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 March 2011
EPL, 93 (2011) 57002 www.epljournal.org
doi: 10.1209/0295-5075/93/57002

Direct observation of Ni3+ and Ni2+ in correlated LaNiO3−δ films

Liang Qiao and Xiaofang Bi(a)

School of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics
Beijing 100083, PRC

received 23 September 2010; accepted in final form 7 February 2011

published online 1 March 2011

PACS 79.60.-i – Photoemission and photoelectron spectra

PACS 71.20.-b – Electron density of states and band structure of crystalline solids

Abstract – The X-ray photoelectron spectroscopic deconvolution analysis is applied to quan-

titatively distinguish valence states of Ni and to obtain the δ value in LaNiO3−δ films on Si
substrates. The mechanism of the Ni3+ /Ni2+ ratio dependent transport is clarified by the combi-
nation of transport measurements and first-principle calculations. At lower Ni3+ /Ni2+ ratio of
0.39, the LaNiO2.64 film exhibits semi-conductive behavior with carriers mainly being hopping
polarons, while higher Ni3+ /Ni2+ ratio transfers the LaNiO2.84 film to an electronic conduc-
tor. The observed reduction of the electron-phonon interaction, shortened mean free path, and
increased electron-electron coupling are suggested to be correlated to high Ni3+ /Ni2+ ratio.

c EPLA, 2011
Copyright

Among the diverse family of strongly correlated 3 d
perovskite oxides, the ternary La-Ni-O system (LaNiO3−δ
or Lan+1 Nin O3n+1 ) exhibits unique physical properties,
e.g. the metal-insulator transition is often coupled to the
magnetic ordering transition (paramagnetic to ferromag-
netic or antiferromagnetic) and the microstructural (NiO6
octahedrons to NiO4 square planes) as well as the elec-
tronic structural transition (Ni3+ to Ni2+ ) [1,2]. The rich
variety of physical properties originates from the strong
interplay of structural, electronic, and magnetic degrees
of freedom [3]. Very recently, the technological interest in
the development of highly conductive electrodes for spin-
tronic film devices has aroused significant attention to the
compounds [4–8].
LaNiO3 (LNO) is a paramagnetic metal in the temper-
ature range 1.5–300 K, however, this compound exhibits
a relatively narrow conduction bandwidth and a large
carrier effective mass [9]. Furthermore, the properties of
LaNiO3 are very sensitive to oxygen stoichiometry. Defi-
ciency of oxygen during fabrication process will lead to the
creation of Ni2+ ions and deteriorate conductive proper-
ties. Several groups have investigated the oxygen-content–
dependent conductivity for LNO bulks and films [1,10],
which demonstrates that the physical origin of the unique
properties of these strongly correlated nickelates is asso-
ciated closely with the electronic structure. Dobin et al.
studied the electronic structure of fully strained LaNiO3
films by first principles and found that the chemical
(a) E-mail: bixf@buaa.edu.cn
bonding in LaNiO3 is not purely ionic, but exhibits
substantial covalent (Ni-O and La-O) and metallic (Ni-O-
Ni) parts [4]. Using X-ray absorption spectroscopy (XAS),
Abbate et al. found that the metal-insulator transition
was related to the disappearance of the charge carri-
ers and observed a band gap opening with decreasing
oxygen stoichiometry in bulk LaNiO3−δ [3]. Meanwhile,
X-ray photoelectron spectroscopy (XPS) is also a promis-
ing and effective approach to study the electronic prop-
erties experimentally. However, due to overlapping of Ni
2p3/2 and La 3d3/2 peaks, it is impossible to exactly distin-
guish the Ni3+ and Ni2+ in LaNiO3−δ by XPS. Recently,
Mickevičius et al. have developed a method to separate Ni
2p3/2 peaks from La 3d3/2 peaks in XPS spectra to inves-
tigate the composition and valence states of La in LNO
films [11], but it is not related to the separation of differ-
ent valence states of Ni, which is essential to understand
the electronic and transport properties of LNO. Direct
observation of various Ni valence states is required to
shed light on the physical origin of the unique properties
for these strongly correlated oxides. In addition, although
the transport properties for LNO have been greatly inves-
tigated, very few of them are done for LNO films on
Si substrates, which is important from the viewpoint of
compatibility with current semiconductor technology. In
this letter, we report a method to clearly distinguish Ni3+
and Ni2+ in LNO films on Si (001) by XPS deconvolu-
tion analysis and investigate their effects on conductive
and electronic properties for LNO based on both trans-
port measurements and first-principle calculations.

