Thin Solid Films 520 (2012) 59655970

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Thin Solid Films

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Ab initio investigation on a promising transparent conductive oxide, Nb:SnO2

Guanglei Zhang a, b, Guoqiang Qin a, b,, Gang Yu a, Qianku Hu b, c, Hua Fu a, Changtao Shao a
a
School of Materials Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang, Hebei Province, 050043, China
b
State Key Laboratory of Metastable Materials Science and Technology (Yanshan University) 066004 Qinhuangdao, China
c
School of Material Science and Engineering, Henan Polytechnic University, Jiaozuo, Henan Province, 454010, China

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

Article history: The effects of Nb dopant on the lattice structure, thermal, electronic, and optical properties of rutile-phased
Received 18 November 2010 SnO2 were investigated via ab initio calculations. The corresponding effects of Sb and Ta dopants were also
Received in revised form 19 April 2012 studied for comparison. Results indicated that after SnO2 was doped with Nb, the differences in ionic radii,
Accepted 19 April 2012
electron congurations, and electronegativities between the native element and the heterogeneous dopant
Available online 28 April 2012
led to the variations in lattice structure, thermal stability, and electron distribution, while the tetragonal sym-
Keywords:
metry of the rutile phase is conserved. The partially lled bands around Ef originated from Nb dopant led to
Tin compounds the severe enhancement of conductivity, electron excitation in infrared region, and the consequent optical
Simulation properties except for the band gaps and the selection rule restricting the electron excitation in the visible
Dopants light region. Therefore, the visible transparency of Nb:SnO2 is expected to be comparable with or even better
Electrical properties than Ta:SnO2.
Optical properties 2012 Elsevier B.V. All rights reserved.

1. Introduction the electron conductance; 2) minimizing the changes in the lattice

Transparent conductive oxides (TCOs) have been regarded as key
materials because of their superior electronic and optical properties,
and their signicant applications in various elds, such as solar cells
and at panel displays [1]. However, due to the limitations in element
enrichment and physical properties of indium tin oxide (ITO, In2O3
doped with Sn as n-type donor), which is recognized as the dominant
TCO material with both high sheet conductance and transparency for
visible light [2], it is urgent to explore high-performance, and low-
cost TCO material. SnO2-based TCO is one of the promising candidates,
but further detailed studies should be carried out to promote its per-
formance, such as the lower electron conductance among others.
Electron conductivity is determined by the density of the charge
carrier and its mobility, which can be altered by the doping method,
as frequently employed in literature. Optical transparency can also
be altered by the dopant through the changes in lattice and electronic
structure. Unfortunately, the effects of dopant on the electron con-
ductance and optical transparency are often in different directions
at the same time. Therefore, an initial comprehensive estimation
should be done to obtain a primary principle or criterion, and to fur-
ther obtain the material with optimized properties. Normally, the
general principle to select a dopant in TCO includes two crucial
trends: 1) increasing the density of the charge carrier to promote
structure to reduce the density of defects to keep a high visible trans-
parency. For SnO2-based TCO with n-type conductivity, the suitable
dopant should provide more valence electrons than Sn or O atoms
and possess ionic radii close to or the same as Sn 4+ or O 2. Toyosaki
[3] validated the simple selection principle through experiments
where the ionic radii of Sn 4+ (0.069 nm), Sb 5+ (0.060 nm), and
Ta 5+ (0.064 nm) were considered before Ta was chosen as dopant.
The as-prepared Sn0.95Ta0.05O2 (TTO) lms exhibited a resistivity as
low as 1.1 10 4 cm, which is comparable to the optimal value
of the In2O3 lm. Other studies revealed that TTO lms can grow on
Al2O3 (0001) substrates or rutile TiO2 and NbO2 seed-layers on bare
glass [4,5], indicating a weak dependence of Ta-doped SnO2 thin
lm on the environment, thus showing a strong intrinsic stability.
Considering the ionic radii, the value of Nb 5+ is 0.069 nm, just the
same as that of Sn 4+. Following the selection principle proposed
above, Nb:SnO2 is expected to possess superior electronic and optical
properties to Ta:SnO2 as TCO material. However, there are only a few
reported theoretical studies on Nb:SnO2. To obtain a better under-
standing and helpful guidelines, the current paper, focused on the ef-
fects of Nb dopant on the thermal, structural, electronic, and optical
properties of SnO2.
2. Theoretical methods

