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Materials Chemistry C
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Investigation of the physical properties of

Fe:TiO2-diluted magnetic semiconductor
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Cite this: DOI: 10.1039/c7tc00233e

nanoparticles
a
Brijmohan Prajapati, Shiv Kumar,b Manish Kumar,a S. Chatterjeeb and
Anup K. Ghosh *a

Received 15th January 2017,
Accepted 30th March 2017
DOI: 10.1039/c7tc00233e
rsc.li/materials-c
The structural, optical, magnetic, and electrical properties of solgel-derived Ti1xFexO2 (0.00 r x r 0.05)
nanoparticles were investigated. Rietveld refinement of the X-ray diffraction data and TEM measurements
were carried out to analyze the crystalline structure and quality of all the samples. Raman spectroscopy
revealed a decrease in intensity and broadening of the characteristics peaks of Fe-doped TiO2 with respect
to those of the pristine sample, which signifies a structural distortion of the lattices. FT-IR, UV-vis, and PL
spectroscopy were used to investigate the optical properties. Magnetic measurements showed a weak
ferromagnetism at room temperature in both the pristine and Fe-doped TiO2 (x = 0, 0.02, and 0.05)
nanoparticles. Temperature-dependent resistivity measurements showed the semiconducting nature of the
samples and revealed that the thermally activated conduction (Arrhenius) mechanism is valid in the high-
temperature region, whereas Mott variable range hopping (VRH) mechanism is valid in the low-temperature
region. Dielectric properties of the samples were studied as a function of temperature in the frequency
range of 1 kHz to 1 MHz.

1. Introduction a number of studies have been reported on magnetism in oxide-

In recent years, dilute magnetic semiconductors (DMSs) have
gained significant attention from researchers due to their wide
range of potential applications in the developing fields of
optoelectronics, spin-based devices, transparent conductors,
gas sensors, photocatalysis, and photovoltaic devices.15 These
materials could be useful for the spintronic devices, where both
spin and charge can be utilized. Moreover, metal oxide nano-
structures, such as titanium dioxide (TiO2), have been extensively
studied for their potential in several technological applications
and for their high efficiency, low cost, photostability, and
chemical inertness. At normal pressure, TiO2 has three poly-
morphs, namely anatase, brookite, and rutile, all of which can be
described in terms of distorted TiO6 octahedra with different
symmetries or arrangements.6 Anatase and rutile both exist
in the tetragonal phase with the space groups I41/amd and
P42/mnm, respectively, whereas brookite holds an orthorhombic
structure with the space group Pbca.7 In the bulk, the rutile
phase is more stable, whereas when the particle size is less than
B11 nm, the anatase phase is more stable.810 In recent years,
a
Department of Physics, Banaras Hindu University, Varanasi 221005, India.
E-mail: akghosh@bhu.ac.in; Tel: +91-542-670-1556
b
Department of Physics, Indian Institute of Technology (BHU), Varanasi 221005,
India
based DMSs such as TM-doped TiO2, ZnO, and SnO2.1116 More-
over, transition metal (TM)-doped TiO2 has drawn the attention
of researchers for its potential as a promising DMS.1113
To explain the origin of the ferromagnetism in magnetic semi-
conductors, several models such as the F-center exchange
mechanism, carrier-mediated exchange, and super exchange
magnetic polarons have been used.1720 However, despite many
investigations, the origin and control of ferromagnetism at room
temperature in TM-doped TiO2 is one of the most controversial
issues in condensed matter physics. Due to a very low concen-
tration of the magnetic elements, to date, there is no definite
and conclusive model for DMSs. In DMSs, the most studied
model for a better explanation of the origin of the ferromagnetism
is the bound magnetic polaron (BMP) model, which mainly
focuses on the indirect interaction of two polarons via a localized
magnetic moment as the intermediate stage.11,20,21 Moreover, the
existence of oxygen vacancies is also one of the most important
tools to explain the origin of ferromagnetism in doped and
undoped metal oxides.22 Recently, Larde et al. investigated the
chemical homogeneity of dopants distributed in the framework of
a host semiconductor, which provided the knowledge on the origin
of ferromagnetism (intrinsic or extrinsic) in DMSs.23 Yuji Matsumoto
started work on ferromagnetism above room temperature in cobalt-
doped TiO2 anatase thin films and observed a systematic enhance-
ment in magnetization with an increasing Co concentration.24

