Thin Solid Films 405 (2002) 35–41

Optical properties and charge transport in nanocrystalline TiO2 –In2O3

composite films
Sergey K. Poznyaka,*, Dmitri V. Talapina,b, Anatoly I. Kulakc
a
Institute of Physico-Chemical Problems, Belarusian State University, Leningradskaya St. 14, Minsk 220050, Belarus
b
Institute of Physical Chemistry, University of Hamburg, Bundesstr. 45, 20146 Hamburg, Germany
c
Institute of General and Inorganic Chemistry, Belarusian Academy of Sciences, Surganova St. 9, Minsk 220072, Belarus

Received 19 December 2000; received in revised form 27 November 2001; accepted 6 December 2001

Abstract

This work involves a comparative study of nanocrystalline titanium and indium oxides as well as TiO2 –In2O3 composites
prepared by a sol–gel method from concentrated hydrous titanium dioxide and indium hydroxide sols. Highly transparent uniform
films were fabricated from the sols by a spin-coating technique. TiO2 –In2 O3 nanocomposites possess pronounced extreme
dependencies of both the apparent bandgap and the refractive index on the film composition. No chemical interaction between
the oxides was observed during annealing to temperatures between 200 and 700 8C. This behavior was attributed to the effect of
surface states formed at the nanocrystallite interfaces. Other possible causes of the pronounced dependence of the optical and
electronic properties on the TiO2 -to-In2 O3 ratio are also discussed. Abrupt changes in resistivity, photoresistivity and photocurrent
decay time of the composite films were observed for composites where the TiO2 content ranged from 25 to 50 wt.% and are
associated with the formation of a three-dimensional infinite cluster of interconnected In2 O3 nanoparticles. 䊚 2002 Elsevier
Science B.V. All rights reserved.

Keywords: Indium oxide; Nanostructures; Optical properties; Electrical properties and measurements

1. Introduction than 25% of atoms comprise the surface), the contribu-

tion from interparticle boundaries will play an important
During the past decade, there has been considerable role even if no new phases are formed. In other words,
interest in the structural, optical and transport properties in a composite material prepared by sintering of two
of thin films consisting of nanometer sized semiconduc- kinds of nanocrystals, a significant portion of atoms will
tor particles w1x. Sol–gel derived films are very attractive belong to the third ‘component’, i.e. the interface
candidates for a variety of new applications in microe- between the nanocrystals.
lectronics, integrated optics, electro- and photoelectro- Titanium dioxide and indium (III) oxide are com-
chemistry, sensor devices, etc. Preparation of monly used materials in optical thin film filters w4x,
nanocrystalline heterogeneous composites also offers antireflection coatings w5x, and sensors w6x. In addition,
new possibilities to the development of novel materials. the optical and electrical properties of doped In2O3 films
In this case, properties of the composite obtained often make them well suited in applications such as conduct-
cannot be considered as a simple superposition of the ing window coatings w5,7x. In this work, the fabrication
properties of the pure components. This is due to strong of highly transparent TiO2 –In2O3 composite films with
surface interactions between closely packed nanoparti- various TiyIn ratios using concentrated TiO2 and
cles in the composite w2,3x. Indeed, taking into account In(OH)3 sols as well as characterization of their struc-
that for nanocrystals the surface-to-volume atomic ratio tural, optical and charge transport properties is presented.
can be appreciable (e.g. in 5 nm CdSe particles, more
2. Experimental
* Corresponding author. Tel.: q375-172-264-696. TiO2 –In2O3 nanocrystalline films were obtained from
E-mail address: elchem@[Link] (S.K. Poznyak). stabilized hydrous titanium dioxide and indium hydrox-

0040-6090/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 1 . 0 1 7 6 1 - 8
36 S.K. Poznyak et al. / Thin Solid Films 405 (2002) 35–41

Fig. 1. X-Ray diffractograms of TiO2 –In2 O3 nanocrystalline composites annealed at 200, 400 and 700 8C: (1) TiO2 100 wt.%; (2) TiO2 75 wt.%–
In2O3 25 wt.%; (3) TiO2 50 wt.%–In2O3 50 wt.%; (4) TiO2 25 wt.%–In2O3 75 wt.%; (5) In2O3 100 wt.%. The line spectra in the left panel
(200 8C) indicate the reflections of bulk TiO2 (anatase) and In2O3 (cubic phase). The line spectrum in the right panel (700 8C) indicates the
reflections of bulk TiO2 (rutile).