57002-p1
Liang Qiao and Xiaofang Bi
Fig. 1: (Colour on-line) (a) Angle-resolved XPS measurements
of O 1s peaks at a function of polar angles (7◦ –91◦ ) for LNO-
1 film. (b) O 1s peak for LNO-1 after Ar+ sputtering. The
inset in (b) is the Ni 3p spectrum for LNO-1 before and after
sputtering.
LNO films were deposited on Si (001) substrates by
the radio frequency (rf) sputtering method with a base
vacuum of 2 × 10−4 Pa. A stoichiometric dense and crack-
free LNO ceramic target (
= 60 mm) was fabricated by
sintering a cold pressed pallet from mixed La2 O3 (99.95%)
and Ni2 O3 (99.99%) powders with a molar ratio of 1 : 1.
The substrate temperature was maintained at 600 ◦ C and
the target-to-substrate distance was kept at 70 mm. The
total rf output power was set at 62 W. For comparison,
depositions were done under two different conditions: pure
argon of 4.0 Pa (LNO-1) and mixture of 0.5 Pa argon
plus 3.5 Pa oxygen (LNO-2). To ensure the film structural
quality [7], both LNO films were designed to be 600 nm in
thickness, which was measured by a DektakII profiler and
calibrated by scanning electron microscopy observations
and X-ray reflectivity measurements.
Valence states of different elements were determined
by X-ray photoelectron spectroscopy (XPS, AXIS-Ultra,
Kratos Analytical) using monochromatic Al Kα radiation
with photon energy of 1486.6 eV (225 W, 15 mA, 15 kV)
and low-energy electron flooding for charge compensation.
The base pressure for the XPS chamber is 5.0 × 10−9 torr
and the wide scan for both films indicates that there is
no detectable extrinsic contamination except for surface
carbon and OH. Since lanthanum oxides are easily hygro-
scopic and the appearance of lanthanum hydroxide may
complicate the quantification [12,13], all the samples were
in situ sputtered by Ar+ (500 V) for 2 minutes previously
to avoid the surface hydroxylation effect, as discussed in
the following part. All of the binding energies at differ-
ent peaks were calibrated by using the C 1s photoelec-
tron binding energy of 285.0 eV. Temperature-dependent
electrical resistivity measurements were carried out by the
standard four-probe testing system with silver glue as the
contacts [14].
57002-p2
Fig. 2: (Colour on-line) XPS spectra of La 3 d and Ni 2p core-
level lines for (a) LNO-2 and (b) LNO-1. The insets show the
corresponding Ni 3p core level spectra.
Lanthanum oxides are known to be easily hydroscopic at
ambient conditions. Figure 1(a) shows the angle-resolved
XPS (ARXPS) measurements of O 1s peaks as a function
of the polar angle θ (taken with respect to the film surface)
from 7◦ to 91◦ for LNO-1 film. Each O 1s peak can be
further deconvoluted into two peaks, with the one at lower
binding energy (∼531 eV) corresponding to lattice oxygen
and the one at higher binding energy (∼533 eV) is asso-
ciated with surface absorbed OH. It is seen that at shal-
low angle (∼7◦ ) the OH peak intensity (IOH ) is stronger
than that of the lattice oxygen peak (ILNO ), while with
increasing the polar angle, the IOH /ILAO ratio decreases
significantly, indicating that the OH only segregates at the
film surface. In order to get rid of this surface hydroxyla-
tion layer, an in situ sputtering is employed. As shown in
fig. 1(b), the sputtered surface is free of any hydroxylation
and is ready for XPS quantification measurements. Also,
we show in fig. 1(b) the Ni 3p spectrum for LNO-1 before
and after sputtering, it is clear that this slightly sputtering
process will not change Ni valence state.
Figures 2(a) and (b) present the La 3 d and Ni 2p core-
level spectra. Due to the coupling of spin-orbit splitting
(SOS) and multi-splitting [15], both La 3 d and Ni 2p
core-level spectra show very complicated multi-component
structures [16]. Standard energy positions for Ni3+ 2p3/2
and Ni2+ 2p3/2 [17] are marked by the dotted lines in fig. 2.
It is seen that the Ni 2p3/2 lines for both Ni2+ and Ni3+
are strongly overlapped with the existing La 3d3/2 satellite
line. As a result, it is impossible to precisely determine
the Ni3+ /Ni2+ ratio in this La-dominated region. On
the other hand, note that the line shapes of Ni 3p peak
(inset of fig. 2) for the two films are significantly different,
which also indicates different components of Ni. Therefore,
here we use the Ni 3p core-level spectrum to distinguish
Ni2+ and Ni3+ . Although its intensity is relatively weak
compared to that of the Ni 2p3/2 core-level peak, it
 Direct observation of Ni3+ and Ni2+ in correlated LaNiO3−δ films