This journal is The Royal Society of Chemistry 2017 J. Mater. Chem. C


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This work clearly demonstrated that the reason for the ferro-
magnetism in the samples was not due to the Co clusters, as
was also demonstrated by Park et al.25 and Mi et al.26 On the
other hand, Kim et al. concluded that Co clusters in the host
structure were responsible for the high-temperature magnetic
behavior.27 This suggests that the ferromagnetism was due to a
secondary phase, instead of being an intrinsic property of the
material, which is desirable for spintronics applications. More-
over, remarkable ferromagnetism at or above room tempera-
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ture has been observed in undoped reduced TiO2d films and
Fe-doped TiO2, which suggests that oxygen vacancies and/or
defects might be the source of magnetism for the so-called d0
magnetism.13,28 In similar consequences, it was reported that
TM-doped TiO2 exhibits ferromagnetism at room temperature,
not only in thin films but also as nanoparticles.2931 In spite of
this, many researchers have claimed that the observed RTFM in
doped TiO2 was likely due to the extrinsic impurity phases,
such as metal oxides or due to their clusters.32,33 These con-
flicting results among research groups suggest that the induced
or intrinsic magnetic properties of TiO2 are critically dependent
on the fabrication, doping, and growth conditions.
In this article, we mainly focus on the in-depth study of the
eect of iron doping on the structural, optical, magnetic, and
electrical properties and on understanding the origin of the
ferromagnetism in this system. To the best of our knowledge,
there is no report on the dielectric properties of anatase-phase
TiO2 nanoparticles doped with transition metals (Fe ion) except
for a few reports on the rutile phase.34,35
2. Experimental details
2.1. Synthesis of the nanoparticles
Pristine and Fe-doped TiO2 (Ti1xFexO2, 0.005 r x r 0.05)
nanoparticles were synthesized via the solgel technique.
Ti[OCH(CH3)2]4 (Aldrich 99%), Fe(NO3)39H2O (99.9% purity),
(CH3)2CHOH, and double-distilled water were used for the
material synthesis. All the chemicals were reagent grade and
used as received. The main scheme of the sample preparation
involved the hydrolysis of titanium(IV) isopropoxide (TTIP) in
water under controlled pH. Initially, two solutions in two
separate beakers, one containing Ti[OCH(CH3)2]4 (say: beaker-I)
and another containing double-distilled water in 2-propanol
(say: beaker-II), respectively, were prepared in an appropriate
proportion at room temperature. A drop-wise addition of the
solution from beaker-II into the former solution (of beaker-I)
led to the formation of the sol. This sol immediately changed
into the gel under vigorous stirring. The gel transformed into a
light yellowish block after heating at 100 1C for 12 h. Then, the
dried blocks were thoroughly ground with the help of an agate
mortarpestle and calcined at 500 1C temperature for 6 h to give
the undoped TiO2 (i.e., Fe0) nanoparticles. Fe: TiO2 (Fe0.5, Fe1,
Fe2, Fe3, Fe4, and Fe5, where the digit after Fe indicates the
atom percentage of Fe) samples, were prepared using the same
procedure with the appropriate stoichiometry ratio of Fe/Ti
(mass fraction).
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2.2. Characterization and measurements
For the structural analysis of the samples, an X-ray diract-
ometer (Model: Miniflex-II, Rigaku, Japan) with CuKa radiation
(l = 1.5406 ) was used. Transmission electron microscopy
(TEM) and HRTEM measurements were carried out on a
Techani-20 G2 microscope for the structural and microstruc-
tural characterization. To examine the structural modifications
and disorder of the TiO2 lattices, the Raman spectra in the
range of 100700 cm1 were studied at room temperature using
a Raman spectrometer (Renishaw Model: RM 1000) using
514.5 nm as the excitation source. Fourier transmission infra-
red (FT-IR) spectra of the samples were recorded in the range of
4000400 cm1 with a resolution of 1 cm1 using an FT-IR
spectrometer (Spectrum One, Perkin-Elmer Instrument, USA).
The KBr pellet technique was used to record the FT-IR spectra
at room temperature. UV-vis spectroscopy (Model: JASCO V-750,
Japan) and photoluminescence spectroscopy (LS-45, Perkin-
Elmer, USA) were conducted to examine the optical properties
of the samples. Magnetic measurements at room temperature
were carried out using the MPMS-03 SQUID (Quantum Design)
magnetometer. Variation of resistivity with temperature was
recorded by the conventional two-probe method using an electro-
meter (Keithley, 6517B, USA). Dielectric measurements as a func-
tion of temperature at different frequencies were performed using
an LCR meter (Model: E4980A, Agilent Technologies, USA).
3. Results and discussion
3.1. X-ray diraction
Powder X-ray diraction (XRD) data with Rietveld refinement are
plotted in Fig. 1. From Fig. 1, it can be clearly observed that the
diraction pattern of the samples (with iron doping up to 5 atom%)
Fig. 1 Rietveld refinement profiles of the X-ray diraction data of the
Fe-doped TiO2 samples. The circle represents the observed data (Obs)
while the solid line through the circles is the calculated profile (Calc), and
the vertical tics below the curves represent the allowed Bragg-reflections
for the anatase phase. The dierence pattern of the observed data and
calculated profile (ObsCalc) is given below the vertical tics.
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Fig. 2 Variation of the (101) peak intensity and shifting of the angle with
doping. The insets (a), (b) and (c) represent the variation of FWHM, the
crystallize size, and the d101-spacing with Fe concentration, respectively.
