Article

pubs.acs.org/JPCC

Structure, Morphology, and Optical Properties of Amorphous and

Nanocrystalline Gallium Oxide Thin Films
S. Sampath Kumar,†,‡ E.J. Rubio,† M. Noor-A-Alam,† G. Martinez,† S. Manandhar,§ V. Shutthanandan,§
S. Thevuthasan,§ and C.V. Ramana*,†
†
Department of Mechanical Engineering, University of Texas at El Paso, El Paso, Texas 79968, United States
‡
Department of Electrical and Computer Engineering, University of Texas at El Paso, El Paso, Texas 79968, United States
§
Environmental Molecular Sciences Laboratory (EMSL), Pacific Northwest National Laboratory (PNNL), Richland, Washington
99352, United States

ABSTRACT: Gallium oxide (Ga2O3) thin films were produced by sputter deposition
by varying the substrate temperature (Ts) in a wide range (Ts = 25−800 °C). The
structural characteristics and optical properties of Ga2O3 films were evaluated using X-
ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray
spectrometry (EDS), Rutherford backscattering spectrometry (RBS), and spectro-
photometric measurements. The effect of growth temperature is significant on the
chemistry, crystal structure, and morphology of Ga2O3 films. XRD and SEM analyses
indicate that the Ga2O3 films grown at lower temperatures were amorphous, while
those grown at Ts ≥ 500 °C were nanocrystalline. RBS measurements indicate the
well-maintained stoichiometry of Ga2O3 films at Ts = 300−800 °C. The spectral
transmission of the films increased with increasing temperature. The band gap of the
films varied from 4.96 to 5.17 eV for a variation in Ts in the range 25−800 °C. A
relationship between microstructure and optical property is discussed.

■ INTRODUCTION
There has been a great deal of interest in the wide band gap
oxide materials for electronics, electro-optics, opto-electronics,
and magneto-electronics. These materials find a wide range of
applications in photoresistors, photodiodes, luminescent
phosphors, electronic switches, and gas sensors. Gallium
oxide (Ga2O3), which is a stable oxide of Ga, is a wide band
gap material. 1−6 Ga2O3 finds attractive applications in
luminescent phosphors,7 high-temperature sensors,8−11 antire-
flection coatings, and solar cells.10 Ga2O3 has been recognized
as a deep ultraviolet transparent conducting oxide (UV−
TCO),1−5,13 which makes the material a potential candidate for
transparent electrode applications in UV optoelectronics.6,14−16
While conventional transparent oxides such as In2O3, SnO2,
ZnO, and ITO are opaque in the UV region due to a small
band gap (∼3 eV), Ga2O3 exhibits a wide band gap (∼5 eV)
and deep transparency to the UV region.4,6,12−16
Gallium oxide can crystallize in five different crystal
structures: α, β, γ, δ, and ε phases.17,18 Among these phases,
β-Ga2O3 is the most stable form with thermal and chemical
stability. The melting point of β-Ga2O3 is 1780 °C10,17 which is
useful to readily integrate the material in high-temperature
applications. The crystal structure of β-Ga2O3 is base-centered
monoclinic (space group C2/m)17,18 where the oxygen ions are
in a distorted cubic packing arrangement and the gallium ions
are in distorted tetrahedral and octahedral sites.18 The lattice
parameters of β-Ga2O3 are a = 12.2140(3) Å, b = 3.0371(9) Å,
c = 5.7981(9) Å, and β = 103.83°.19−23 Despite great promise,
studies on β-Ga2O3 are rather scarce compared to other well-
explored wide band gap oxides. While there are a number of
reasons, the most important and challenging ones are: (a)
difficulties in preparing single crystals, thin layers and/or their
surfaces with sufficient quality, and (b) complications due to a
large band gap, which is a major hindrance for the powerful
electron-based spectroscopic methods.2 Additionally, for thin
films grown using either physical or chemical vapor deposition
methods, properties and phenomena of β-Ga2O3 films depend
on the processing conditions such as base pressure,9 growth
temperature,24,25 reactive pressure (if any), deposition rate, and
annealing conditions. Therefore, the controlled growth and
manipulation of specific crystal structures of β-Ga2O3 at the
nanoscale dimensions has important technological implications.