ide sols mixed in a definite proportion before their cal transmission and absorption spectra as well as the
deposition onto a substrate. The titanium dioxide sol specular reflection of the films were measured using
was prepared as described in detail in Poznyak et al. Cary 500 UV-Vis-NIR spectrometer (Varian). The
w8x. Briefly, the hydrous titanium dioxide precipitate was refractive indexes were calculated from the specular
obtained by titration of TiCl4 in aqueous HCl solution reflection data for the p-component of monochromatic
with NH4OH solution at 0 8C. The precipitate was then light incident on the film at variable angles w9x. Electri-
thoroughly washed and ultrasonically treated after addi- cal and photoconductivity measurements were carried
tion of HNO3 to obtain an opalescent stable TiO2 sol out using a pair of comb-shaped Au electrodes deposited
with a concentration of approximately 80 gyl. Variation on the quartz substrates (electrode spacing was 100
of both the amount of HNO3 added and the duration of mm). All measurements were made by the DC method
the ultrasonic treatment enabled the mean size of the with a solid state electrometer 610C (Keithley Instru-
particles in the sol to be varied. The indium hydroxide ments). The polychromatic light from a 100-W xenon
sol was prepared in an analogous fashion using indium lamp equipped with an infrared filter was used for the
nitrate solution (0.25 M) as a starting material. Thin photocurrent generation. It should be noted that the
films were deposited onto quartz substrates by spin resistivity of the films studied is strongly influenced by
coating and subsequently heated at 200 8C for 20 min. some environmental factors such as humidity and expo-
This procedure was repeated several times to achieve sure to the scattered visible light. Therefore, the dark
the required film thickness. Finally, the samples were resistance of the samples as well as the resistance under
annealed at different temperatures ranging from 200 to illumination were measured in a closed vessel equipped
700 8C for 1 h in air. Film thicknesses were estimated, with an optical quartz window and containing P2O5 as
using transmission electron microscopy data, to be 0.12– a drying agent.
0.15 mm after four deposition cycles.
Powder X-ray diffraction analysis of the films was 3. Results and discussion
performed on a Philips X’Pert diffractometer (Cu Ka-
radiation). High-resolution transmission electron micros- 3.1. Structural measurements
copy (HRTEM), microelectron diffraction and
energy-dispersive X-ray analysis (EDX) were carried Fig. 1 shows a set of the X-ray diffraction (XRD)
out using a Philips CM 300 UT microscope operating patterns obtained for TiO2, In2O3 and TiO2 –In2O3 com-
at 300 kV. TEM samples were prepared from finely posite films annealed at 200, 400 and 700 8C. XRD
divided xerogels annealed at the required temperatures analysis demonstrates that individual sol–gel derived
and dispersed in ethanol under sonification. The disper- In2O3 and TiO2 films heated at temperatures from 200
sion was dropped onto a 400-mesh carbon-coated copper to 450 8C consist of nanocrystallites of cubic phase
grid and the solvent was evaporated immediately. Opti- In2O3 and anatase TiO2, respectively. In the individual
 S.K. Poznyak et al. / Thin Solid Films 405 (2002) 35–41 37

Table 1
The average size (nm) of TiO2 and In2O3 nanocrystallites estimated from the XRD analysis of TiO2 –In2O3 composites annealed at different
temperatures

Composition Anatase phase Cubic In2O3 phase

200 8C 400 8C 700 8C 200 8C 400 8C 700 8C
TiO2 (100%) 5.1 7.9 62a
TiO2 (75%)–In2O3 (25%) 4.6 4.6 13 61
TiO2 (50%)–In2O3 (50%) 4.3 4.5 11 16 18 23
TiO2 (25%)–In2O3 (75%) 10 15 17 19
In2O3 (100%) 18 19 35
a
The average size of rutile crystallites.