calcined at 500 1C for 6 h appear to be the merely in the anatase
phase ( JCPDS: #21-1272) with a pure crystalline nature without any
secondary phase. With increasing the Fe-concentration (x), the
intensity of the peaks gradually decreases, and the peaks become
wider and shift toward a higher 2y value. Full width at half maxima
(FWHM) analysis of the diraction peaks based on the Debye
Scherrer formula gave the crystallite size of the undoped and
Fe-doped samples of TiO2 as ranging from 17 nm to 7 nm, as x
varied from 0 to 0.05, respectively. In other words, with increasing
Fe concentration, the crystallite size of TiO2 decreases, as was also
observed by other researchers.3638 Fig. 2 shows the decrement of
the peak height, shifting toward higher 2y value and a widening
of the (101) plane with increasing Fe concentration. The gradual
decrement of the peak height signifies the incorporation of Fe ions
into the Ti-sites. The insets (a) and (b) of Fig. 2 show the variation
of FWHM and the variation of the crystallite size (D) with the
Fe-concentration (x). The crystallite size (D) was estimated from
Scherrers equation:39,40
0:9l
D (1)
b cos y
where l is the wavelength of the radiation used (l = 1.5406 ), y is
the Bragg angle, and b is the full width at half maxima (FWHM).
The decrease in the crystallite size of Fe-doped TiO2 nano-
crystals may be explained by the growth kinetic mechanism.
Actually, the chemical reactions follow two steps. In the first
step, nucleations and interactions among those nucleations
take place to reach the critical size. In the second step, these
critical sizes grow into the nanocrystals. The growth rate can be
explained on the basis of the binding energy of the bonds. In
the absence of Fe ions, the binding energy of TiO bonds on
a growing nucleation is at the maximum, but the presence
of Fe ions reduce the binding energy of FeO bonds.41 As the
consequence, the growth rate of the crystallites slows down,
leading to (an exponential) decrease in the crystallite sizes as x
increases. Similar observations were also reported in the
literature,12,38 namely that with the increase in Fe concen-
tration into TiO2, the crystallite size decreases.
With increasing the Fe concentration (x), a small shift of the
(101) peak toward higher 2y values is observed (Fig. 2), which
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leads to a decrease in the interplanar spacing. The inset (c) of
Fig. 2 shows that the interplanar spacing of the (101) plane
(d101) decreases with increasing x. This result can be explained
as follows: there are two simultaneous eects of the Fe-doping:
(i) an eect from the ionic radius and (ii) an eect from the
oxygen vacancies. The ionic radius of the Fe3+ ion (0.64 ) is
slightly larger than that of the Ti4+ ion (0.60 ) for the
coordination number 6. This leads to an increase in the
interplanar spacing and consequently a decrease in the 2y
value. On the other hand, substitution of Fe3+ for Ti4+ leads
to the creation of oxygen vacancies (to maintain charge neutrality).
The increase of these oxygen vacancies (confirmed from the PL
study, as discussed latter) tends to decrease the interplanar
spacing by increasing the 2y value.16,42 The latter eect dominates
over the former one. Hence, with increasing the doping concen-
tration (x), the interplanar spacing decreases, causing a shift of
the 2y value to the higher side.16,42 The substitution of Fe3+ ions
into the Ti4+ sites may be expected because the ionic radius of Fe3+
ions (0.64 ) is very close to that of Ti4+ ions (0.60 )43 for the
coordination number 6. The values of the crystallite size, lattice
parameters a and c, interplanar spacing (d101), and the unit
cell volume (V) obtained from the Rietveld refinement (using
the Fullprof program) of the samples are summarized in
Table 1(a) and (b), respectively. From these values, it can be
observed that there is no appreciable change of the lattice
parameters (only a negligible small elongation of the a-axis
and a negligible small contraction of the c-axis) with increasing
Fe substitution. The variation of dierent structural para-
meters, namely a, c, and V with the Fe-concentration is shown
in Fig. 3. The negligible change in the lattice parameters due to
Fe-doping may be attributed to the small dierence in the ionic
radii of Fe3+ and Ti4+ ions. The linear dependence of the lattice
constants on Fe-ion doping suggests the pure-phase formation
of anatase TiO2 (up to x r 0.05) and obeys Vegards law,
confirming the incorporation of Fe ions into the host lattice.44
3.2. Transmission electron microscopy
The morphology and microstructure of the nanoparticles were
examined by transmission electron microscopy (TEM). Typical
low-magnified TEM micrographs of Fe0 and Fe5 are shown in
Fig. 4(a) and (b). From the images, it is clear that most
nanoparticles are more or less spherical in shape and that
the average crystallites size are B16 nm for Fe0 and B07 nm
for Fe5, respectively, which corroborates the result obtained
from the XRD measurements. Fig. 4(c) and (d) show the high-
resolution TEM (HRTEM) images of Fe0 and Fe5, respectively.
The HRTEM micrograph (Fig. 4(c)) shows that the interplanar
spacing of the (101) plane (d101) of Fe0 is about 0.357 nm, while
Fig. 4(d) shows that the interplanar spacing of the (101) plane
(d101) of Fe5 is about 0.345 nm, which is slightly smaller than
that of Fe0. The d101 value of Fe0 and Fe5 were determined from
the HRTEM measurements are well matched with those of the
XRD measurements. Moreover, a decrease in the d101 value for
the Fe5 samples compared to Fe0 was also observed in the XRD
measurements (Table 1(b)). Selected area electron diraction
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Crystallite size (nm)