The fundamental, microscopic characteristics such as the
optical properties and electrical conductivity mechanism of β-
Ga2O3 films are not well understood, specifically at the reduced
dimensions, compared to the best studied wide band gap
transparent conducting oxides. Sin-Liang Ou et al.25 have
fabricated gallium oxide thin films by pulsed laser deposition
(PLD) under variable substrate temperature. The structural,
optical, and etching properties of the films were investigated.
The phase transition of the films was observed; crystallinity of
gallium oxide was enhanced; and the etching rate decreased
with increasing temperature. Baban et al.26 have reported the
oxygen sensing mechanism of gallium oxide thin films prepared
Received: November 15, 2012
Revised: December 29, 2012
Published: February 15, 2013

© 2013 American Chemical Society 4194 dx.doi.org/10.1021/jp311300e | J. Phys. Chem. C 2013, 117, 4194−4200
The Journal of Physical Chemistry C
by RF magnetron sputtering. Hyoun Woo Kim et al.24 have
deposited gallium oxide on silicon by metal organic chemical
vapor deposition (MOCVD) by reacting trimethylgallium with
oxygen. The investigations on the growth and structure of the
films showed that the films were amorphous with roughness
increasing as a function of temperature. Guzman-Navarro et
al.27 have discussed the cathodoluminescence study of gallium
oxide films grown by thermal evaporation of GaN. Con-
densation and subsequent oxidation of metallic Ga is suggested
as the growth mechanism of gallium oxide nanowires. Thermal
annealing of oxygen vacancies is proposed as the responsible
mechanism for the observed behavior. Orita et al.1 have
fabricated the gallium oxide thin films on silica glass substrates
by the PLD method and have demonstrated high conductivity
and high transparency by reducing the oxygen pressure in the
chamber and increasing the substrate temperature. Mohamed et
al.2 have fabricated gallium oxide by the Czochralski method
and have shown that the (100) cleavage plane gives a surface of
high perfection and the degree of correspondence of the
electronic band structure between hybrid density functional
theory (DFT) and angle-resolved photoelectron spectroscopy
(ARPED) measurements for valence bandwidth, band mass,
and individual dispersions is good. Rebien et al.15 have prepared
gallium oxide films on GaAs by electron-beam evaporation of
gallium oxide pellets and also with RF magnetron sputter
deposition. The linear optical functions of the thin film in the
ultraviolet−visible−near-infrared (UV−vis−NIR) spectral
range were in good agreement. However, microscopic
characteristics such as the optical properties and electrical
conductivity mechanism of β-Ga2O3 films are still under debate,
which calls for further investigations specifically at the reduced
dimensions. The present work was, therefore, performed to
determine the effect of growth temperature in a wide range on
the structural and optical characteristics of Ga2O3 films made by
sputter deposition. The results obtained are presented and
discussed to derive a structure−property relation.
■ EXPERIMENTAL SECTION
A. Fabrication. Gallium oxide films were deposited onto
silicon (Si) wafers and quartz substrates by radio frequency
magnetron sputtering. All the substrates were thoroughly
cleaned and dried with nitrogen before introducing them into
the vacuum chamber, which was initially evacuated to a base
pressure of ∼10−6 Torr. Gallium oxide target (Plasmaterials,
Inc.) of 2 in. diameter and 99.999% purity was employed for
sputtering. The Ga2O3 target was placed on a 2 in. sputter gun,
which is placed at a distance of 8 cm from the substrate. A
sputtering power of 40 W was initially applied to the target
while introducing high-purity argon (Ar) into the chamber to
ignite the plasma. Once the plasma was ignited the power was
increased to 100 W for reactive deposition. The flow of the Ar
was controlled using an MKS mass flow meter. Before each
deposition, the Ga2O3 target was presputtered for 10 min with a
shutter above the gun closed. The deposition was carried out
for 30 min. The thickness of the films was in the range of 40−
33 (±3) nm. The samples were deposited at different
temperatures varying in the range of 25−800 °C. Substrate
rotation is maintained during the entire deposition time to
ensure uniform coverage on the substrate surface.
