
with their molecular plane parallel to the sample surface, as depicted
in Fig. 1a, b.
Another interesting aspect of this study concerns the orientation of
the adsorbed molecules. Two distinct congurations are visible in the
STM images. A tentative structural model for these adsorption congu-
rations is proposed in Fig. 1c, where the black arrows represent the
crystallographic directions of the Cu(100) surface. An interesting obser-
vation for the sub-monolayer coverage is that the molecular axes of

FePc are aligned along [037] (as well as [037]) azimuth, namely the mo-
lecular axes rotate in clockwise or anticlockwise about 22 with respect
to the [001] direction. This suggests that the orientation of the adsor-
bates at RT is indeed affected by the substrate directions.
The relative apparent frequencies of these molecular congura-
tions evidently give a measure of their distribution. A careful analysis
of 481 FePc molecules in different STM images with the same
[011]
[001]
d 7
2.70
[001]
 R.A. Rehman et al. / Surface Science 606 (2012) 17491754
coverage indicates that the number of molecules with their axes
 azimuth.
along [037] azimuth is nearly the same as that along [037]
Due to the fourfold symmetries of the Cu(100) surface and FePc mol-
ecule, an adsorption geometry with a clockwise rotation is identical to
that in anticlockwise which yields a mirror structure similar to the re-
sults of a previous study [26].
The experimental ndings are qualitatively discussed in terms of
density functional theory calculations. During DFT calculations,
performed for an isolated FePc molecule adsorption, a unit cell with
dimensions of 20.5 20.5 2 was used. This unit cell, by denition,
contained only one molecule and was large enough to avoid the inter-
actions between two FePc molecules in neighboring unit cells. Three
adsorption models for FePc molecule adsorbed on the Cu(100) sur-
face were selected as initial structures. At the initial stage, the mole-
cule was adsorbed onto the top, hollow and bridge sites, labeled as
T, H and B respectively. Here, the adsorption sites refer to the posi-
tions at the rst layer of copper surface where the iron atom of FePc
molecule is located. The energy of an isolated molecule together
with the substrate supercell was calculated and the adsorption struc-
ture was optimized with the minimum energy. A generalized expres-
sion for the determination of the adsorption energy Ead can be written
as follows:
Ead EFePc ECuEFePc=Cu
where E(FePc), E(Cu) are energies of the adsorbate and substrate, and
E(FePc/Cu) is the total energy of the substrateadsorbate system. DFT
calculation results of an isolated FePc molecule deposited on the
Cu(100) surface, presented in Table 1, indicate that molecules prefer
to adsorb on the top site in a at-lying geometry with a separation
of 2.70 between the molecule and the substrate. The symmetry
axis of the adsorbed FePc molecule is observed close to the [037] az-
imuth, and four-lobed cross structure of the molecule is almost on the
top of the Cu atom. The DFT calculations suggest that the molecular
plane is bent, with an angle of about 7, at the expense of strong
molecule-substrate interactions.
In fact, the molecular interaction with the substrate by the molecular
orbitals signicantly changes the electronic structure of the adsorbed
FePc compared to the gas phase molecule. The metalmolecule interac-
tions is expected to be between the -orbitals of organic molecules and
metal d-bands which ultimately lead to display interesting features like
bending of molecule [27] and/or charge transfer [28].
The interaction process between the molecule and sample surface is
directly conrmed by the electronic density of states (DOS) calculated
for free and adsorbed molecule, as presented in Fig. 2. The structures
A, B, C, D and E results from the states located on the aromatic rings
and from the states localized on the benzene and hybrid FeN orbitals.
Little difference in electronic density of states can be found from the
molecule on top and hollow sites, but a great difference in electronic
density of states can clearly be observed between the bare and adsorbed
molecule; especially in the energy range of 0.25 eV. The changes in the
electronic structure of the adsorbed molecule demonstrate that FePc
molecule interacts with the underlying substrate not only through the
benzopyrrole legs but also through singly occupied dz2 orbital [29]. In
other words the structures A, B, C, D and E results from the states lo-
cated on the aromatic rings and from the states localized on the ben-
zene and hybrid FeN orbitals.
Table 1
DFT calculation results for a FePc molecule on Cu(100) surface in domain A.
Site Eads (eV) Separation () Angle between molecular
axes and [037] azimuth ()
T 4.101 2.70 1 domain A. FePc molecules form a quasi-quadratic structure with the
H 3.928 3.60 2 lattice vectors a1 and b1 separated by an angle of 95 3. The molec-
B 3.738 2.90 0
1751
E D B
C
A
Hollow
DOS(a.u)
Top
Bare
-20 -10 0 10
Binding Energy(eV)
Fig. 2. DOS of an isolated and adsorbed FePc molecule. The bottom curve is from bare
molecule, the middle one is from the molecule on the top site and the top one is
from the molecule on the hollow site.
The reduction in intensity of the molecular features, the shift in
energy and the change in the shape of the adsorbed molecular or-
bitals are a clear signature of the strong moleculesubstrate interac-
tions. As mentioned earlier, FePc molecules prefer to lie at on the
Cu(100) surface at the initial stage of growth leading to maximize the
interaction between the d-band of the substrate and the -molecular
orbitals. With further increasing the molecular coverage, no ordered
structure is observed at RT. After subsequent annealing, ordered struc-
ture can be observed particularly when the annealing temperature is
equal to or higher than 383 K. The STM image, shown in Fig. 3a, is
obtained after 10 h of annealing. Fig. 3b denotes the monolayer STM
image of FePc molecules on the sample surface after annealing the sam-
ple at about 433 K.
A bird's eye view of these structures reveals two types of ordered
domains; marked with A and B in Fig. 3b. Clearly, all the FePc mole-
cules in domains A and B posses the same orientation which are im-
aged as bright spots surrounded by four less bright lobes. The
enhanced brightness at the molecular center is ascribed to the partial-
ly lled d-orbital of the Fe atom [17]; whereas the four lobes could be
attributed to the four isoindole units of the molecules. High resolution
STM images of domains A and B are shown in Fig. 3c and e respective-
ly. The corresponding models for the domains A and B are given in
Fig. 3d, f and their relative superstructure matrices are represented
with Eqs. (1) and (2). Relevant details of these matrices are given
therein.
K. Manandhar et al. have reported the post-deposition annealing of
CuPc thin lms on Ag (111) surface [7]. The transition of the symmetry
of the overlayer lattice from an oblique to a square lattice at 580 K [7],
and the LEED patterns of CoPc and FePc grown on Au (001) surface at
elevated temperature demonstrates that these overlayers are highly or-
dered [30]. Ordered domains are much easier to be observed after
annealing. This may be understood in terms of the increasing diffusion
of adsorbed molecules on the substrate. As the temperature is in-
creased, the mobility of the adsorbing molecules increases; illustrating
the fact that sufciently high surface mobility is required for diffusing
species to nucleate and, subsequently, to form a smooth overlayer sur-
face [31].
The preferred adsorption position of FePc in domain A is the top
site as determined by DFT results. Fig. 3d displays the real-space con-
guration of the molecules and the periodic structure of the ordered
 