0.28447
0.04741
0.00351
Table 1 (a) The average crystallite sizes of the anatase phase for Ti1xFexO2 (0.00 r x r0.05) with dierent Fe-ion concentrations. (b) Values obtained from the Rietveld refinement: the lattice

0.2721




3.78810
9.48250
3.51577
136.0710
Fe5
17
15
13
11
09
08
07

0.28367
0.04728
0.00352
0.2713
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9.4555
3.5161
3.78780

135.6621
Fig. 3 Variation of the lattice parameters of Ti1xFexO2 (0.00 r x r 0.05)

Fe4
with Fe concentration.

0.04732
0.00355
0.28392

0.2716




3.78850
9.46390
3.51710
135.8382
Ti1xFexO2

Fe3
Fe0.5
Fe0

Fe1
Fe2
Fe3
Fe4
Fe5

0.28471
0.04745
0.00352
0.2723




3.78770
9.49030
3.51780
136.1542
Fe2
0.28487
0.04748
0.00351
0.2724

Fig. 4 (a) TEM image of Fe0. (b) TEM image of Fe5. (c) HRTEM image of
Fe0 with SAED (inset). (d) HRTEM of Fe5 with SAED (inset).




3.78770

136.2303
9.49560
3.51810

(SAED) patterns, shown in the inset of Fig. 4(c) and (d), reveal
Fe1
parameters a and c, interplanar spacing (d101), and the unit cell volume (V)

the polycrystalline nature of the materials.

x (Fe weight%)

3.3. Raman spectroscopy

0.28511
0.04752
0.00352
0.2727

Raman spectroscopy has proven to be one of the most sensitive

and important tools to detect local structural changes due
0.005
0.01
0.02
0.03
0.04
0.05






to the incorporation of TM ions into a host lattice. Raman

0

136.3537
3.78780
9.50370
3.51860

spectroscopy was thus employed to confirm the crystalline quality

Fe0.5

of Fe-doped TiO2 nanoparticles. Anatase TiO2 possesses a tetra-

gonal structure and belongs to the space group D19 4h (I41/amd).
45

According to the group theory analysis at the G point of the

0.28528
0.04754
0.00351
0.27282

Brillouin zone, 15 optical phonons of TiO2 have the irreducible

representation as:45 Gopt = 1A1g + 1A2u + 2B1g + 1B2u + 3Eg + 2Eu.
The modes A1g, B1g, and Eg are Raman active, while the modes A2u




136.4110
3.78770
9.50820
3.51870

and Eu are infrared active. The B2u mode is inactive both in the
Sample

Raman spectra and in the infrared spectra. Therefore, the Raman

Fe0

spectrum contains six fundamental lattice vibrations, namely

one A1g, two B1g, and three degenerate Eg modes. Again, it is
reported that due to the overlapping of A1g (B513 cm1) and B1g
Parameters

(B519 cm1) modes at room temperature (which can be resolved

d101 ()
V (3)

only in low-temperature measurements), the Raman spectrum of

a ()
c ()
No.

(b)
(a)

the anatase TiO2 shows major five Raman bands at 144, 197, 399,
1
2
3
4
5
6
7

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ionic radii, and reduces the translational symmetry giving rise to

local distortions in the lattice. Such local distortion disrupts the
long-range ordering in TiO2 and weakens the electric field
associated with a specific mode.50 Moreover, with increasing
the Fe-doping concentration, OTiO bonds may be disturbed,
causing new bond formation e.g., FeO bonds. Such disturbance
and new FeO bonds formation may affect the Raman-active
modes, resulting in a broadening of the peaks.

3.4. FT-IR spectroscopy

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The FT-IR spectroscopy gives information about the functional

Fig. 5 Raman spectra of the undoped and Fe-doped TiO2 nanoparticles
using 514.5 nm Ar+ laser as the excitation source. The variation of the peak
height and FWHM at 144 cm1 with the Fe-concentration shown in insets
(a) and (b).
515, and 639 cm1.46,47 The normalized Raman spectra of
undoped and Fe-doped TiO2 nanocrystals measured at room
temperature are shown in Fig. 5. The Raman spectra were