B. Characterization. Ga2O3 films were characterized by
performing structural and optical measurements. X-ray
diffraction (XRD) measurements on Ga2O3 films grown on Si
were performed using a Bruker D8 Advance X-ray diffrac-
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tometer. All the measurements were made ex situ as a function
of growth temperature. XRD patterns were recorded using Cu
Kα radiation (λ = 1.54056 Å) at room temperature. Surface
imaging analysis was performed using a high-performance and
ultra-high-resolution scanning electron microscope (Hitachi S-
4800). Secondary electron imaging was performed on Ga2O3
films grown on Si wafers using carbon paste at the ends to
avoid charging problems.
Ion beam analysis of the Ga2O3−Si(100) samples was
performed to understand the chemical composition and
elemental depth distribution. Rutherford backscattering spec-
trometry (RBS) experiments were carried out in the accelerator
facility at the Environmental Molecular Sciences Laboratory
(EMSL) within the Pacific Northwest National Laboratory
(PNNL). The RBS experiments were performed at the
National Electrostatic Corporation (NEC) RC43 end station.
An incident ion probe containing 2 MeV He+ ions with a 7°
angle of incidence measured from the sample normal was used.
The backscattered ions were detected using a silicon barrier
detector at a scattering angle of 150°. Composition profiles
were determined by comparing SIMNRA computer simulations
of the spectra with the experimental data.29 The detailed
procedure on using this simulation to obtain the stoichiometry
and atomic concentration in the films has been outlined
elsewhere.30,31
The optical properties of Ga2O3 films were evaluated using
spectrophotometry measurements employing a Cary 5000
UV−vis−NIR double-beam spectrophotometer. Films grown
on optical grade quartz were employed for optical property
measurements. The quartz substrates employed extend the
transparency range down to ∼190 nm and determined the
absorption edge extending into the ultraviolet (UV) region,
which is more than sufficient to determine the band gap shift in
deficient or stoichiometric or metal incorporated Ga2O3 films.
The measurements were made using the film grown on quartz
under a sampling beam while keeping the bare quartz substrate
under the reference beam.
■ RESULTS AND DISCUSSION
A. Crystal Structure. X-ray diffraction patterns of Ga2O3
films are shown in Figure 1 as a function of Ts. The XRD curve
Figure 1. XRD patterns of Ga2O3 films. It is evident from the curves
that the films grown at RT−400 °C are amorphous, whereas films
grown at Ts ≥ 500 °C are nanocrystalline. Ga2O3 films grown at Ts =
800 °C exhibit the presence of an additional small peak, which could
be due to the Si−Ga2O3 reaction at the interface.
dx.doi.org/10.1021/jp311300e | J. Phys. Chem. C 2013, 117, 4194−4200
The Journal of Physical Chemistry C
(Figure 1) of Ga2O3 films grown at Ts = RT−400 °C did not
show any peaks indicating their characteristic amorphous (a-
Ga2O3) nature. The diffraction peaks began to appear in the
XRD pattern when Ts = 500 °C, indicating the film
crystallization at this temperature. The appearance of peaks
corresponds to the diffraction from β-Ga2O3 as indicated in
Figure 1. It is evident (Figure 1) that the intensity of the
substrate peak (Si(200)) increases for films grown at Ts = 800
°C, which might be due to interfacial reaction at the substrate−
film interface.
