Fullerene film on metal surface: Diffusion of metal atoms and interface model

Wen-jie Li, Peng Wang, Xiao-Xiong Wang, Jia-Ou Wang, Rui Wu, Hai-Jie Qian, Kurash Ibrahim, Hai-Yang Li,
and Hong-Nian Li

Citation: Applied Physics Letters 104, 191606 (2014); doi: 10.1063/1.4878404

View online: http://dx.doi.org/10.1063/1.4878404
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 APPLIED PHYSICS LETTERS 104, 191606 (2014)

Fullerene film on metal surface: Diffusion of metal atoms and interface model
Wen-jie Li,1 Peng Wang,2 Xiao-Xiong Wang,3 Jia-Ou Wang,4 Rui Wu,4 Hai-Jie Qian,4
Kurash Ibrahim,4 Hai-Yang Li,1 and Hong-Nian Li1,a)
1
Department of Physics, Zhejiang University, Hangzhou 310027, China
2
Department of Applied Physics, Shandong University of Science and Technology, Qingdao 266590, China
3
College of Science, Nanjing University of Science and Technology, Nanjing 210094, China
4
Laboratory of Synchrotron Radiation, Institute of High Energy Physics, Chinese Academy of Sciences,
Beijing 100039, China
(Received 2 April 2014; accepted 6 May 2014; published online 14 May 2014)
We try to understand the fact that fullerene film behaves as n-type semiconductor in electronic
devices and establish a model describing the energy level alignment at fullerene/metal interfaces.
The C60/Ag(100) system was taken as a prototype and studied with photoemission measurements.
The photoemission spectra revealed that the Ag atoms of the substrate diffused far into C60 film
and donated electrons to the molecules. So the C60 film became n-type semiconductor with the Ag
atoms acting as dopants. The C60/Ag(100) interface should be understood as two sub-interfaces on
both sides of the molecular layer directly contacting with the substrate. One sub-interface is Fermi
level alignment, and the other is vacuum level alignment. V C 2014 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4878404]

Fullerenes (C60, C70, and C84) and their derivatives
(PC61BM, PC71BM, etc.) have exhibited important applica-
tions in organic electronics such as field effect transistors
(FETs),1–4 solar cells,5–8 and memory devices.9,10 The appli-
cations require thorough understanding of the electronic
property of fullerene film on metal (electrode) surface. One
amazing phenomenon is that C60 acts as n-doped semicon-
ductor,5,11 and nobody knows where the dopant comes from.
Another long-standing problem is how to properly describe
the energy level alignment at fullerene/metal interfaces.
One significant progress on the geometric structure of
fullerene/metal interfaces has been achieved in recent years:
fullerene molecules dig pits on various metal substrates.12–16
Accompanied with the pit formation, some metal atoms are
dug out from the substrate and become so-called adatoms.
The adatoms may be highly mobile, as suggested by two
most recent works16,17 to interpret the scanning tunneling
microscopy observations of some extremely bright mole-
cules emerging in the C84 and C60 monolayers (MLs) on
Ag(111) surface. We guess that the adatoms diffuse far into
fullerene lattice and act as dopants when an interface is
formed between a thick fullerene film and a metal substrate.
One purpose of the present work is to verify our guess.
Large quantity of works has demonstrated that the full-
erene layer in direct contact with a metal substrate is metal-
lic, and thus this molecular layer should be considered
separately from other semiconducting molecular layers.
Therefore, we suggest that the interface between a thick full-
erene film and a metal substrate be constituted by two sub-
interfaces. One sub-interface is between the metal substrate
and the fullerene ML in direct contact with the substrate;
another is between the fullerene ML and the fullerene multi-
layer. The former should be Fermi level alignment consider-
ing that fullerene molecules intimately combine with the
metal substrates through strong covalent bonds14,18 and
a)
Author to whom correspondence should be addressed. Electronic mail:
Phylihn@mail.zju.edu.cn
some charge transfer. The energy level alignment at the
ML/multilayer sub-interface is, however, not clear at
present.