Table 1: Fitting results of binding energy (BE), relative area (RA) and full width at half-maximum (FWHM) from Ni 3p XPS
spectra for the LNO films.
Peak Peak parameters Peak identification
LNO-1 LNO-2 Species Line
BE RA FWHM BE RA FWHM
(eV) (%) (eV) (eV) (%) (eV)
A 66.90 48.53 2.65 66.94 21.60 2.80 NiO 3p3/2
B 68.90 25.27 2.65 68.94 11.25 2.80 NiO 3p3/2
C 71.03 17.24 3.30 71.06 44.14 3.00 Ni2 O3 3p3/2
D 73.03 8.96 3.30 73.06 23.01 3.00 Ni2 O3 3p3/2

Fig. 3: (Colour on-line) Experimental and deconvoluted Ni 3p
XPS data for (a) LNO-2 and (b) LNO-1. The black circles:
the raw data; red lines: Ni2+ 3p3/2 (solid) and Ni2+ 3p3/2
(dashed) components; blue lines: Ni3+ 3p3/2 (solid) and Ni3+
3p3/2 (dashed) components; green lines: the spectra envelope.
is not interfered by other peaks thus the accuracy can
be guaranteed. Since the SOS energy between Ni 3p3/2
and Ni 3p1/2 is very small for both Ni3+ and Ni2+
∼ 2.2 eV [16,17], it can be assumed that the peak shape
and relative intensity ratio (RIR) for Ni3+ and Ni2+ are
the same in both Ni 3p3/2 and Ni 3p1/2 . To ensure the
quality of the peak fitting, a Shirley background and a
combined Lorentzian-Gaussian method is applied. The
fitting results for both films are presented in fig. 3 and
table 1. The peak at 66.9 eV (A) and 71.0 eV (C) can be
assigned to Ni2+ 3p3/2 and Ni3+ 3p3/2 which is consistent
with the reported results [18]. The obtained RIR of Ni
3p3/2 /Ni 3p1/2 is 1.92 for Ni2+ and Ni3+ in LNO-1 and
1.91 in LNO-2, which are very close to the theoretical
RIR value of 2 due to spin-orbit splitting. Based on these
results, the Ni3+ /Ni2+ ratios can thus be calculated, which
are 27.9/72.1 in LNO-1 and 67.2/32.8 in LNO-2. As a
result, the exact chemical formula for LNO-1 and LNO-2
Fig. 4: (Colour on-line) Temperature-dependent electric resis-
tivity for (a) LNO-1 and (b) LNO-2. The upper inset of (a)
shows the ln(ρ/T ) vs. 1000/T curve above 200 K, and the lower
inset shows the ln(ρ) vs. 1000/T curve for the LNO-1. The
upper inset of (b) shows the ρ vs. T 1.5 curve at 260–150 K,
and the lower inset shows the ρ vs. T 2 curve. (c) Schematic
diagram for the Ni3+ /Ni2+ ratio dependent transport mecha-
nism of LaNiO3−δ .
should be LaNiO2.64 (δ = 0.36) and LaNiO2.84 (δ = 0.16),
respectively. The results, in turn, confirm the experimental
observations that an increase in oxygen/argon ratio (from
0 : 4 to 3.5 : 0.5) results in an increased Ni3+ /Ni2+ ratio.
In order to understand the correlation between the
Ni3+ /Ni2+ ratio and electrical transport properties,
low-temperature resistivity measurements for both
LNO films have been carried out. Figure 4(a) displays
the temperature-dependent resistivity for LaNiO2.64 .
Obviously, lower Ni3+ /Ni2+ ratio in the film leads to
a semi-conducting behavior with a negative resistivity-
temperature coefficient (RTC). Based on the adiabatic
small polaron conduction mechanism, ρ(T ) can be
expressed by ρ(T ) = ρ0 T exp(Ea /kB T ) [19], where Ea
is the activation hopping energy for polarons and kB is
the Boltzmann constant. As seen in the upper inset of