B. Surface Morphology and Growth Behavior. The
scanning electron microscopy (SEM) images of Ga2O3 films are
shown in Figure 2. The amorphous nature is clearly evident in
Figure 2. High-resolution SEM images of Ga2O3 thin films as a
function of Ts. The scale bar is 500 nm in all these images. It is evident
from the SEM images that the surface morphology of Ga2O3 films is
sensitive to the growth temperature. The morphological changes are
correlated with the changes in crystal structure and specific phase
formation of Ga2O3 films as a function of growth temperature.
the SEM images of Ga2O3 films grown at Ts = RT−400 °C. A
fine microstructure and uniform distribution of dense particles
can be seen in Ga2O3 films grown at Ts = 500−700 °C. It is
evident that the average size increases with Ts. It must be
emphasized that the presence of some particles for the Ga2O3
film surface is noted in SEM for Ts = 400 °C, although most of
the film volume is amorphous and did not reveal even a sign of
localized structural order with any other spectroscopic or X-ray
diffraction analysis. The most significant point is the remarkable
effect of deposition temperature on the surface morphology of
Ga2O3 films. The average grain size increases from 15 ± 2 to 35
± 3 nm with increasing Ts from 400 to 600 °C and finally drops
to 30 ± 2 nm for Ts = 800 °C. The origin for the significant
change in morphology with spherical shaped particles for films
at 800 °C is not clear. Perhaps an intermixing or Si−Ga2O3
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reaction may be occurring at the interface when the
temperature is increased to 800 °C.
On the basis of SEM and XRD data as a function of Ts, the
growth behavior of Ga2O3 films can be conveniently divided
into two zones, where the morphology differences are
significant. The first category or zone contains the set of
Ga2O3 films grown at temperatures <500 °C. The second is the
set of Ga2O3 films grown at temperatures ≥500 °C. No features
can be seen for Ga2O3 films grown at RT even at very high
magnifications (Figure 2). This observation is in agreement
with the XRD results indicating the complete amorphous
nature of the samples. If temperature is low such that the period
of the atomic jump process of adatoms on the substrate surface
is very large, the condensed species may stay stuck to the
regions where they are landing, thus leading to an amorphous
Ga2O3 film. The adatom mobility on the surface increases with
increasing temperature. The small, dense particles spherical in
shape can be noticed in SEM images for Ga2O3 films grown at
400−500 °C. The SEM data along with the appearance of
diffraction peaks in XRD clearly indicate that 500 °C is the
critical temperature to promote the growth of nanocrystalline
Ga2O3 films. For the given set of experimental conditions, a
temperature of 500 °C is, therefore, favorable to provide
sufficient energy for Ga2O3 film crystallization.
The XRD and SEM results suggest that a further increase in
temperature beyond 500 °C results in changes in the crystal
structure and morphology. Ga2O3 films continue to show
preferred growth along with an increase in average particle size
with increasing Ts. A functional relationship obtained between
the average particle size (L) and the temperature fits to an
exponential growth function as shown in Figure 3. The data
Figure 3. Variation of grain size of Ga2O3 films with substrate
temperature. The data obtained from SEM analysis are shown.
(Figure 3) support the thermally activated growth process of
nanocrystalline Ga2O3 films. Therefore, similar to the diffusion
coefficient equation32,33 L can be expressed as
L = Lo exp( −ΔE /kBT ) (1)
where L is the average particle size; L0 is a pre-exponential
factor or proportionality constant which depends on the
specific film and substrate materials involved; ΔE is the
activation energy; kB is the Boltzmann constant; and T is the
absolute temperature. It is important to recognize the
functional linear relationship which is indicative of thermally
driven growth behavior of nanocrystalline Ga2O3 films.
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Figure 4. RBS spectra of Ga2O3 films grown at various temperatures. The experimental and simulated curves are shown for each and every data set.
The peaks due to ion backscattering from Ga, Si, and O atoms are as indicated.