In this work, we selected C60/Ag(100) system as a proto-
type. C60 digs the 4- or 5-atom pit (4 or 5 Ag atoms are dug
out by each C60 molecule) on the surface of Ag(100),19 in
contrast to the case of the 1-atom pit on some other metal
surfaces.18,20,21 The large quantity of the adatoms should
make the diffusion of the adatoms be easily observed by pho-
toemission measurements. For the study of the
ML/multilayer sub-interface, we prepared a well-defined C60
monolayer (1 ML C60/Ag(100)) by annealing a C60 multi-
layer at 300  C in ultra-high vacuum (UHV). The 1 ML
C60/Ag(100) then acted as the substrate for growing thicker
film.
Our experiments were carried out at the Photoelectron
Spectroscopy Endstation of the Beijing Synchrotron
Radiation Facility. The base pressure of the UHV system
was better than 1  1010 millibar. An Ag(100) single crystal
of 8 mm in diameter was cleaned by standard bombarding
and annealing procedure. Thoroughly degassed C60 was sub-
limed from a Ta boat onto the Ag(100). The C60 source was
a crowd of tiny single crystals of very high purity,22 and the
electric current through the Ta boat was kept constant for
each round of deposition. After the preparation of the 1 ML
C60/Ag(100), succeeding deposition of C60 was performed
with the substrate kept at 150  C to assure the layer-by-layer
growth manner. The thickest C60 film studied here was 20
MLs. A Gammadata Scienta R4000 analyzer was used to
collect the photoelectrons with a collecting angle of 38 . The
sample normal coincided with the entrance of the energy an-
alyzer. Valence band photoemission (ht ¼ 21.2 eV) and
core-level photoemission (ht ¼ 700.0 eV) were measured for
every stage of the sample preparation history. The 4f7/2 pho-
toemission of an Au film (deposited on the sample holder
just before the measurements) was also recorded after each
round of the Ag 3d and C 1s measurements, for the purposes
of normalizing the spectral intensities and checking the

0003-6951/2014/104(19)/191606/4/$30.00 104, 191606-1 C 2014 AIP Publishing LLC

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 191606-2 Li et al.
photon energies. The energy resolution of the spectra was
better than 0.05 and 0.65 eV at the photon energies of 21.2
and 700.0 eV, respectively. Unless otherwise specified, the
sample position was adjusted to assure the incident synchro-
tron light (with the spot sizes of 0.5  0.2 mm2 for the
21.2 eV photons and 1.0  0.5 mm2 for the 700 eV photons)
illuminating on the central region of the sample.
Figure 1 illustrates the spectral determination of the dep-
osition rate of C60 molecules onto the 1 ML C60/Ag(100).
The C60 ML cannot completely attenuate the signal from the
Ag(100), as indicated by the dashed-dotted vertical lines.
After two rounds of 5 min deposition, line (b) has negligible
contribution from the Ag(100). Additional 1.5 min deposi-
tion slightly shifts the highest-occupied-molecular-orbital
(HOMO) and HOMO-1 features towards higher binding
energy. Then the spectrum keeps almost invariant with 1.5
and 4 min more depositions. The spectral evolutions indicate
that line (c) corresponds to a coverage very near 2 ML, i.e.,
another C60 ML covers the 1 ML C60/Ag(100). The thicker
films up to 20 ML were prepared by taking the integral depo-
sition time (11.5 min) of line (c) as the time needed for 1 ML
deposition.