57002-p3
Liang Qiao and Xiaofang Bi
fig. 4(a), over the high temperature range (T > 200 K),
the ln(ρ/T )-1000/T plot exhibits a clearly linear relation.
This result suggests that the conductivity originate from
the activated hopping of small polarons in the tempera-
ture range. From the ln(ρ/T )-1000/T curve, Ea of 46 meV
is obtained from the slope of the fitted line, which is
similar to the values reported in the cerium-doped LNO
system [20]. On the other hand, the classic Arrhenius
conduction model, ρ(T ) = ρ0 exp(Ea /kB T ), which is
commonly recognized in perovskite oxides [21], has also
been applied. As shown in the lower inset in fig. 4(a),
an obvious deviation is observed when T > 250 K, indi-
cating that the Arrhenius relation cannot describe well
the conducting behavior over this temperature range.
The Ea for electrons estimated from the initial slope
of the ln ρ-1000/T curve is 31 meV, which is smaller
than the value obtained from the small polaron hopping
mechanism. The extra energy required for the polarons
hopping compared to electrons transferring is also indica-
tive of a relatively large effective mass for the polarons in
LaNiO2.64 [19,22].
With increasing the Ni3+ /Ni2+ ratio, a different trans-
port behavior for the LaNiO2.84 is observed, as shown
fig. 4(b). Clearly, the increase of Ni3+ composition results
in a metallic conductive behavior with a positive RTC.
The corresponding transport mechanisms are discussed in
terms of various temperature ranges. At higher temper-
atures (T > 275 K), the ρ(T ) follows a linear relation:
ρ = ρ0 + AT , which is characterized by electron-phonon
(el -ph) scattering. The McMillan el-ph coupling constant
λ can be calculated by λ = (
ωP 2
/8π 2 kB )[ρ(T ) − ρ(0)]/T =
2
0.246(
ωP ) A, where
ωP is the plasma energy and A is
the slope of ρ(T ) [23]. Despite the lack of experimental
data,
ωP can be estimated by the Drude plasma energy:
(
ωP )2 = (ΩP )2 = (4/3)e2 NF (vF )2 , NF is the density
of states at the Fermi surface and vF is the Fermi
velocity [24]. Using NF and vF of LNO in ref. [25], the
corresponding values for the LaNiO2.84 are approximated
to be
ωP ∼ 1.14 eV and λ ∼ 0.1, respectively. Compared
with λ values of ∼0.14 for metallic LaNiO3 [26],
∼0.3 for superconductive YB2 Cu3 O7 [23], and ∼9
for strongly Jahn-Teller distorted LaMnO3 [27], the
rather smaller λ obtained here indicates a weak el -ph
coupling in LaNiO2.84 . In addition, using the relation
 = 4.95 × 10−4 vF /ρ(298 K)(
ωP )2 [23], the room temper-
ature mean free path () for LaNiO2.84 can be obtained as
∼13 Å. Although this value is greater than the dimensions
of its unit cell (∼3.84 Å), it is still much smaller than
the  value for either stoichiometric LaNiO3 (∼31 Å) or
metal Cu (∼390 Å) [26,28]. Over medium temperature
range (260 K–150 K), the ρ(T ) shows an obvious T 1.5 -
dependence (upper inset in fig. 4(b)). As the temperature
further decreases, the ρ(T ) deviates from T 1.5 -dependence
and gradually follows the relation, ρ = ρ0 + AKW T 2 at
T < 110 K (lower inset in fig. 4(b)). According to the
Landau–Fermi-liquid theory [29], the T 2 -dependence,