normalized by the Min/Max method [using the relation:
Inom = (I  Imin)/Imax], where, I is the unnormalized intensity.
In the present work, five bands were also observed for Fe0 at 144,
196, 396, 516, and 639 cm1 (Table 2). Three Raman bands at
144, 197, and 639 cm1 were assigned to the Eg modes, while the
396 cm1 band was assigned to one of the two B1g modes. The
Raman band at 516 cm1 represents the overlapping of A1g and
B1g modes. The Eg peak was associated with the symmetric
stretching vibration of OTiO in TiO2, while the B1g peak was
due to the symmetric bending vibration of OTiO, and the A1g
peak was the result of the antisymmetric bending vibration of
OTiO.48 Fig. 5 reveals that the Raman spectra of Fe-doped TiO2
are similar to that of the undoped anatase TiO2 and that the
intensity of the Raman peaks gradually decrease with increasing
the dopant concentration. This result supports the incorporation
of Fe ions into the substitution site of the host lattice. Further-
more, doping also causes a small broadening of the Raman
peaks. The monotonic decrement of the peak at 144 cm1 and its
gradual broadening (FWHM) are shown in the insets (a) and (b)
of Fig. 5. The decrease in the peak intensity and peak broadening
might be related to the crystal size eects (as in the spatial
correlation model for the phonon confinement) and/or increase
of the microscopic structural distortion in the lattice.49 Fe3+
substitution induces a microscopic structural distortion in the
periodic Ti4+ sub-lattice due to dierences in the charges and
groups present in the compound, the molecular geometry, and
the inter- or intramolecular interactions. In the present study,
FT-IR spectroscopy was employed at room temperature to study
the vibrational bands of the Fe:TiO2 samples for metaloxygen
bonds, and any changes due to Fe substitution. The FT-IR
spectra of the samples are shown in Fig. 6. The different bands
observed in the FT-IR spectra of TiO2 and Fe-doped TiO2
nanoparticles are summarized in Table 3. The broad band
appearing around 3450 cm1 corresponds to the stretching
vibration of OH groups linked with titanium atoms TiOH,
while the band around 1630 cm1 was the characteristic bend-
ing vibrations of HOH. However, the peak at 1384 cm1 may
be due to a CO stretching bond present in residual organics.
This peak may be a result of the organic radical (OC3H7),
which is adsorbed in the nanoparticles. The bands centered at
B540 cm1 are due to metaloxygen bonds (TiO, FeO) of the
(Ti, Fe)O2 solid solution.51,52 Furthermore, neither the peak
corresponding to a-Fe2O3 nor to other oxides of iron appears in
the spectra. This reveals that Fe3+ is introduced into the
titanium framework. This result corroborates the XRD results
and the other above-mentioned measurements.
3.5. UV-vis diuse reflectance spectra
UV-vis diused reflectance spectra (DRS) were obtained to
investigate the light absorption characteristics of all the sam-
ples. BaSO4 was used as a reference. The spectra were recorded
at room temperature in the wavelength range of 200800 nm.
Fig. 7(a) shows the UV-vis DRS of the samples: Fe0, Fe0.5, Fe1,
Fe2, Fe3, Fe4, and Fe5, respectively. The absorption band edge
for Fe0 was around 391 nm (3.17 eV), which is similar to the
intrinsic band-gap of pure anatase TiO2 (B3.2 eV). Again, the
iron-doped samples show an absorption in the visible region of
the spectrum. The indirect transition in this Fe-doped TiO2
system was confirmed from the plot of [F(RN)hn]1/2 vs. hn, as
shown in Fig. 7(b) for various compositions. The symbol used,