C. Chemical Composition. The Rutherford backscattering sotichiometry of Ga2O3 corresponds to a concentration of

(RBS) spectra Ga2O3 films are shown in Figure 4. The Ga:40 atom % and O:60 atom %, leading to an O/Ga ratio of
backscattered ions observed were due to various elements, and 1.5. The O/Ga ratio variation of the Ga2O3 films as a function
the positions are indicated by arrows for the experimental of growth temperature as revealed by RBS measurements is
spectrum. The scattering from Ga, the heaviest among the shown in Figure 5. The results obtained indicate that a
elements present in either the film or substrate, occurs at higher temperature of 300 °C or higher is required for the formation
backscattered energy (1580 keV) as shown in RBS curves for
of stoichiometric Ga2O3 films. The concentration of Ga and O
Ga2O3 films (Figure 4). The measured height and width of this
peak is related to the concentration and thickness distribution determined from RBS for films grown at room temperature is
of Ga atoms in the oxide film and serves as a calibration check 38 and 62, respectively, leading to a O/Ga ratio of 1.6, which is
for composition and thickness since known Rutherford slightly higher than that (1.5) of the stoichiometric Ga2O3. The
scattering cross section and experimental parameters can be
used to calculate this height and width.30,31 As indicated in the
figure, the step edge and peaks due to ion backscattering from
Si (substrate) and O atoms (film) are observed at 1100 and 660
keV, respectively. The composition and thickness of the films
were determined by simulating the experimental spectrum for
the set of experimental conditions. The procedure utilized to
derive the chemical composition of the grown films is
represented for all the samples (Figure 4). The experimental
curve (circles) along with the simulation curve (lines)
calculated using SIMNRA code is as shown in Figure 4. The
simulated curve was calculated using SIMNRA code29 for the
fixed set of experimental parameters: (1) incident He+ ion
energy, (2) integrated charge, (3) energy resolution of the
detector, and (4) scattering geometry. It can be seen in Figure 4
that the simulated curves (solid line) calculated using the
experimental parameters are in good agreement with the Figure 5. Variation of oxygen to gallium ratio in the Ga-oxide films as
experimental RBS spectra. This observation indicates that film a function of Ts. The ratio is determined from RBS measurements.
composition reasonably simulates the spectra and, hence, Slightly higher values than expected for films grown at RT indicate
provides the estimate of film composition. The theoretical excess oxygen in the films.

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The Journal of Physical Chemistry C
concentration of O was found to be much higher than Ga
concentration. The O/Ga ratio deviates from the expected
stoichiometry, and formation of excess oxygen with a metal
deficiency was also reported for Y2O3 films on Si.31 Although
the deposition conditions are different, the samples with a
deviation of stoichiometry in this work agree with those
reported for Y2O3 films.31
The EDS spectra obtained from representative samples
grown at various temperatures are shown in Figure 6. All the
Figure 6. EDS spectra of Ga2O3 films. The peaks due to X-rays
emitted from Ga, Si, and O present in the films are as labeled.
spectra exhibit characteristic peaks corresponding to Ga and O
atoms. The X-rays emitted from the sample as a result of
electron beam bombardment are characteristic of individual
atoms.34,35 The EDS measurements, therefore, can be used to
qualitatively discuss the chemical characteristics of the grown
samples. The EDS curve displays the peaks due to Ga K, Ga L,
and O K lines. The absence of any other peaks except those due
to Ga and O is evidence that the sample consists exclusively of
the Ga-oxide phase with no other detectable impurities from
other elements. The XRD, SEM, and EDS results indicate that
the Ge-oxide samples synthesized exhibit high structural quality
in terms of physical and chemical structure. Finally, based on
the XRD, SEM, EDS, and RBS measurements, we propose the
phase diagram for the microstructure evolution of Ga2O3 films
as shown in Figure 7. The phase diagram summarizes the
Figure 7. Phase diagram summarizing the microstructure evolution of
GaO3 films as a function of temperature.
observed changes in structure, chemistry, and morphology of
the films as a function of substrate temperature and could
provide a roadmap while considering the Ga2O3 films for the
desired set of applications.