indicating the existence of electron localization, originates
57002-p4
from strong electron-electron (el -el ) scattering, whereas
the T 1.5 -dependence is due to the combination of
both el-ph and el-el interactions. To quantify the el-el
coupling, the Kadowaki-Woods ratio can be calculated
by rKW ≡ AKW /γ 2 from the slope of the ρ(T 2 ) line,
where γ is the electronic specific-heat coefficient [30].
Using the γ value for bulk LNO as an approxima-
tion (γ = 13.8 mJ/mol K2 ) [27–29], the rKW value is
determined to be ∼1.44a0 (a0 ≡ 10 µΩ cm mol2 K2 J−2 ).
Compared with heavy-fermion UPt3 (rKW ∼0.5a0 )
and quasi-2D Fermi-liquid Sr2 RuO4 (rKW ∼0.9a0 ), the
larger rKW value here indicates a strong el-el Coulomb
interaction in LaNiO2.84 , which is typical in a strongly
correlated 3 d electron system, such as La1.7 Sr0.3 CuO4 and
LiV2 O4 [30]. In addition, the effective mass for the electron
is estimated as mr = m∗ /m0 = ne2 ρ(298 K)/m0 vF ≈ 15,
where m0 is the static electron mass [25]. The large value
of mr and enhanced el-el scattering are suggested to be
the result of high electron concentration in the conduction
band due to the narrowing of conduction bandwidths,
which is probably caused by the proximity of the nearby
charge transfer (CT) type Mott transition [9,30]. It
should be noted that the effective mass value obtained
here is slightly higher than angle-resolved photomission
data (∼5) and the thermodynamic calculations (∼10) by
Eguchi et al. [31], and this may be driven by the slightly
oxygen non-stoichiometry.
The Ni3+ /Ni2+ ratio dependent transport mechanisms
of LaNiO3−δ films is thus schematically suggested, as
shown in fig. 4(c). Note that the metallic state for stoi-
chiometric LaNiO3 (Ni3+ ) arises from the overlapping of
occupied O 2p valence band and unoccupied Ni 3d-e∗g
conduction band [9]. With decreasing Ni3+ /Ni2+ ratio,
both the valence and conduction bandwidths are narrowed
due to the larger Ni2+ ionic radius and increase of Ni-O
bond length. As a result, the overlapping between these
two bands is reduced. A critical state between weak
metallic and semi-conductive exists for the LaNiO2.75 ,
where CT band gap between the two bands is nearly
zero, as reported by Sánchez et al. [1]. It can be there-
fore proposed that a further decrease in Ni3+ /Ni2+ ratio
from LaNiO2.75 to LaNiO2.64 continues to narrow the two
bands, leading to the presence of a small band gap. Mean-
while, the lattice vibration-induced phonons will facilitate
the hopping of electrons from valence bands to conduc-
tion bands, which may account for the observed small
polarons hopping behavior in the LaNiO2.63 lattice. Also,
the metallic behavior for LaNiO2.84 is obviously due to
the increase of Ni3+ /Ni2+ ratio, which leads to the clos-
ing of the CT band gap. However, the weaker conduc-
tion behavior of LaNiO2.84 with respect to stoichiometric
LaNiO3 is considered to be the result of reduced over-
lapping of the two bands. Moreover, narrowed conduc-
tion bandwidth will lead to higher electron concentra-
tion in the conduction band, which may also be respon-