ular lattice vectors a1 and b1 are along [041] and 014  azimuths,
1752 R.A. Rehman et al. / Surface Science 606 (2012) 17491754

a b

c d [001]

b1 a1

e
f [001]

a2

b2

Fig. 3. a) STM image (120 nm 120 nm) of a monolayer FePc on Cu(100) surface after annealing the sample at 383 K, V= 0.45 V, I = 0.29 nA. b) STM image (30 nm 30 nm) of a
saturated FePc layer on Cu(100) surface, two types of ordered domains are labeled with A and B.&& c) High resolution image (7.5 nm 7.5 nm) of the ordered domain A. d) The
model for one unit cell of FePc molecule monolayer on Cu(100) of domain A. e) High resolution image (7.5 nm 7.5 nm) of the ordered domain B. f) The geometry of a unit
cell of FePc molecule monolayer on Cu(100) for domain B.

respectively. The relationship between the unit cells of the adsorbate 2.70 between the molecule and the substrate. The molecular axis
and substrate yields the following commensurate superstructure of FePc is along [037] azimuth; same as that of an isolated FePc mol-
matrix: ecule on Cu(100) surface, indicating that the inter-molecular inter-
0 1 actions are weak compared to that between the FePc molecules and
  3 5   substrate.
a1 A a
@ 1 In domain B, molecules adsorb on the hollow site of the substrate
b1 b
5 3 as conrmed by DFT calculations. Fig. 3f displays the real-space con-
guration of the ordered domain B. The structure consists of an
where vectors a and b are
h primitive
i lattice vectors of Cu(100) surface oblique lattice with the lattice vectors a2 and b2 separated by an
along the [011] and 011 directions, respectively. Since a = b = angle of
 90 3 . The molecular
 lattice vectors a2 and b2 are aligned
2.6 , so a1 = b1 = 15.0 . The packing density of domain A is along 032  and 02 3
 azimuth respectively. Based on the relation-
0.444 molecules/nm 2, namely coverage is about 0.8 ML. Recently, ship between the unit cells of the adsorbate and substrate, the follow-
similar STM images of FePc thin lm on Ag (111) surface have been ing commensurate superstructure matrix is deduced:
reported [32]. Ordered regions of FePc molecules were measured 0 1
up to a size of 150 nm 50 nm without any molecular vacancies.   3 5  
a1 A a
Our DFT ndings for domain A indicate that molecules prefer to ad- @ 2
b1 b
sorb on the top site in a at-lying geometry with a separation of 5 3
 R.A. Rehman et al. / Surface Science 606 (2012) 17491754 1753