The core level photoemission data of the 1, 2, 4, 7, 10,
15, and 20 ML samples are shown in Figs. 2(a) and 2(b). The
C 1s spectra in (b) were measured with smaller pass energy
(better resolution). The intensities of all the spectral lines in
Fig. 2 are normalized to the Au 4f photoemission (also meas-
ured with two different pass energies), and thus reflect the
absolute variations with different film thickness. The most
striking observation is that the Ag 3d signal can be still
observed on the 20 ML sample in Fig. 2(a)! The Ag 3d pho-
toemission should have been completely attenuated at the
coverage of 10 ML according to the inelastic-mean-free-
path data.23
Figure 2(c) exhibits the quantitative analyses of the
spectral intensities. The blue filled squares are the Ag 3d5/2
intensity ratios of the C60 samples to the clean Ag(100). For
the layer-by-layer growth manner, the substrate signal should
be attenuated according to tn, where t is the transmission ra-
tio of the Ag 3d5/2 photoelectrons through one molecular
layer23 and n denotes the number of molecular layer. The
FIG. 1. Determining deposition rate of C60 molecules onto the 1 ML
C60/Ag(100) with valence band photoemission. The deposition time (in min)
is indicated for each spectrum. The spectral lines are normalized to the
height of the HOMO feature except that the spectrum of the clean Ag(100)
is fitted to the scale of the figure.
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Appl. Phys. Lett. 104, 191606 (2014)
transmission ratio t is 0.5 as calculated from the spectral
intensities of the 1 ML sample and the clean Ag(100) in Fig.
2(a). Then we can draw the expected intensity ratios as the
blue curve in Fig. 2(c), which is, however, evidently smaller
than the experimental values. There are two possible reasons
for the discrepancy. First, the nominal thickness might be
overestimated. Second, the Ag adatoms diffused far into the
C60 multilayer as we suggested previously. We can preclude
the first possible reason by analyzing the C 1s intensity
ratios. The red filled circles in Fig. 2(c) are the C 1s intensity
ratios of the C60 multilayers to the 1 ML C60/Ag(111), which
were calculated based on the spectra in Fig. 2(b) (the ratios
calculated from Fig. 2(a) were almost the same). The inten-
sity of the C 1s signal saturates at the coverages greater than
7 ML, coinciding with the inelastic-mean-free-path data of
Ref. 23. Besides, these experimental data can be fitted fairly
well with the equation23
In 1  t0n
¼ ;
Imono 1  t0
where In and Imono denote the C 1s photoemission intensities
of n layer C60 and 1 ML C60, and t0 is the transmission ratio
of the C 1s photoelectrons. The best fitted value of t0 is 0.525
FIG. 2. (a) Ag 3d and C 1s core-level photoemission of the samples meas-
ured with the pass energy of 20 eV. (b) C 1s photoemission measured with
the pass energy of 10 eV. The double-arrowed vertical lines in (a) and (b)
indicate the binding energy range used to calculate the spectral areas.
Shirley background was subtracted for both the Ag 3d (not shown) and the
C 1s photoemission (the bottom green line in (b)). (c) Comparison of the ex-
perimental intensity ratios (the scattered symbols) with that expected on the
basis of the layer-by-layer growth manner (the blue and red curves). The Ag
3d5/2 intensity ratios are relative to the clean Ag(100), while the C 1s ratios
are relative to the 1 ML C60/Ag(100).
 191606-3 Li et al.
(see the red curve in Fig. 3(c)), reasonably slightly greater
than t considering the increased kinetic energy of the C 1s
photoelectrons as compared with the Ag 3d5/2 photoelec-
trons. Therefore, the film thickness estimated on the basis of
Fig. 1 should be rather accurate, and the Ag 3d signal
observed on the 10, 15, and 20 ML samples is from the Ag
adatoms that diffused into the C60 films.
The valence band photoemission shown in Fig. 3 affords
more direct evidence of the diffusion of the Ag adatoms.
After magnifying the spectral signal near the Fermi level
(the red lines in Fig. 3(a)), we can clearly observe the photo-
emission of the lowest-unoccupied-molecular-orbital
(LUMO) electrons at least for the coverages up to 10 MLs.
