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Origin of Photo Luminescence in Indium Oxide Ron Structures
Origin of Photo Luminescence in Indium Oxide Ron Structures
The strong photoluminescence 共PL兲 of indium oxide transmission electron microscopy 共HRTEM兲 共Tecnai G20-
共IO兲 in the visible and ultraviolet range along with its Stwin at 200 kV兲. The PL spectrum was recorded at room
chemical inertness and heat stability makes it an important temperature using a He–Cd laser with an excitation source
material for optical device applications. Although the PL has wavelength of 325 nm. The measurement conditions were
been reported in IO thin film and nanostructures, the mecha- kept identical for all the three samples. The EPR spectros-
nism is still not clear.1–6 Guha et al. reported PL emission copy measurements were performed on an X-band Elexsys
from IO nanopyramids and nanocolumns at a wavelength of 500 EPR spectrometer 共Bruker Instrument兲 operating at a
about 470 nm.1 Whereas, Cao et al.2 and Wu et al.3 have frequency of 9.383 GHz, equipped with a TE102 cavity. The
observed PL emission at 398 and 416 nm from IO nanowires EPR measurements were carried out at room temperature to
and at 480 and 520 nm from IO nanoparticles.4 In some stud- analyze the presence of paramagnetic oxygen vacancies in
ies, In2O3 samples exhibiting strong PL have been observed the IO octahedron samples. Typically, four scans were col-
to show electron paramagnetic resonance 共EPR兲 signal due lected per spectrum under nonsaturating conditions at a mi-
to paramagnetic nature of the oxygen vacancies.1,7 This crowave power of 10 mW. The spectra were acquired at a
has lead to an assumption that oxygen vacancies are respon- modulation frequency of 100 kHz with modulation ampli-
sible for PL in IO nanoparticles, nanopyramids, and tude of 1 G. The center field of the EPR scans was set to
nanocolumns.1–7 However, no systematic study showing the 3350 G with a sweep width of 100 G. Raman spectroscopy
effect of variation of oxygen vacancy concentration on EPR of the IO octahedron samples was carried out under ambient
and PL signal strength in the case of In2O3 has been reported. conditions by Renishaw micro-Raman setup having Ar ion
Nevertheless, such a study is really essential to understand laser with an excitation wavelength of 514.5 nm and a spot
the role of oxygen vacancies and other defects for PL signal size of about 1.7 m.
in IO. In this letter, a number of experimental techniques GAXRD studies 共not shown here兲 of samples A, B, and
such as energy dispersive x-ray 共EDX兲 analysis, micro- C show the presence of cubic In2O3 with a lattice constant of
Raman spectroscopy, along with EPR spectroscopy have 1.011 nm. The scanning electron micrographs of samples A
been employed to understand the origin of PL in IO octahe- and C are shown in Figs. 1共a兲 and 1共b兲. Samples A and C
dron structures. contain octahedron structures of about 1 and 2 m sizes,
The IO octahedron structures were grown using a hori- respectively. The octahedrons have sharp facets with trun-
zontal tube furnace maintained at a temperature of 960 ° C cated tips, as shown in the inset of Figs. 1共a兲 and 1共b兲. The
and one atmosphere pressure. An alumina boat with a 1:1 HRTEM images in Figs. 1共c兲 and 1共d兲 show the single crys-
mixture of IO and active carbon powder was placed at the talline nature of IO octahedrons. The lattice spacing of
center of the tube furnace. The p-Si共100兲 substrates were samples A and C with of 0.29 and 0.71 nm corresponds to
positioned exactly above the alumina boat. The reaction was 共222兲 and 共110兲 planes of cubic IO, respectively. Similar oc-
carried out under constant Ar flow rate of 100 ml/ min. The tahedrons structures with smooth surfaces and single crystal-
deposition was carried out for 3 h 共sample A兲, 6 h 共sample line nature have been previously reported.8 Figure 2共a兲
B兲, and 12 h 共sample C兲. These samples are characterized by shows PL spectra of IO octahedron samples. The PL is cen-
glancing angle x-ray diffraction 共GAXRD兲, scanning elec- tered at 590 nm for all the three samples. It is interesting to
tron microscopy 共SEM兲 共Ziess EVO 50兲, and high resolution 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
a兲
Authors to whom correspondence should be addressed. Electronic ad-
to 12 h 共sample C兲. The sample grown by 6 h deposition
dresses: jpsingh@physics.iitd.ac.in and brmehta@physics.iitd.ac.in. FAX: time 共sample B兲 has PL intensity in between samples A and
⫹91-11-26581114. C. To investigate the effect of growth time on the stoichiom-
be a dominant defect in IO and Ini stays in the triplet charged is confirmed by EPR and EDX results. This may cause a
12,16
i 兲.
state 共In3+ i 共关Kr兴4d 兲
It is interesting to notice that In3+ 10
relatively much lower concentration of In3+
i defects in sample
is nonparamagnetic in nature and hence will not give an EPR C than in sample A and hence a difference in the PL intensity
signal. In order to confirm the hypothesis of In3+ i induced PL at cathode and anode sides was not observed.
emission in IO, samples A and C were heated at 700 ° C for In summary, a strong PL signal was observed from the
30 min in presence of a constant electric field of 200 V / cm. sample A deposited for 3 h having lack of oxygen vacancies.
