APPLIED PHYSICS LETTERS 92, 171907 共2008兲

On the origin of photoluminescence in indium oxide octahedron structures

Mukesh Kumar,1 V. N. Singh,1 F. Singh,2 K. V. Lakshmi,3 B. R. Mehta,1,a兲 and
J. P. Singh1,a兲
1
Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
2
Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110067, India
3
Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, 110 8th Street, Troy,
New York 12180, USA
共Received 4 February 2008; accepted 25 March 2008; published online 1 May 2008兲
A sixfold decrease in photoluminescence signal intensity at 590 nm with increase in deposition time
from 3 to 12 h has been observed in single crystalline indium oxide octahedron structures grown by
vapor-phase evaporation method. Electron paramagnetic resonance and energy dispersive x-ray
analysis confirm that the concentration of oxygen vacancies increases with deposition time. These
results are contrary to the previous reports where oxygen vacancies were shown to be responsible
for photoluminescence in indium oxide structures. Our results indicate that indium interstitials
and their associated complex defects other than oxygen vacancies are responsible for the
photoluminescence in In2O3 microstructures. © 2008 American Institute of Physics.
关DOI: 10.1063/1.2910501兴

The strong photoluminescence 共PL兲 of indium oxide
共IO兲 in the visible and ultraviolet range along with its
chemical inertness and heat stability makes it an important
material for optical device applications. Although the PL has
been reported in IO thin film and nanostructures, the mecha-
nism is still not clear.1–6 Guha et al. reported PL emission
from IO nanopyramids and nanocolumns at a wavelength of
about 470 nm.1 Whereas, Cao et al.2 and Wu et al.3 have
observed PL emission at 398 and 416 nm from IO nanowires
and at 480 and 520 nm from IO nanoparticles.4 In some stud-
ies, In2O3 samples exhibiting strong PL have been observed
to show electron paramagnetic resonance 共EPR兲 signal due
to paramagnetic nature of the oxygen vacancies.1,7 This
has lead to an assumption that oxygen vacancies are respon-
sible for PL in IO nanoparticles, nanopyramids, and
nanocolumns.1–7 However, no systematic study showing the
effect of variation of oxygen vacancy concentration on EPR
and PL signal strength in the case of In2O3 has been reported.
Nevertheless, such a study is really essential to understand
the role of oxygen vacancies and other defects for PL signal
in IO. In this letter, a number of experimental techniques
such as energy dispersive x-ray 共EDX兲 analysis, micro-
Raman spectroscopy, along with EPR spectroscopy have
been employed to understand the origin of PL in IO octahe-
dron structures.
The IO octahedron structures were grown using a hori-
zontal tube furnace maintained at a temperature of 960 ° C
and one atmosphere pressure. An alumina boat with a 1:1
mixture of IO and active carbon powder was placed at the
center of the tube furnace. The p-Si共100兲 substrates were
positioned exactly above the alumina boat. The reaction was
carried out under constant Ar flow rate of 100 ml/ min. The
deposition was carried out for 3 h 共sample A兲, 6 h 共sample
B兲, and 12 h 共sample C兲. These samples are characterized by
glancing angle x-ray diffraction 共GAXRD兲, scanning elec-
tron microscopy 共SEM兲 共Ziess EVO 50兲, and high resolution
a兲
Authors to whom correspondence should be addressed. Electronic ad-
dresses: jpsingh@physics.iitd.ac.in and brmehta@physics.iitd.ac.in. FAX:
⫹91-11-26581114.
transmission electron microscopy 共HRTEM兲 共Tecnai G20-
Stwin at 200 kV兲. The PL spectrum was recorded at room
temperature using a He–Cd laser with an excitation source
wavelength of 325 nm. The measurement conditions were
kept identical for all the three samples. The EPR spectros-
copy measurements were performed on an X-band Elexsys
500 EPR spectrometer 共Bruker Instrument兲 operating at a
frequency of 9.383 GHz, equipped with a TE102 cavity. The
EPR measurements were carried out at room temperature to
analyze the presence of paramagnetic oxygen vacancies in
the IO octahedron samples. Typically, four scans were col-
lected per spectrum under nonsaturating conditions at a mi-
crowave power of 10 mW. The spectra were acquired at a
modulation frequency of 100 kHz with modulation ampli-
tude of 1 G. The center field of the EPR scans was set to
3350 G with a sweep width of 100 G. Raman spectroscopy
of the IO octahedron samples was carried out under ambient
conditions by Renishaw micro-Raman setup having Ar ion
laser with an excitation wavelength of 514.5 nm and a spot
size of about 1.7 ␮m.