CASTEP code [6] was employed to calculate the structural, elec-

Corresponding author at: School of Materials Science and Engineering, Shijiazhuang
Tiedao University, Shijiazhuang, Hebei Province, 050043, China. Tel.: +86 31187936084;
fax: +86 31187935416.
E-mail address: sjzqgq@126.com (G. Qin).
tronic, and optical properties of SnO2 by rst principle calculations
based on a plane wave basis set with periodic boundary conditions.
The electronelectron exchange and correlation effects were

0040-6090/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2012.04.049
5966 G. Zhang et al. / Thin Solid Films 520 (2012) 59655970

described by PerdewBurkeEruzerhof in the generalized gradient

approximations (GGA) [7] within the density functional theory
(DFT). Ultrasoft pseudo-potentials [8], known for their high efciency
in calculating structural and electronic properties, were used for the
electron ion interactions. Norm-conserving pseudo-potentials [9]
were adopted to obtain optical properties for its higher reliability in op-
tical property description. Sn 5s25p 2, O 2s22p 4, and Nb 4s24p 64d 45s 1
were treated as valence states.
Supercell technology was employed to model the Nb-doped SnO2,
where a 2 2 1 supercell (containing 8 SnO2 formula units) and a
larger 2 2 2 supercell (containing 16 SnO2 formula units) were
built. The Brillouin zone integration was performed over a
3 3 8 K and a 3 3 4 K points set for these two supercells, respec-
tively. The differences in the energies/atom as well as the electronic
and optical properties obtained by these two supercells with the
same dopant contents were found negligible.