sible for the observed high el -el Coulomb interaction
in LaNiO2.84 .
 Direct observation of Ni3+ and Ni2+ in correlated LaNiO3−δ films
Fig. 5: (Colour on-line) Schematic supercell structure for
(a) LaNiO3 , (b) LaNiO2.75 , (c) LaNiO2.5 and calculated DOS
for the three systems near the EF .
Finally, first-principle calculations are also used
to investigate the electronic structure of the system
with different Ni3+ /Ni2+ ratios. The calculations were
performed within the framework of density functional
theory by the local-density approximation, with the
exchange correlation potential of Ceperley and Alder as
parametrized by Perdew and Zunger [32,33]. A plane-
wave basis set with an energy cutoff of 300 eV, k-point
of 3 × 7 × 3, and ultrasoft pseudopotentials is used.
Figures 5(a)–(c) are schematic supercells of La4 Ni4 O12 ,
La4 Ni4 O11 and La4 Ni4 O10 , which were used to model
the crystal structure of metallic LaNiO3 , semi-conductive
LaNiO2.75 and insulate LaNiO2.5 . All the structures were
optimized by the Broyden-Fletcher-Goldfarb-Shanno
method [34], and the forces on each ion were converged to
less than 0.01 eV/Å. Figures 5(d)–(f) show the obtained
electronic density of states (DOS) for the three systems
near the Fermi level (EF ). For stoichiometric LNO the
valence band maximum (VBM) and conduction band
minimum (CBM) is actually overlapped with each other,
which enables transport of free electrons across the EF
level and maintains the metallicity. Decreasing the oxygen
content to LaNiO2.75 , both conduction band and valence
band are narrowed and a critical state exists where VBM
and CBM is un-overlapped with a zero band gap. At
this stage, due to a small band gap, with the facilitation
of lattice phonons, the polarons can still be formed
and transferred between lower valence band and upper
conduction band to maintain the semi-conductivity. While
57002-p5
for LaNiO2.5 , the two bands continue narrowing and a
giant band gap appears, making it a totally electronic
insulator.
In summary, using XPS deconvolution and peak fitting
analysis, Ni3+ and Ni2+ in LaNiO3−δ films are distin-
guished and their ratio is quantified. The Ni3+ /Ni2+ ratio
dependent transport mechanism of LaNiO3−δ is clarified
based on transport measurements and first-principle calcu-
lations. It is suggested that higher Ni3+ /Ni2+ ratio be
correlated with reduced el -ph interaction, shortened mean
free path, and increased el-el coupling in the strongly
correlated system.
∗∗∗
This work is supported by the Innovation Foundation of
BUAA for PhD Graduates and program for New Century
Excellent Talents in university (NCET-04–0160).
REFERENCES
[1] Sánchez R. D., Causa M. T., Caneiro A., Butera A.,
Vallet-regı́ M., Sayagués M. J., González-calbet
J., Garcı́a-sanz F. and Rivas J., Phys. Rev. B, 54
(1996) 16574.
[2] Wu G. Q., Neumeier J. J. and Hundley M. F., Phys.
Rev. B, 63 (2001) 245120.
[3] Abbate M., Zampieri G., Prado F., Caneiro A.,
González-calbet J. M. and Vallet-regı́ M., Phys.
Rev. B, 65 (2002) 155101.
[4] Dobin A., Nikolaev K. R., Krivorrotov I. N.,
Wentzcovitch R. M., Dahlberg E., Dan and