GAXRD studies 共not shown here兲 of samples A, B, and
C show the presence of cubic In2O3 with a lattice constant of
1.011 nm. The scanning electron micrographs of samples A
and C are shown in Figs. 1共a兲 and 1共b兲. Samples A and C
contain octahedron structures of about 1 and 2 ␮m sizes,
respectively. The octahedrons have sharp facets with trun-
cated tips, as shown in the inset of Figs. 1共a兲 and 1共b兲. The
HRTEM images in Figs. 1共c兲 and 1共d兲 show the single crys-
talline nature of IO octahedrons. The lattice spacing of
samples A and C with of 0.29 and 0.71 nm corresponds to
共222兲 and 共110兲 planes of cubic IO, respectively. Similar oc-
tahedrons structures with smooth surfaces and single crystal-
line nature have been previously reported.8 Figure 2共a兲
shows PL spectra of IO octahedron samples. The PL is cen-
tered at 590 nm for all the three samples. It is interesting to
note that the intensity of PL emission decreases by a factor of
about 6 as the deposition time increases from 3 h 共sample A兲
to 12 h 共sample C兲. The sample grown by 6 h deposition
time 共sample B兲 has PL intensity in between samples A and
C. To investigate the effect of growth time on the stoichiom-

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171907-2 Kumar et al.
FIG. 1. SEM micrographs of 共a兲 sample A and 共b兲 sample C. Both samples
A and C contain truncated octahedron structures. The inset show high mag-
nified images. 共c兲 and 共d兲 show the high resolution TEM of samples A and
C, respectively with their TEM micrographs in the inset.
etry of IO samples, spot EDX measurements were performed
over individual IO octahedrons. The EDX analysis reveals
that the sample A has an indium to oxygen 共In/ O兲 ratio of
38:60 which is in close agreement to the stoichiometric In/ O
ratio of 40:60. While sample C is found to be oxygen defi-
cient with In/ O ratio of 38:52. The spot EDX measurements
were performed with a reduced beam size and low acceler-
ating potential to eliminate any possible interference in oxy-
gen signal from the native oxide on silicon substrate. Raman
spectroscopy was also performed to investigate the change in
the stoichiometry with deposition time and the results are
shown in Fig. 2共b兲. Samples A and C exhibit strong Raman
FIG. 2. 共Color online兲 共a兲 PL spectra of IO samples deposited for different time leads to an increase in the oxygen vacancies, the PL
time. Sample A has six times higher PL intensity than the sample C without intensity results do not seem to follow the common trend and
any peak shift. 共b兲 Raman spectra of IO samples. Raman shift at
307.95 cm−1 is sensitive to the oxygen vacancies and more asymmetric in
the sample C. Inset: representative Raman spectra of sample C. 共c兲 The EPR
spectra of samples A and C. Sample A does not show any EPR signal while
sample C shows a strong EPR signal. 共d兲 PL spectra of sample C heated at
700 ° C for 30 min in presence of a constant electric field of 200 V / cm. The
PL intensity is found to increase at cathode side 共curve 1兲 while it decreases
at anode side 共curve 2兲 with respect to the pristine sample A 共curve A兲. Inset
shows the schematic of sample annealed in presence of an electric field. The共1.38 Å兲 with respect to the cell volume reduces the possi-
A, B, and C in figures denoted the samples A, B, and C, respectively.