3. Results and discussions

Stannic oxide posses the tetragonal symmetric lattice in the P42/

mnm (No. 136) space group with the face-centered cubic phase. The
unit cell of SnO2 is characterized by the two lattice constants a, c,
and the internal parameter u. The positions
of the four oxygen
atoms are (u, u, 0) and
12 u; 12 u; 12 , respectively. To conrm
the convergence of calculations, the dependences of the total energy
required in calculating the solid state with respect to the scheme of
Lin [10], the lattice parameters on the cutoff energy, and the
Brillouin-zone k-point set mesh (according to the MonkhorstPack
grid) were investigated.
As shown in Fig. 1a, for the rutile-phase SnO2, if the k-point set
mesh is xed at 5 5 8, the change in total energy is less than
10 meV when the cutoff energy is higher than 1100 eV. On the other
hand, if the cutoff energy is xed at 700 eV, the convergence in total
energy is good when the k-point set mesh exceeds 7 7 10. The lat-
tice parameters were also affected by the congurations of the cutoff
energy and the k-point set mesh (Fig. 1b). Considering the computa-
Fig. 1. Dependences of the total energy (a) and lattice parameters (b) on the cutoff en-
tional cost, the cutoff energy (1200 eV) and the k-point set ergy and the Brillouin-zone k-point set mesh.
(8 8 12) for the rutile-phase SnO2 were chosen, which makes the
separation of the reciprocal space to be less than 0.02 1. Under
this conguration, the obtained lattice constants of a and c were
4.831 1 and 3.247 1, respectively (Table 1). Due to the well-
known over-estimation of GGA on atomic bonding, the optimized (Ecoh) and the standard enthalpy of formation (Hf). Ecoh is often de-
primitive cell in the current research is larger than the experimental ned as the work needed when the crystal decomposes into single
cell by a few percent [1113], but the discrepancy is comparative to atoms, while Hf as the enthalpy change associated with the forma-
other local density approximation (LDA) or GGA calculations. [1416]. tion of a compound from its constituent elements in their standard
The doped structure is usually deformed to some extent due to the states. Using the similar method in Ref. [19], Hf is determined as:
differences in ionic radii, electronegativity, and electron congura- Hf (DxSn1 xO2) = xIn + (1 x) Sn + 2O, where the chemical po-
tions between the native elements and dopants. In the current tentials O, Sn, and D are referred to the calculated total energies
study, the tetragonal symmetry of the rutile phase is conserved of O in O2 molecules [1/2 Etot (O2)], Sn in -Sn phase (Fd-3m, number
after it was doped with Nb [17], whereas the lattice constants elon- 227, primitive face-centered-cubic (FCC) structure) [Etot (Sn 0)] and
gated and the volume of crystal lattice cell (V) expanded. The volume dopant in its most stable mono-composition phase. For dopant such
of crystal lattice cell is expanded by 4.21% when the Nb dopant level as Sb, the corresponding phase takes the same FCC structure and
was at 12.5% (corresponding to a molecular formula Sn7NbO16). In space group as -Sn but different lattice parameters, thus is a kind
view of the same ionic radii of Sn 4+ and Nb 5+, the volume change of deformed -Sn. For Ta and Nb dopants, the corresponding phase
in Nb:SnO2 is mainly attributed to the different electronegativity takes the Im-3m space group (number 229) with primitive body-
and electron congurations, which induce the rearrangement of centered-cubic (BCC) structure. The calculated values of Ecoh and
local atomic congurations. On the other hand, if the dopant with dif- Hf for pure rutile-SnO2 are 6.18 eV/atom and 5.75 eV/atom, re-
ferent ionic radii (i.e. Sb:SnO2 or Ta:SnO2) is involved the dopant with spectively, giving a good quantitative accord with respect to the ex-
smaller ionic radii will lead to a larger volume expansion (Table 1), perimental and theoretical values [1922]. The large absolute values
where the values of V for Sn7SbO16 and Sn7TaO16 are 6.05% [18] of Ecoh and Hf for SnO2 showed that SnO2 is the most thermodynam-
and 5.24%, respectively. Moreover, the relative change in volume ically stable form of tin oxides, as conrmed by Duan [16].
does not depend on the absolute value of the ionic radii but on the Due to the mistness of the ionic radii and valence electron con-
differences between them, i.e., the larger difference causes a larger gurations between the heterogeneous dopant and native elements,
expansion. the absolute values of Ecoh and Hf are always reduced, which indi-
The structural deformation caused by dopant is affected by varie- cates the decline in thermal stability, similar to what happens in Sb:
ties in thermal stability, which can be revealed by the cohesive energy SnO2 [18]. This trend also leads to the limitations in dopant
 G. Zhang et al. / Thin Solid Films 520 (2012) 59655970 5967

Table 1
Lattice constants, cell volume (V), cohesive energy (Ecoh) and the standard enthalpy of formation (Hf) of pure and doped rutile-SnO2.

a/ c/ u V/3 Ecoh/(eV/atom) Hf/(eV/atom)

SnO2 (primitive cell) 4.831 3.247 0.3061 75.780 6.18 5.75

Experiment 4.737 [11,12] 3.186 [11,12] 0.307 [11,12] 71.491 0.44 Ryd [20] 5.98 [19]
4.73 [13] 3.18 [13] 4.79 [21]
4.80 [22]
DFTLDA 4.738 [14] 4.580 [15] 3.188 [14] 3.080 [15] 0.30756 [14] 0.3044 [15] 5.89 [21]
5.17 [22]
DFTGGA 4.825 [15] 3.245 [15] 0.3065 [15] 5.39 [16] 5.21 [19]
4.821 [16] 3.236 [16]
GGA + U 303.12 6.03 [19]
Sn7SbO16 9.806 3.305 321.453 6.16 5.69
Sn7TaO16 9.855 3.284 318.989 6.48 6.04
Sn7NbO16 9.824 3.273 315.888 6.59 6.17