The LUMO signal is not background noise because the
Fermi cutoffs are distinct in the spectra of the 2–7 ML sam-
ples. We also precluded the possibility of the contribution
from the substrate or the 1 ML C60/Ag(100) by measuring
the spectra with the incident photons illuminating on some
different regions of the 4 ML and 7 ML samples. It is well
known that the valence band signal is mainly from the top
molecular layer for fullerene sample. Therefore, the Ag ada-
toms definitely diffused far into the C60 film and donated
their 5s electrons to the LUMO of C60. Some adatoms surely
diffused to the top layer of the thicker (15, 20 MLs) samples,
but the LUMO signal was weak due to the limited number of
the adatoms.
We could clearly observe the diffusion because the num-
ber of the adatoms was relatively large in the C60/Ag(100)
system. Besides, the substrate temperature (kept at 150  C
during the C60 deposition) facilitated the diffusion. For those
fullerene/metal systems with fewer adatoms or formed at
room temperature, the number of adatoms diffused into the
fullerene films may be smaller but definitely nonnegligible
from the point of view of semiconductor doping. So, the dif-
fusion of the adatoms interprets the mystery of n-type semi-
conducting behavior for fullerene film in those electronic
devices (FET, memory device and some types of solar cells)
having fullerene/metal junctions. It is needed to point out
that the Fermi cutoffs observed in Fig. 3(a) does not mean
FIG. 3. (a) Valence band photoemission of the C60 overlayer on Ag(100)
surface. The spectral lines are normalized to the height of the HOMO feature
except that the spectrum of the clean Ag(100) is fitted to the scale of the fig-
ure. The red lines magnify the spectral signal near the Fermi level. (b)
Secondary electron cutoffs. The work function (U) data are determined by
the tangent of the cutoff and the base line.
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Appl. Phys. Lett. 104, 191606 (2014)
the C60 multilayers being metallic. There should be a small
portion of metallic AgxC60 (x  7) compounds24 dispersed in
the n-type C60 semiconductor.
We previously suggested two sub-interfaces for fullerene/
metal systems. Figure 4 illustrates this interface model for the
C60/Ag(100) system, in which the energies of the vacuum lev-
els and the HOMO centers are from Fig. 3. The vertical red
line indicates the sub-interface between the Ag(100) and the
C60 ML. This sub-interface is obviously Fermi-level align-
ment because of the charge transfer from the Ag(100) to the
C60 ML. In addition, the HOMO and LUMO of C60 hybridize
with the Ag 4d5s states, resulting in splitting of the molecular
orbitals and nonnegligible occupied electronic states distribut-
ing continuously in the HOMO–LUMO gap (see Fig. 3(a) and
Ref. 19). The C60 ML loses its semiconducting property and
becomes a metallic layer. The work function of the C60 ML
on the Ag(100) surface is 4.71 eV, greater than that of the
clean Ag(100) by 0.31 eV.
The crucial issue is the energy level alignment at the
sub-interface between the C60 ML and the C60 multilayer.
This sub-interface is indicated with a vertical blue line in
Fig. 4 and is referred to as blue-line interface in the follow-
ing. On the basis of the noticeable LUMO electrons of the
C60 multilayers (Fig. 3(a)) and the metallic nature of the C60
ML, we might anticipate the blue-line interface to reach elec-
trical equilibrium (Fermi level alignment) through charge
flow. Fermi level alignment is generally accompanied with
distinct shift of vacuum level as the case of the sub-interface
between the Ag(100) and the C60 ML. However, the vacuum
level shift is very small (no more than 0.1 eV) from the 1
ML sample to the 20 ML sample in Figs. 4 or 3(b), and may
be regarded as negligible considering the possible error of
the measurements. If the blue-line interface were Fermi level
alignment, the negligible shift of the vacuum level could
only be understood with the intrinsic work function of the
C60 multilayers being accidentally identical to that of the 1
ML C60/Ag(100). This kind of situation is unlikely to
happen.