TiO2 films, anatase-to-rutile transformation starts to SO2y4 inhibit this reaction w13,14x. It may be assumed
occur at 450–500 8C and is completed in the temperature that indium (III) ions as an impurity also inhibit the
interval from 700 to 750 8C. XRD patterns of TiO2 – conversion of anatase to rutile in the TiO2 –In2O3 com-
In2O3 films heated at different temperatures up to 800 posites. However, we suppose that another reason is,
8C do not reveal any additional phases other than those probably, responsible for the effect observed. According
observed for the individual oxide samples. This indicates to Zhang and Banfield w15x, the thermodynamic stability
that the chemical interaction of TiO2 with In2O3 does of the TiO2 phases is particle size-dependent, and at
not occur in the temperature range mentioned. The particle diameter below approximately 11 nm, anatase
average sizes of the oxide nanocrystallites estimated is more stable than rutile. Since the growth of anatase
from the X-ray line broadening according to Scherrer’s particles is retarded in the TiO2 –In2O3 systems, these
equation are collected in Table 1. These data show particles reach a size of approximately 11 nm only at
evidence that in the binary oxide films, there is a marked 700 8C for the TiO2 (50%)–In2O3 (50%) composite
suppression of the anatase crystallite growth during the and namely, at this temperature, traces of rutile appear
thermal treatment up to 700 8C in comparison with the in this composite.
individual oxide films. Therefore, for TiO2 (50%)– Fig. 2 presents typical high-resolution TEM images
In2O3 (50%) films, the anatase crystallites grow only of the TiO2 (50%)–In2O3 (50%) composite annealed at
from 4.3 to 11.1 nm in the temperature interval from 400 8C. The images show TiO2 and In2O3 particles with
200 to 700 8C. This process, which inhibits crystal mean sizes consistent with those calculated from the
growth, was previously observed in a number of multiple XRD data. The HRTEM patterns show lattice fringes
oxide systems such as CuO–Fe2O3, Cr2O3 –Fe2O3, for most particles indicating nanocrystalline material.
NiO–Al2O3, Al2O3 –ZrO2 and others w10,11x. In these Microelectron diffraction patterns (not shown) confirm
systems the addition of 10–30 mol% of foreign com- that the constituent crystallites of the annealed sample
ponent tended either to retard or even prevent the are anatase and cubic indium oxide. The EDX measure-
crystallization of the major component. This effect may ments indicate the presence of In, Ti and O in the
be explained by the fact that the particles of one samples, with the InyTi ratio being very close to the
component hinder the interaction between the particles calculated one.
of another component during the heat treatment. The
fact that In2O3 nanoparticles in the binary TiO2 (75%)– 3.2. Optical properties
In2O3 (25%) system start to grow more rapidly at T)
500 8C in comparison with the individual In2O3 samples, Optical transmission spectra of the sol–gel derived
is rather unusual. The nature of this effect is not clear nanocrystalline films reveal their high transparency ()
and further studies are needed. 90%) in the visible region of the spectrum. The spectra
In addition, the anatase-to-rutile transformation in the of TiO2 –In2O3 composite films are characterized by an
TiO2 –In2O3 samples occurs at markedly higher temper- absorption edge shifted to shorter wavelengths in com-
atures as compared with that in the individual oxide parison with those of the individual oxide films (Fig.
samples. It was previously reported that the rate of the 3). To estimate the direct band gap values of different
anatase-to-rutile conversion is very strongly dependent samples, we have plotted (A "v)2 against "v (where
on impurities and much work has dealt with the influ- A is the absorbance, which is proportional to the absorp-
ence of additives on this process w12,13x. Thus, the tion coefficient a, and "v is the photon energy) in
addition of Liq, Cu2q, Co2q, Mn4q and Cd2q as oxides accordance with common practice w16x. We have not
or fluorides (approx. 1%) was found to promote the estimated the indirect transition energy from the optical
polymorphic transformation while Nb2O5, PO43y and spectra due to the possible influence of thin film
38 S.K. Poznyak et al. / Thin Solid Films 405 (2002) 35–41

Fig. 4. Dependencies of the apparent direct band gap on the film

composition for samples annealed at (–m–) 200, (–s–) 400 and (–
j–) 700 8C.

on the composition cannot be explained by the Bur-

stein–Moss effect since the TiO2 (50%)–In2O3 (50%)
films show no decrease in the resistivity in comparison
with the TiO2 films (Fig. 5b).
We suppose that the causes of the behavior observed
can be rather different for the samples heated at 200,
400 and 700 8C. In a case of the films annealed at 200
8C, removal of the structural water from the films with
different composition may substantially affect their opti-
cal properties. For films heated at 700 8C, the suppres-
sion of the anatase-to-rutile transformation discussed
above should be taken into account for adequate analysis
of the optical properties. Therefore, XRD analysis shows
Fig. 2. Overview TEM image of TiO2 (50 wt.%)–In2O3 (50 wt.%) mainly the rutile phase in the pure TiO2 samples
composite annealed at 400 8C (top) and high resolution TEM image
of the same sample (middle). FFTs of areas of the HRTEM image annealed at 700 8C, while the anatase phase is the
bounded by squares (bottom) show that the area (a) corresponds to predominant component in the TiO2 (50%)–In2O3
(101)-oriented anatase TiO2 (distance between the arrows 0.351 nm) (50%) composites. The band gap of rutile is known to
and the area (b) corresponds to (211)-oriented cubic In2O3 (distance be somewhat lower (by 0.15–0.20 eV) than that of
between the arrows 0.413 nm).
anatase w17,18x. The most intriguing case is that of the
films heated at 400 8C when the X-ray patterns show
interference on the low-energy part of the absorption only anatase and cubic In2O3 phases for all compositions
edge. The direct band gap energy vs. film composition and no anatase-to-rutile transformation occurs. A blue
dependencies are presented in Fig. 4 for annealing shift of the absorption edge for the TiO2 –In2O3 com-
temperatures of 200, 400 and 700 8C. In all cases, the posites in comparison with the single-component films
Egd values are markedly higher in the binary oxide films could be explained by the quantum size effect in oxide
than in the individual oxides. Maxima of the apparent nanoparticles. However, this explanation is partly con-
Egd were obtained for the composite TiO2 (50%)–
In2O3 (50%) (Fig. 4). These extreme dependencies of
the absorption edge shift as well as the direct band gap