Goldman A. M., Phys. Rev. B, 68 (2003) 113408.
[5] Berini B., Keller N., Pigeau B., Dumont Y.,
Popova E., Franco N. and Dasilva R. M. C., J. Appl.
Phys., 104 (2008) 103539.
[6] Scherwitz R., Zubko P., Lichtensteiger C. and
Triscone J. M., Appl. Phys . Lett., 95 (2009) 222114.
[7] Qiao L. and Bi X. F., J. Phys. D: Appl. Phys., 41 (2008)
195407.
[8] Qiao L. and Bi X. F., Acta. Mater., 57 (2009) 4109.
[9] Torrance J. B., Lacorre P., Nazzal A. I., Ansaldo
E. J. and Niedermayer Ch., Phys. Rev. B, 45 (1992)
8209.
[10] Escote M. T., Pontes F. M., Leite E. R., Varela
J. A., Jardim R. F. and Longo E., Thin Solid Films,
445 (2003) 54.
[11] Mickevicius S., Grebinskij S., Bondarenka V.,
ˇ
Vengalis B., Sliuziene K., Orlowski B. A., Osinniy
V. and Drube W., J. Alloys Compd., 423 (2006) 107.
[12] Asha A. M. D. E., Critchley J. T .S. and Nix R. M.,
Surf. Sci., 405 (1998) 201.
[13] Novosselov A., Talik E. and Pajaczkowska A.,
J. Alloys Compd., 351 (2003) 50.
[14] Qiao L. and Bi X. F., J. Cryst. Growth, 310 (2008) 3653.
[15] Mullica D. F., Lok C. K. C., Perkins H. O. and
Young V., Phys. Rev. B, 31 (1985) 4039.
Liang Qiao and Xiaofang Bi
[16] Clauberg R., Gudat W., Kisker E., Kuhlmann E.
and Rothberg G. M., Phys. Rev. Lett., 47 (1981)
1314.
[17] Moulder J. F., Stickle W. F., Sobol P. E. and
Bomben K. D., Handbook of X-ray Photoelectron Spec-
troscopy (Perkin-Elmber Corporation, Minnesota) 1992.
[18] Marco J. F., Gancedo J. R., Ortiz J. and Gautier
J. L., Appl. Surf. Sci., 227 (2004) 175.
[19] Mott N. F., Metal-Insulator Transition, 2nd edition
(Taylor & Francis, London) 1990, p. 59.
[20] Lekshmi I. C., Gayen A., Sarma D. D., Hegde M. S.,
Chockalingam S. P. and Chandrasekhar N., J. Appl.
Phys., 98 (2005) 093527.
[21] Richter J., Holtappels P., Vogt U., Graule T. and
Gauckler L. J., Solid State Ionics, 177 (2006) 3105.
[22] Elliot S. R., The Physics and Chemistry of Solids
(Wiley, Chinchester) 1998, p. 513.
[23] Gurvitch M. and Fiory A. T., Phys. Rev. Lett., 59
(1987) 1337.
[24] Chakraborty B., Pickett W. E. and Allen P. B.,
Phys. Rev. B, 14 (1976) 3227.
[25] Xu X. Q., Peng J. L., Li Z. Y., Ju H. L. and Greene
R. L., Phys. Rev. B, 48 (1993) 1112.
57002-p6
[26] Mambrini G. P., Leite E. R., Escote M. T., Chiq-
uito A. J., Longo E., Varela J. A. and Jardim R. F.,
J. Appl. Phys., 102 (2007) 043708.
[27] Pal S., Banerjee A., Rozenberg E. and Chaudhuri
B. K., J. Appl. Phys., 89 (2001) 4955.
[28] Rajeev K. P. and Raychaudhuri A. K., Phys. Rev. B,
46 (1992) 1309.
[29] Horiba K., Eguchi R., Taguchi M., Chainani A.,
Kikkawa A., Senba Y., Ohashi H. and Shin , Phys.
Rev. B, 76 (2007) 155104.
[30] Li S.Y., Taillefer L., Hawthorn D. G., Tanatar
M. A., Paglione J., Sutherland M., Hill R. W.,
Wang C. H. and Chen X. H., Phys. Rev. Lett., 93 (2004)
056401.
[31] Eguchi R., Chainani A., Taguchi M., Matsunami M.,
Ishida Y., Horiba K., Senba Y., Ohashi H. and Shin
S., Phys. Rev. B, 79 (2009) 115122.
[32] Ceperley D. M. and Alder B. J., Phys. Rev. Lett., 45
(1980) 566.
[33] Perdew J. P. and Zunger A., Phys. Rev. B, 23 (1981)
5048.
[34] Fischer T. H. and Almlof J., J. Phys. Chem., 96
(1992) 9768.