We think that the negligible vacuum level shift of the
C60 multilayers is the indication of vacuum level alignment
at the blue-line interface. That is to say, the LUMO electrons
FIG. 4. Interface model and energy level diagram of the C60/Ag(100) sys-
tem. The red and blue vertical lines represent two sub-interfaces. The ener-
gies of the HOMO centers (filled circles) and the vacuum levels (open
circles) are from Fig. 3 and referenced to the Fermi level of the metal
substrate.
 191606-4 Li et al.
are not itinerant throughout the multilayer samples (unless layer. Further works are needed to verify the applicability of
applied with external driving force such as the electric field the conclusions to the interfaces formed between fullerene
in FET). This can be understood by the fact that the mole- derivatives and metals.
cules are combined with weak van de Waals interaction. The
Ag adatoms only fill a small part of the interstitial sites of
the C60 lattice and do not substantially alter the bonding na- Science Foundation of China under Grant Nos. 11374258
ture of the C60 multilayers. So the blue-line interface cannot and 11079028 and the Beijing Synchrotron Radiation
reach electrical equilibrium. The vacuum level alignment at Facility.
the blue-line interface is further supported by the work func-
1
tion data in the literature. Here, we mention a published
work of Hayashi et al.25 For film thickness not too large, say,
2
smaller than 50 nm that is the typical thickness of fullerene
film in electronic devices, the work functions of the C60 films 3
4
differed distinctly from one metal substrate to another.
5
However, the work function for each metal substrate kept
almost invariant above the coverage of 1 ML (well-defined 6
1 ML samples were not prepared in Ref. 25). By the way, the
7
vacuum level alignment indicates that the work function data
8
in Fig. 3(b) simply mean the energy of the vacuum level in
relative to the Fermi level of the 1 ML C60/Ag(100), rather 9
than the intrinsic work function of the C60 multilayers. The
10
movements towards higher binding energy for the HOMO
11
(Fig. 3(a)) and C 1s (Fig. 2(b)) levels are due to the screening
effect of the metallic substrate,26–28 rather than band 12
bending.
The significance of our interface model is the manifesta-
13
tion of the vital role of the second molecular layer (from the
metal substrate) in deciding the property of the fullerene/me-
14
tal interface. Actually, the substrate and the C60 ML can be
considered as an integral whole because of the Fermi level
15
alignment at the sub-interface between them. The integral
whole behaves as a new metal electronically characterized 16
by the work function of the 1 ML C60/Ag(100). The HOMO
17
and LUMO of the C60 ML play no role in device perform-
ance. The second molecular layer then becomes the surface
18
layer of the n-type C60 film; its HOMO and LUMO energies,
together with the work function of the 1 ML C60/Ag(100),
19
determine the electrical property. Please note that the
HOMO energy of the second molecular layer differs dis-
20
tinctly (by 0.3 eV in Figs. 3 and 4) from that of the C60
ML. Also, the work function of the 1 ML C60/Ag(100) dif-
fers distinctly from that of the pristine metal substrate. 21
In conclusion, atoms of the Ag(100) substrate can dif-
22
fuse into C60 film and act as dopants. So C60 film behaves as
n-type semiconductor in electronic devices. The
23
C60/Ag(100) interface is constituted by two sub-interfaces.
The sub-interface between the metal substrate and the metal- 24
lic C60 ML is Fermi level alignment, and another
25
sub-interface between the metallic ML and the n-type semi-
conducting C60 multilayer is vacuum level alignment. These 26
conclusions can be readily applied to C70, C84, and other
27
metal substrates. The electrical performance of fullerene/me-
tal interface in various devices should be primarily deter- 28
mined by the work function of the first molecular layer and
the HOMO and LUMO energies of the second molecular
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Appl. Phys. Lett. 104, 191606 (2014)
This work was supported by the National Natural
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