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Appl. Phys. Lett. 92, 171907 共2008兲
shifts at 133.3, 307.9, 366.9, and 496.9 cm−1. The Raman
peak observed at 307.9 cm−1 is symmetric in sample A
whereas as this peak is asymmetric in sample C. This asym-
metric peak in sample C is deconvoluted and the lower in-
tensity Raman peak at 321.2 cm−1 can be ascribed to quan-
tum confinement effect or the nonstoichiometry in the
sample.9,10 Zuo et al. have reported an additional Raman
peak due to quantum confinement in tin oxide nanoparticles9
while, in an another report, Mcguire et al. pointed out non-
stoichiometry responsible for the same.10 It is important to
notice that the size of the observed IO octahedron structures
共typical Bohr radius of In2O3 is 2.14 nm兲 are too big to ob-
serve any significant quantum confinement effects. The
Raman peak at 307.9 cm−1 corresponds to the stretching
mode of the IO and is very sensitive to presence of oxygen
vacancies.11 Thus, the observed asymmetry of Raman mode
at 307.9 cm−1 in sample C has been attributed to the oxygen
vacancies. The change in stoichiometry in IO octahedron
samples with deposition time is explained as follows. The
precursor IO powder is carbothermally reduced into In and
InxO 共x = 1,2兲 vapor at 960 ° C. The vapor species are driven
by argon gas and get deposited on the silicon substrate.3 With
the passage of deposition time, IO powder in the source boat
and thus the InxO in vapor phase become oxygen deficient.
Therefore, continuous deposition for 12 h results in oxygen
deficiency in sample C compared to sample A which was
deposited for 3 h. Hao et al. reported that lengthening in
deposition time leads to the oxygen deficiency during the
growth process.8
To probe the defects responsible for PL emission in IO
octahedron samples, EPR spectroscopy was performed on
samples A and C at room temperature. The results are shown
in Fig. 2共c兲. It is evident that no EPR signal is observed in
sample A while sample C showed a strong EPR signal. The
absence of EPR signal in sample A indicates a complete
absence of paramagnetic centers. In contrast, the strong EPR
signal in sample C indicates the presence of paramagnetic
centers such as singly charged oxygen vacancies 共VO ·
兲, in-
dium interstitial in doublet charged state 关Ini 兴, and other
2+
complex defects. In the earlier reports, the presence of EPR
signal was universally taken as a signature of oxygen vacan-
cies, which was attributed to be the reason for the observa-
tion of PL in IO.1,7 Besides the oxygen vacancies, the pres-
ence of other defects has also been reported in IO.12,13 Gurlo
et al. reported three types of paramagnetic centers in IO
films.13 Also, the impurities and point defects could form
different complexes and associates. Thus, the EPR signal
may arise due to the presence of several types of defects
enumerated above and oxygen vacancies is one of these. It
should be mentioned that the PL intensity is observed to be
significantly lower in sample C, having larger number of
oxygen vacancies in comparison to sample A, as confirmed
by EDX and EPR results. Since increase in the deposition
so our results are in contradiction with the previous reports
where oxygen vacancies were shown to be responsible for
PL emission.1,7 There are other defects like oxygen antisite
共OIn兲, indium interstitial 共Ini兲, oxygen interstitial 共Oi兲, and
indium vacancies 共VIn兲 which may be responsible for PL
emission in IO.14 The large diameter of oxygen atom
bility of forming the Oi.15 The indium interstitial is found to
171907-3 Kumar et al.
be a dominant defect in IO and Ini stays in the triplet charged
12,16
i 兲.
state 共In3+ i 共关Kr兴4d 兲
It is interesting to notice that In3+ 10
is nonparamagnetic in nature and hence will not give an EPR
signal. In order to confirm the hypothesis of In3+ i induced PL
emission in IO, samples A and C were heated at 700 ° C for
30 min in presence of a constant electric field of 200 V / cm.
The Ar gas flow was maintained during the experiment. The
samples were thereafter cooled down to room temperature.