Fig. 5. (a) Dependence of the refractive index at ls600 nm on the

film composition for films heated at 400 8C. (b) Dark resistivity and
Fig. 3. Absorption spectra of TiO2 (50 wt.%)–In2 O3 (50 wt.%) com- resistivity under illumination as a function of the film composition
posite films (solid line) as well as single-component TiO2 (dashed for films heated at 400 8C. The dashed vertical line shows the cal-
line) and In2O3 (dotted line) films annealed at different temperatures: culated film composition corresponding to the formation of three-
(a) 200 8C; (b) 400 8C; (c) 700 8C. dimensional infinite cluster of In2O3 nanoparticles.
 S.K. Poznyak et al. / Thin Solid Films 405 (2002) 35–41 39

troversial when compared to recent work of Serpone et 3.3. Electrical measurements

al. where no evidence has been found for the band edge
shift in anatase sols with the particles’ size ranging from Fig. 5b presents the specific electrical resistivity (r)
2.1 to 26.7 nm w17x. measured in the dark and under UV illumination as a
The blue-shifted band edge of the TiO2 –In2O3 com- function of the composition of the nanocrystalline films
posite films may be associated with an effect of various heated at 400 8C. The dark resistivity of the binary
surface and interface species on the optical spectra. This oxide films rises abruptly from 34 to 3.4=107 V cm as
assumption is based on the results of recent studies the TiO2 content changes from 25 to 50 wt.% (Fig. 5b).
Values of the specific resistivity for the composites
devoted to the spectroscopic and structural characteri-
containing -25 wt.% and )50 wt.% of TiO2 are close
zation of other binary oxide systems. The occurrence of
to the resistivity of the individual In2O3 (approx. 2 V
Ti–O–Si or Ti–O–Al cross-linking bonds has been cm) and TiO2 (approx. 8=107 V cm) films, respective-
revealed for titanium dioxide supported on Vycor glass ly. In a similar manner, the photoresistivity measured
and silica or dispersed into SiO2 and Al2O3 matrices under UV illumination changes as a function of the
w19–24x. These bonds modify strongly the electronic TiO2 content in the nanostructured films. According to
state of oxygen and titanium atoms at the particle the previously reported data w30,31x, the electronic
interface and may be responsible for the band gap transport in nanostructured TiO2 films is dispersive and
enhancement observed w20,22x. Another important con- mainly controlled by trapping and detrapping of elec-
sideration is related to the geometry of the oxygen trons in nanoparticle surface intra-band-gap states. The
coordination around Ti. Tetrahedrally coordinated tita- conductivity of the TiO2 films is rather low in contrast
nium atoms have been shown to be present in TiO2 – to the In2O3 films having significantly higher conductiv-
SiO2 and TiO2 –Al2O3 systems w20,22,23x. Moreover, ity (Fig. 5b). In this case, the sharp decrease in the
five-coordinate Ti sites on anatase surfaces have been resistivity upon lowering of the TiO2 content in the
composites may be explained in terms of conduction by
revealed by EXAFS and XANES methods in nanostruc-
a percolation mechanism. The percolation threshold
tured TiO2 xerogels w25x. As proposed in these various
cannot be predicted theoretically in composite materials
works, the occurrence of such species, as well as surface made of a mixture of conducting and insulating phases
species with dangling bonds we.g. HO–Ti–(OTi)5 or having particles with different sizes and shapes w32,33x.
H2O–Ti–(OTi)5x might induce a marked blue shift in Therefore, to calculate the content of In2O3 (Ccrit) in
the band edge. It should be noted that in the case of the composite films which should correspond to the
nanocrystalline samples, the effect of such species on formation of three-dimensional infinite clusters of inter-
the optical properties can be significantly more dramatic connected In2O3 nanoparticles, we used a value of the
due to the very high surface-to-volume ratio. critical volume fraction of the conducting phase (xc)
For the TiO2 –In2O3 composites, an extreme depend- which was determined experimentally by Abeles et al.
ence of the refractive index (n) on the film composition w34x. They studied nanoparticulate W–Al2O3 films with
is also observed (Fig. 5a). The values of n vary through the particle sizes being close to those in the
a wide range from 1.67 for TiO2 (25%)–In2O3 (75%) TiO2–In2O3 composites and revealed that the resistivity
of the films increased abruptly in the vicinity of xc equal
composite film to 2.30 for individual TiO2 samples.
to 0.47. A value of the Ccrit (;62 wt.%), calculated for
Characteristically, the refractive index of the sol–gel the TiO2 –In2O3 composites using xcs0.47, coincides
derived TiO2 films matches the range of values (2.2– with the concentration range within which the film
2.4) reported for different anatase films, whereas the n resistivity changes abruptly (Fig. 5b).
value of 1.74 obtained for nanocrystalline In2O3 samples Fig. 6 shows the photocurrent transients after applying
is markedly lower than that (approx. 2.0) reported for UV illumination and also upon switching off the illu-
compact In2O3 thin films w26–28x. The reduced index mination. The ordinate presents the photocurrent divided
values for the individual oxides in comparison to their by the dark current for each sample. The photoconduc-
single crystal values seem to be due to the presence of tive sensitivity of the composite films is markedly lower
nanopores in the nanostructured films. The nature of the than that of the single-component TiO2 films. The
anomalous decrease in refractive index of the composite decrease in the photosensitivity may be related to the
films with decreasing the TiO2 content is not yet recombination losses at centres which exist predomi-
completely clear, and additional investigations are need- nantly at the interfaces between TiO2 and In2O3 nano-
ed. A composition-dependent pore volume may account particles. The rise and, especially, decay of photocurrents
for the observed anomaly. For example, an extreme are rather slow, indicating that it is not a pure electronic
dependence of the average pore size and pore volume process. The time for the photocurrent to decay by a
on the silica content has been previously revealed for factor of 10 and 50 is shown in Fig. 6 (inset) for
nanostructured TiO2 –SiO2 composites w29x. different film compositions. This time increases sharply
40 S.K. Poznyak et al. / Thin Solid Films 405 (2002) 35–41