concentrations, as reported in the literature [19,23]. Ecoh and Hf
could be treated as indicators of the strength of chemical bonding,
which is related to chemical stability. The reduced Ecoh and Hf also
suggests a weakening in bonding strength and chemical stability. Fur-
thermore, changes in Ecoh and Hf on the ionic radii of dopant can be
clearly afrmed. Ecoh and Hf from Ta and Nb dopant is even larger
than pure SnO2, which reveals a development in thermal stability of
the doping system. Despite the disadvantage of DFT in predicting
the behavior of the electron in d orbital (which might cause inaccu-
rate energy calculations), it can be implied that the closer the ionic
radii to Sn 4+, the more stable the doping system is. This conclusion
leads to a natural evolvement that a higher dopant level can be
achieved in Ta:SnO2 and Nb:SnO2 than Sb:SnO2.
Fig. 2 shows the energy band structure and density of states (DOS)
of pure rutile-SnO2 and Sn7NbO16 (which corresponds to a dopant
concentration of 12.5%). For SnO2, the Sn 5p-like non-bonding orbitals
dominate the DOS in the highest occupied molecular-orbital (HOMO)
level, while the lowest unoccupied molecular orbital (LUMO) in con-
duction band is composed mainly of Sn 5s states, which shows the
free-electron-like character of the conduction band in the -Z and -
M directions [24]. The locations of peaks in the valence and conduc-
tion band as well as the width of valence band are in accordance

Fig. 2. Energy band structure and density of states (DOS) of pure rutile-SnO2 and Sn7NbO16. The Fermi level (Ef) is set as relative zero. (a) Band structure of rutile-SnO2, (b) DOS of
rutile-SnO2, (c) band structure of Sn7NbO16, and (d) DOS of Sn7NbO16.
5968 G. Zhang et al. / Thin Solid Films 520 (2012) 59655970