Table 2
DFT calculation results for a FePc molecule on Cu(100) surface in domain B.
Site Eads (eV) Separation () Angle between molecular
axes and [037] azimuth ()
T 5.042 2.70 8 wards towards the substrate. However, the symmetry reductions
H 5.186 3.30 6.7
where vectors a and b are primitive
h i lattice vectors of Cu(100)
surface along the [011] and 011 directions, respectively. Since
a = b = 2.6 , so a2 = b2 = 13.3 . The packing density of domain
B is 0.535molecules/nm 2, and the coverage is close to 1.0 ML. DFT
calculation results of an FePc molecule deposited on Cu(100) sur-
face for domain B are shown in Table 2, suggesting that molecules
prefer to adsorb on the H site in a at-lying geometry with a sepa-
ration of 3.30 between the adsorbate and substrate. In the
oblique structure, the neighboring molecules within the unit cell
rotate their molecular axes with respect to the [037] azimuth by
an angle of 6.7 , as shown in Fig. 3f. As a result of this rotation,
the nearest neighbor distance between the molecules is reduced
compared to the quasi-quadratic lattice, by an amount of 1.12, per-
haps to increase the intermolecular attractive interactions.
From the above discussion we reach at the conclusion that theo-
retically identied molecular geometry and orientation reasonably
match with the experimentally measured structures. When FePc mol-
ecules go further to the second layer, no ordered pattern is observed
at room temperature (see Fig. 4a); rather a single FePc molecule on
the second layer is clearly identiable. The unusual shape in this g-
ure is neither an island nor a cluster; rather it is a distorted form of
the single molecule adsorbed on the rst monolayer and it belongs
to the second layer molecules. Unfortunately, we could not record a
high resolution image of this single molecule adsorbing on the rst
monolayer.
A further analysis of Fig. 4a discloses that the molecule is tilted to-
wards the substrate surface plane with its two lobes pointing down-
observed in the STM images derive not only from the topographic ef-
fects but also from the electronic effects. As we know the tunnelling
current depends on the local density of states of the surface and the
voltage dependence in STM can be used to obtain information on
the local density of states of a surface. Nevertheless, the STM image
remains unchanged when the bias voltage is changed from 3.4 V
to 0.8 V, so the electronic effects can be excluded. A similar STM
image was observed by Z. H. Cheng et al. Their results show that
FePc molecule ish tilted i about 40 towards the substrate surface
plane along the 101 direction. Trapped at the central hole of a
unit cell in the rst layer, the lobe of ad-molecule points downward
to the Au(111) substrate and a perfectly periodic structure of the sec-
ond FePc layer is subsequently formed at 5 K [33].
By comparing the STM molecular images, shown in Fig. 1 (a, b), 3
(b, c, e)) and 4a, we nd that the images have four fold symmetry
which completely agrees with the molecular structure of FePc. It is im-
portant to realize that at low coverage inter-molecular forces are weak
van der Waals forces that preserve the individuality of the molecules. To
clarify the effect of inter-molecular interactions and metalmolecule
interaction on the morphology of the organic lm, we further deposited
FePc on the sample surface at room temperature. We noticed that at the
coverage of 1.3 ML, nucleation of the second layer takes place.
A quick inspection of Fig. 4b shows the formation of molecular
clusters; especially near the step edges. Since layers at higher coverage
are not in direct contact with the sample surface, therefore the strength
of inter-molecular interactions is greater than the moleculesubstrate
interaction which eventually drives the formation of clusters [34]. The

Fig. 4. a) STM image (7.5 nm 7.5 nm) of a single molecule adsorbed on the rst layer, V = 3.08 V, I = 0.05 nA. b) STM images of 1.3 ML FePc molecules (120 nm 120 nm) on
Cu(100) surface, V= 0.91 V, I= 0.19 nA. c) Close-up view of the yellow bordered structure (38 nm 38 nm)in (b). d) Line prole along the line AB in (c).
1754 R.A. Rehman et al. / Surface Science 606 (2012) 17491754
lattice mismatch of materials also induces three dimensional aggrega-
tions [31]. Fig. 4c shows a close-up view of the single FePc molecular is-
land at the second layer. A line prole (from A to B in Fig. 4c) is
displayed in Fig. 4d. The height of the second molecular layer is 1.8 ,
but that of the rst layer is 1.6 . The results also show that FePc mole-
cules at the second layer do not adsorb on the Cu(100) surface in a
at-lying geometry.
4. Conclusions
The growth behavior of FePc molecules deposited on the Cu(100)
surface has been investigated by means of both experimental and
theoretical approaches. At low coverage, FePc molecules tend to ad-
sorb dispersedly with their molecular planes parallel to the substrate.
At the saturation coverage, no distinct ordered phase is observed at
RT. However, after 10 h of annealing the sample at 383 K two types
of ordered structurally inequivalent structures are noticed. At the
coverage of 1.3 ML, FePc molecular clusters are formed particularly
near the step edges.
Acknowledgments
The work is supported by the National Natural Science Foundation of
China (Grant Nos. 10974172, 10774129, 61106131), Zhejiang Provincial
Natural Science Foundation of China (Grant No. Y6110072), and the
Fundamental Research Funds for the Central Universities.
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