D. Optical Properties. The spectral transmission character-
istics of Ga2O3 films grown at Ts = 25−800 °C are shown in
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Figure 8. It is evident that the amorphous and nanocrystalline
Ga2O3 films in general show high transparency in the spectral
Figure 8. Spectral transmittance characteristic of Ga2O3 films as a
function of temperature.
range except where the incident radiation is absorbed across the
band gap (Eg). It indicates the transparent nature of all the
Ga2O3 films. A further analysis of the optical spectra is
performed to better understand the effect of microstructure on
the optical properties and to derive a quantitative structure−
property relationship. For β-Ga2O3 with a direct band gap,1,15,36
the absorption follows a power law of the form
(α hν) = B(hν − Eg)1/2 (2)
where hν is the energy of the incident photon, α the absorption
coefficient, B the absorption edge width parameter, and Eg the
band gap. The optical absorption coefficient, α, of the films is
evaluated using the relation37,38
α = [1/t]ln[T/(1 − R)2 ] (3)
where T is the transmittance, R the reflectance, and t the film
thickness. The absorption data and the plots obtained for
Ga2O3 films are shown in Figure 9. It is evident that (αhν)2 vs
hν results in linear plots in the high absorption region,
suggesting direct allowed transitions across Eg of Ga2O3
films.1,15,19,36 Regression analysis (for R2 values 0.9 or better,
see Figure 9) and extrapolating the linear region of the plot to
hν = 0 provide the band gap value as indicated with an arrow in
Figure 9. The Eg variations for Ga2O3 films grown at various Ts
are shown in Figure 10. The Eg value of Ga2O3 films grown at
25 °C is 5.17 (±0.02) eV and decreases to 4.96 (±0.03) films
grown at 800 °C. The higher values of Eg measured for Ga2O3
films may be due to the amorphous nature or excess oxygen of
the films. These two factors contribute disorder, leading to a
slightly higher band gap measured for films grown at room
temperature. It is noted that the measured band gap energy
values in this work compare with those reported in the
literature for β-Ga2O3.1,15,19,36 However, no quantum effects
and band gap enhancement are observed in β-Ga2O3 films
when compared to the other transparent, wide band gap
oxides.37,39,40
■
SUMMARY AND CONCLUSIONS
Ga2O3 thin films were produced by sputter deposition by
varying the substrate temperature in a wide range (Ts = 25−800
°C). The structural characteristics and optical properties of
dx.doi.org/10.1021/jp311300e | J. Phys. Chem. C 2013, 117, 4194−4200
The Journal of Physical Chemistry C
Figure 9. (αhν)2 vs hν plots for GaO3 films grown at different temperatures. Extrapolating the linear region of the plot to hν = 0 provides the band
gap value as indicated with an arrow. To indicate the procedure and clarity purpose, the absorption data scale is shown to slightly negative values side
(below zero).
Figure 10. Variation of band gap with Ts for Ga2O3 films.
Ga2O3 films were evaluated. Ga2O3 films grown at lower
temperatures were amorphous, while those grown at Ts ≥ 500
°C were nanocrystalline. RBS measurements indicate that the
Ga2O3 films grown at RT exhibit slightly excess oxygen, leading
to an O/Ga ratio of 1.6, while films grown at 300−800 °C were
nearly stoichiometric (O/Ga ∼ 1.5). The spectral transmission
of the films increased with increasing temperature. The band
gap of the films varied from 4.66 to 5.17 eV for a variation in Ts
in the range 25−800 °C. Slightly higher band gap for films
grown at lower temperatures may be due to excess oxygen or
structural disorder induced by the amorphous nature of the
films. The A relationship between microstructure and optical
property is discussed.
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■ AUTHOR INFORMATION
Corresponding Author
*E-mail: rvchintalapalle@utep.edu. Tel.: 915-747-8690. Fax:
915-747-5015.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This material is based on the work supported by the
Department of Energy under Award Number DE-PS26-
08NT00198-00. Hitachi 4800 SEM used for the morphology
and X-ray chemical analysis of the samples in this work was
acquired through the support from the National Science
Foundation (NSF-DMR-0521650). A portion of the research
(RBS measurements) was performed using Environmental
Molecular Sciences Laboratory (EMSL), a national scientific
user facility sponsored by the Department of Energy’s Office of
Biological and Environmental Research and located at Pacific
Northwest National Laboratory.
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