with the ultraviolet photoemission spectroscopy measurements

[2527] and previous report [19]. Kawazoe [28] suggested that a
strong localization of the upper edge of the valence band with high ef-
fective mass, along with the free electron-like character of the con-
duction band bottom, leads to a typical n-type semiconductor. The
calculations displayed a direct band gap of about 1.2 eV between
the LUMO and HOMO levels at point, which is comparable to
other DFT results (1.8 eV) [29]. The calculated band gap of SnO2 is
smaller than the experimental measurements due to the underesti-
mation of the excited state energies in the DFT approximations
(3.6 eV) [30]. As presented in Ref. [16], the correlation effects are
large because tin oxides are essentially Mott insulators.
After doping by Nb, three narrow bands with very keen-edged
peaks appear deeply at the low energy region (Figs. 2c, d, and 3).
The bands located at about 57 eV and 34 eV originate from the
Nb 4s and Nb 4p orbitals respectively, whereas the band located at
about 20 eV is dominated by the O 2s orbitals which is partially
mixed with Sn 2s and Sn 2p orbitals. These three bands are not nor-
mally involved in the mechanisms of charge conductivity, electron ex-
citation, and the consequent optical behaviors. Comparatively, the
main shape of valence band remains unaltered, but the location of Ef
is elevated due to the higher valence electron density of Nb with re-
spect to Sn. As a result, a relatively downward movement of about
2.3 eV of the valence band is clearly seen. The originated band gap is
depressed to be 0.8 eV due to the many-body effect. Two partially
lled energy bands covering 1.52 eV to 0.49 eV and 0.15 eV to
0.80 eV (which can also be labeled in the band structure and electron
orbitals), respectively, can be identied in the conduction band. The
former is hybridized by Sn 5s orbitals and O 2p orbitals while the latter
is hybridized by Nb 4d orbitals and O 2p orbitals; slightly mixed with
Sn 5s orbitals. These two bands make up the lower energy part of
the conduction band. A hybridized band by Sn 5s orbitals and O 2p or-
bitals takes the higher energy part, similar to SnO2. Although the ener-
gy gap is very tiny, no direct cross takes place between the two
partially lled bands and the other adjacent bands in the upper region.
A pseudo-band gap (about 0.3 eV) appears between the lower part of
the conduction band and the higher part. Similar with SnO2, the con-
duction band and the other band at higher energy region are separat-
ed by a band gap of about 0.5 eV at ~4 eV. The probability of electron
transition caused by optical excitation strongly relies on the DOS of
ground state and excitation state is recognized. The pseudo-band
gap and band gap above Fermi energy might ercely depress the elec-
tron transition in the middle-energy region, reducing the optical re-
ectivity and absorption of visible light (Fig. 4). To summarize, the
partially lled bands around Ef originated from Nb dopant led to the
remarkable enhancement of conductivity, electron excitation in
low energy region (infrared region), the consequent changes in
dielectricity, absorption, reectivity, refractivity, and other optical
properties. The dielectric function () and all the other optical con-
stants are caused by the real transitions between occupied states (va-
lence bands) and unoccupied electronic states (conduction bands).
However, the electron excitations in the middle energy region
(about 2 eV to 4 eV, visible light region) have no remarkable change Fig. 3. PDOS of Sn7NbO16. Ef is set as relative zero. (a) PDOS of O, (b) PDOS of Sn, and (c)
due to the band gaps and the selection rule. Therefore, the visible PDOS of Nb.
transparency of Sn7NbO16 is likely comparable to SnO2.
The introduction of dopant leads to the changes in electron and the electron and charge distribution is exhibited. For example, the
charge distributions. This can be indicated by Mulliken population, atomic populations for individual Sn and O atom are Sn 5s 25p 2 and
which is calculated using a technique for the projection of plane- O 2s 22p 4, respectively. After incorporating into the tetragonal rutile
wave states onto a linear combination of an atomic orbital basis set lattice, the electrons re-distributed according to the electronegativity
described in Ref. [26]. It is accepted that the absolute magnitude of of the different atoms and interactions of electron orbitals, while the
the atomic charges yielded by population analysis have little physical primary separate electron orbitals expanded into energy bands. As a
meaning because they display a high degree of sensitivity to the result, the corresponding atomic populations changed into Sn
atomic basis set. However, useful information can be obtained by con- 5s 0.905p 1.26 and O 2s 1.882p 5.04, respectively. 1.84 e (1.1 e from Sn 5s
sidering the relative values. electron and 0.74 e from Sn 2p electron) is transferred from the tin
The calculated atomic and bond populations of pure and doped atom to oxygen atom (mainly into O 2p level), hence Sn and O
SnO2 are shown in Table 2, where an evident inuence of species on obtained 1.84 positive charges/atom and 0.92 negative charges/
 G. Zhang et al. / Thin Solid Films 520 (2012) 59655970 5969

is presently unclear and more detailed work is still needed to disclose

the origin.
In addition to providing an objective criterion for bonding be-
tween atoms, the overlap population can be used to assess the cova-
lent or ionic nature of a bond. A high value of the bond population
indicates a covalent bond, while a low value indicates an ionic inter-
action. A zero value indicates a perfectly ionic bond, while values
greater than zero indicate increasing levels of covalency [33]. Calcula-
tions made in the current experiment revealed two kinds of Sn\O
bond in SnO2. The longer bond takes more ionic character and the
shorter bond shows more covalent nature. The rutile SnO2 consists
of a series of neutral groups of O\Sn2O2\O along a (110) direction
where the shorter bond dwells in O\Sn2O2\O neutral group and
the longer Sn\O bond is positioned between adjacent O\Sn2O2\O
neutral groups or parallel (110) planes. Therefore, the chemical
bonds in the neutral O\Sn2O2\O group in SnO2 acquire a more cova-
lent character, while the bonds between different O\Sn2O2\O
groups or parallel (110) planes show more ionic nature.
The introduction of dopant also shows the important inuence on
the bond population. Table 2 shows that the values of X\O (X de-
notes the dopant) bond populations increase with the decreasing
electronegativity of dopant, which indicates the increased contribu-
tion of the covalent nature in local region close to the dopant. Howev-
er, the change in the bond nature of the entire lattice is insignicant
because the concentration of dopant is very low.
Lastly, cost is an important factor to be considered in the actual
application of a real device. Considering the relative abundance of
the chemical elements in the lithosphere, the corresponding values
for Sn, In, Sb, and Ta are 2.2 ppm, 0.049 ppm, 0.2 ppm, and 2 ppm, re-
spectively [34], while the value for Nb is 20 ppm, which is dramatical-
ly larger than all the other elements. Therefore, Nb:SnO2 is expected
to be a promising candidate for a high-performance, and low-cost
TCO material with massive potential applications in solar cells, at
panel displays, heat reection devices, and so on.