The room temperature PL measurements were performed on
the IO sample surface at positions near cathode and anode
electrodes and results are shown in Fig. 2共d兲. The PL inten-
sity on sample A increases by 1.3 times near cathode side
共curve 1兲 while PL intensity decreases by 3.5 times near
anode side 共curve 2兲 compared to the PL intensity measured
over the pristine sample A 共curve A兲. For pristine samples the
PL intensity was found to be same measured over different
positions on the sample surface. The variation of PL intensity
from the sample surface adjacent to the cathode and anode
electrodes is due to the electric field induced change in the
defect density. Similar experiments on ZnO samples heated
in the presence of electric field were performed to investigate
the nature of defects associated with the PL emission from
ZnO samples.17,18 It was concluded that the Zn interstitials
were responsible for PL emission from ZnO. Bylander re-
ported that the electronic transitions from interstitial metal to
metal vacancies were responsible for the luminescence
properties.19 The mobility of In3+ i increases during heating of
the IO sample at 700 ° C and the presence of electric field
provide a drift to In3+ i towards the cathode side. This results
in the higher In3+ defect density on the IO sample surface
i 12
regions near cathode than the anode electrodes. The PL in-
tensity is also found to be higher on the cathode side of the
sample than the anode side. These experimental findings pro-
vide a direct evidence that In+3 i and their associated complex
defects are responsible for PL emission in IO octahedron
structures. The PL signal has not shown any appreciable
change in the intensity on sample C measured at cathode and
anode sides. The lengthening of the deposition time of 12 h
for IO sample C leads to the oxygen deficiency during the
growth process.8 The higher oxygen vacancy concentration
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Appl. Phys. Lett. 92, 171907 共2008兲
is confirmed by EPR and EDX results. This may cause a
relatively much lower concentration of In3+
i defects in sample
C than in sample A and hence a difference in the PL intensity
at cathode and anode sides was not observed.
In summary, a strong PL signal was observed from the
sample A deposited for 3 h having lack of oxygen vacancies.
This PL emission intensity was found to decrease by a factor
of 6 with increase in deposition time from 3 to 12 h and
hence increase in the oxygen vacancies. Our results indicate
that In3+
i playing a significant role and control the optical
properties of IO octahedron samples.
1
P. Guha, S. Kar, and S. Choudhari, Appl. Phys. Lett. 85, 3851 共2004兲.
2
H. Cao, X. Qiu, Y. Liang, Q. Zhu, and M. Zhao, Appl. Phys. Lett. 83, 761
共2003兲.
3
X. C. Wu, J. M. Hong, Z. J. Han, and Y. R. Tao, Chem. Phys. Lett. 373,
28 共2003兲.
4
H. Zhou, W. Cai, and L. Zhang, Appl. Phys. Lett. 75, 495 共1999兲.
5
W. S. Seo, H. H. Jo, K. Lee, and J. T. Park, Adv. Mater. 共Weinheim, Ger.兲
15, 795 共2003兲.
6
A. Murali, A. Barve, V. J. Leppert, S. H. Risbud, I. M. Kennedy, and H.
W. H. Lee, Nano Lett. 1, 287 共2001兲.
7
M. J. Zheng, L. D. Zhang, G. H. Li, X. Y. Zhang, and X. F. Wang, Appl.
8
Phys. Lett. 79, 839 共2001兲.
Y. F. Hao, G. W. Meng, C. H. Ye, and L. D. Zhang, Cryst. Growth Des. 5,
1617 共2005兲.
9
J. Zuo, C. Xu, X. Liu, C. Wang, C. Wang, Y. Hu, and Y. Qian, J. Appl.
Phys. 75, 1835 共1994兲.
10
K. Mcguire, Z. W. Pan, D. Milkie, J. Menéndez, and A. M. Rao, J.
Nanosci. Nanotechnol. 2, 499 共2002兲.
11
W. B. White and V. G. Keramidas, Spectrochim. Acta, Part A 28, 501
共1972兲.
J. H. W. De Wit, J. Solid State Chem. 8, 142 共1973兲.
13
A. Gurlo, M. Ivanovskaya, A. Pfau, U. Weimar, and W. Gopel, Thin Solid
Films 307, 288 共1997兲.
14
M. Mazzera, M. Zha, D. Calestani, A. Zappettini, G. Salviati, and L.
Zanotti, Nanotechnology 18, 355707 共2007兲.
15
A. A. Kaminskii, Laser Crystals 共Springer, Berlin, 1981兲, p. 457.
16
S. H. Lee, J. H. Lee, K. H. Kim, and J. H. Jun, Bull. Korean Chem. Soc.
10, 418 共1989兲.
17
N. O. Korsunska, L. V. Borkovska, B. M. Bulakh, L. Yu. Khomenkova,
and V. I. Markevich, J. Lumin. 102-103, 733 共2003兲.
18
M. Liu, A. H. Kitia, and P. Mascher, J. Lumin. 54, 35 共1992兲.
19
E. G. Bylander, J. Appl. Phys. 49, 1188 共1978兲.