processes in the overall photoconductivity generation

process in the former case.

4. Conclusions

In the present work, highly transparent TiO2 –In2O3

composite films with various TiyIn ratio were fabricated
using concentrated TiO2 and In(OH)3 sols prepared
without organic precursors. Structural transformations in
the binary oxide samples studied by the X-ray diffraction
method during the thermal treatment (up to 700 8C) of
the films show no chemical interaction between indium
and titanium oxides. However, a strong mutual influence
of the components was observed as the suppression of
the anatase crystallite growth during the thermal treat-
ment. Moreover, the optical properties of the composite
films exhibit strongly extreme dependencies of the
apparent optical band gap and the refractive index on
the film composition which could be attributed to an
effect of surface states at semiconductor nanoparticle
boundaries. The electrical charge transport in the com-
posite films occurs mainly through the network of
interconnected In2O3 particles and drastically changes
when a three-dimensional infinite cluster of these parti-
cles is formed. The photoconductivity decay is very
slow for the In2O3-enriched composite films, which
suggests a considerable contribution of oxygen desorp-
tion and adsorption to the photoconductivity generation
process in these nanoparticular films.

Fig. 6. Normalized photocurrent transients with light irradiation and Acknowledgments

with its cessation in air for the nanoparticular films, annealed at 400
8C, with the following composition: (1) TiO2 (100%); (2) TiO2 ¨
We thank Dr A. Eychmuller from the Institute of
(75%)–In2O3 (25%); (3) TiO2 (50%)–In2O3 (50%); (4) TiO2
(25%)–In2O3 (75%); (5) TiO2 (9%)–In2O3 (91%); (6) In2O3 Physical Chemistry of Hamburg University and Dr C.
(100%). Inset shows the time it takes for the photocurrent to decrease McGinley from DESY (Hamburg) for a number of
by 10 (j) and 50 (s) times as a function of the TiO2 content in the fruitful comments and stimulating discussion. We also
composite films. thank J. Kolny, A. Kornowski and S. Bartholdi–Nawrath
for assistance with the powder-XRD and HRTEM
by several orders of magnitude with decreasing the measurements.
TiO2 content from 50 to 25 wt.%. This effect may be
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