The Ar gas flow was maintained during the experiment. The This PL emission intensity was found to decrease by a factor
samples were thereafter cooled down to room temperature. of 6 with increase in deposition time from 3 to 12 h and
The room temperature PL measurements were performed on hence increase in the oxygen vacancies. Our results indicate
the IO sample surface at positions near cathode and anode that In3+
i playing a significant role and control the optical
electrodes and results are shown in Fig. 2共d兲. The PL inten- properties of IO octahedron samples.
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 1
P. Guha, S. Kar, and S. Choudhari, Appl. Phys. Lett. 85, 3851 共2004兲.
anode side 共curve 2兲 compared to the PL intensity measured 2
H. Cao, X. Qiu, Y. Liang, Q. Zhu, and M. Zhao, Appl. Phys. Lett. 83, 761
over the pristine sample A 共curve A兲. For pristine samples the 共2003兲.
3
PL intensity was found to be same measured over different X. C. Wu, J. M. Hong, Z. J. Han, and Y. R. Tao, Chem. Phys. Lett. 373,
positions on the sample surface. The variation of PL intensity 28 共2003兲.
4
H. Zhou, W. Cai, and L. Zhang, Appl. Phys. Lett. 75, 495 共1999兲.
from the sample surface adjacent to the cathode and anode 5
W. S. Seo, H. H. Jo, K. Lee, and J. T. Park, Adv. Mater. 共Weinheim, Ger.兲
electrodes is due to the electric field induced change in the 15, 795 共2003兲.
defect density. Similar experiments on ZnO samples heated 6
A. Murali, A. Barve, V. J. Leppert, S. H. Risbud, I. M. Kennedy, and H.
in the presence of electric field were performed to investigate W. H. Lee, Nano Lett. 1, 287 共2001兲.
7
the nature of defects associated with the PL emission from M. J. Zheng, L. D. Zhang, G. H. Li, X. Y. Zhang, and X. F. Wang, Appl.
ZnO samples.17,18 It was concluded that the Zn interstitials 8
Phys. Lett. 79, 839 共2001兲.
were responsible for PL emission from ZnO. Bylander re- Y. F. Hao, G. W. Meng, C. H. Ye, and L. D. Zhang, Cryst. Growth Des. 5,
1617 共2005兲.
ported that the electronic transitions from interstitial metal to 9
J. Zuo, C. Xu, X. Liu, C. Wang, C. Wang, Y. Hu, and Y. Qian, J. Appl.
metal vacancies were responsible for the luminescence Phys. 75, 1835 共1994兲.
properties.19 The mobility of In3+ i increases during heating of
10
K. Mcguire, Z. W. Pan, D. Milkie, J. Menéndez, and A. M. Rao, J.
the IO sample at 700 ° C and the presence of electric field Nanosci. Nanotechnol. 2, 499 共2002兲.
11
provide a drift to In3+ i towards the cathode side. This results
W. B. White and V. G. Keramidas, Spectrochim. Acta, Part A 28, 501
in the higher In3+ defect density on the IO sample surface 共1972兲.
i 12
J. H. W. De Wit, J. Solid State Chem. 8, 142 共1973兲.
regions near cathode than the anode electrodes. The PL in- 13
A. Gurlo, M. Ivanovskaya, A. Pfau, U. Weimar, and W. Gopel, Thin Solid
tensity is also found to be higher on the cathode side of the Films 307, 288 共1997兲.
sample than the anode side. These experimental findings pro- 14
M. Mazzera, M. Zha, D. Calestani, A. Zappettini, G. Salviati, and L.
vide a direct evidence that In+3 i and their associated complex Zanotti, Nanotechnology 18, 355707 共2007兲.
15
defects are responsible for PL emission in IO octahedron A. A. Kaminskii, Laser Crystals 共Springer, Berlin, 1981兲, p. 457.
16
structures. The PL signal has not shown any appreciable S. H. Lee, J. H. Lee, K. H. Kim, and J. H. Jun, Bull. Korean Chem. Soc.
10, 418 共1989兲.
change in the intensity on sample C measured at cathode and 17
N. O. Korsunska, L. V. Borkovska, B. M. Bulakh, L. Yu. Khomenkova,
anode sides. The lengthening of the deposition time of 12 h and V. I. Markevich, J. Lumin. 102-103, 733 共2003兲.
for IO sample C leads to the oxygen deficiency during the 18
M. Liu, A. H. Kitia, and P. Mascher, J. Lumin. 54, 35 共1992兲.
growth process.8 The higher oxygen vacancy concentration 19
E. G. Bylander, J. Appl. Phys. 49, 1188 共1978兲.
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