Fig. 4. Varieties of reectivity (a) and absorption (b) along (110) and (001) directions
of pure and Nb doped SnO2. Two dash lines give the visible range of the spectrum.
atom, respectively, which is different from what is expected from
Sn 4+ and O 2 but in accordance with Ref. [32]. After doping with
Nb atom, the atomic populations shifted from Nb 4s 24p 64d 45s 1 to
Nb 4s 24p 6.304d 2.915s 0.38, revealing a charge transfer of about 1.41 e
(mainly from Nb 4d electron) to oxygen through orbital hybridiza-
tion, which is less than that of Sn. Electronegativity is known as a
chemical property that describes the ability of an atom to attract elec-
trons (or electron density) toward itself [33]. The inuence of electro-
negativity on the charge transfer is clearly exhibited in the
calculations, where the values of the charge transfer follow the
order of Sb (2.15) > Sn (1.84) > Nb (1.41) > Ta (1.32), in line with de-
creasing order of electronegativity of these elements in Pauling scale
[Sb (2.05) > Sn (1.96) > Nb (1.6) > Ta (1.5)]. The reason for this trend
4. Conclusions
After doping with Nb, the tetragonal symmetry of rutile phase
SnO2 is conserved, the lattice constants are increased, the volume of
crystal lattice cell is expanded, and the thermal stability as well as
the electron distribution is also affected. The differences in ionic
radii, electron congurations, and electronegativity between the na-
tive element and the dopant, account for these changes.
The partially lled bands around Ef originating from the Nb dopant
led to the remarkable enhancement of conductivity, electron excita-
tion in the low energy region (infrared region), and the consequent
optical properties, while the visible transparency of Nb:SnO2 is
expected to be comparable with SnO2 at a dopant level of 12.5% Nb,
because band gaps and the selection rule restrict the electron excita-
tion in the visible light region. Therefore, Nb:SnO2 is a promising TCO
material with application prospects. Moreover, the current study

Table 2
Valence states, atomic and bond populations of SnO2 and X:SnO2, X = Sb, Ta or Nb.

Valence states Atomic population Bond population

s p d Total Charge/e Bond Length/ Population

SnO2 Sn 5s25p2 0.90 1.26 2.16 1.84 Sn-OI 2.123 0.3

[31] O 2s22p4 1.88 5.04 6.92 0.92 Sn-OII 2.119 0.72
1.86 2.030 0.34
0.93 2.023 0.75
Sn7SbO16 Sb 5s25p3 1.23 1.63 2.85 2.15 Sb-OI 2.112 0.52
Sb-OII 2.089 0.25
Sn7TaO16 Ta 5d36s2 0.47 0.34 2.88 3.68 1.32 Ta-OI 2.136 0.97
Ta-OII 2.096 0.55
2 6 4 1
Sn7NbO16 Nb 4s 4p 4d 5s 2.38 6.30 2.91 11.59 1.41 Nb-OI 2.0718 0.86
Nb-OII 1.9995 0.48
5970 G. Zhang et al. / Thin Solid Films 520 (2012) 59655970

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