Table 2 Raman modes of pristine and Fe-doped TiO2 samples

Vibration frequency (cm1)

Process Assignments Fe0 Fe0.5 Fe1 Fe2 Fe3 Fe4 Fe5
Symmetric stretching vibrations of oxygen atoms in OTiO bond. Eg 143 144 145 144 144 144 147
Symmetric stretching vibrations of oxygen atoms in OTiO bond. Eg 196 197 197 197 197 197 197
Symmetric bending vibrations of OTiO bond. B1g 396 397 397 396 396 396 398
Vibration of OTiO bond with Ti atom fixed. A1g & B1g 516 517 517 516 517 516 518
Symmetric stretching vibrations of oxygen atoms in OTiO bond. Eg 638 640 638 639 639 639 639

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Fig. 6 FT-IR spectra of the Fe-doped TiO2 nanoparticles at various

doping concentrations.

Table 3 FT-IR spectra of dierent vibrational bands

Modes (cm1) Fe0 Fe0.5 Fe1 Fe2 Fe3 Fe4 Fe5

OTiO stretching 540 540 541 544 546 547 547
(OHO) bending 1630 1630 1630 1630 1630 1629 1629
(OH) stretching 3456 3456 3456 3456 3456 3455 3456
(CO) stretching 1384 1384 1384 1384 1384 1384 1384
CO2 molecules in air 2347 2347 2347 2347 2347 2347 2347

F(RN), is known as the KubelkaMunk function and can be

calculated from the following equation:53 Fig. 7 (a) UV-vis diuse reflectance spectrum. (b) The plots of [F(RN) hn]1/2
versus photon energy, while the inset shows the variation of band energy
F(RN) = (1  RN)2/2RN, (2) with the Fe-ion concentration.
A
where RN = 10 is the reflectance coecient of the sample and
A is the absorbance of the corresponding samples. The corres-
ponding optical band gaps (Eg) were estimated from the extra-
polation of the linear portion of the curves of Fig. 7(b). The
band gaps estimated from the intercepts were 3.17, 2.92, 2.79,
2.56, 2.40, 2.37, and 2.22 eV for Fe0, Fe0.5, Fe1, Fe2, Fe3, Fe4,
and Fe5, respectively. An exponential decrease in the band gap
with the dopant concentration is shown in the insect of
Fig. 7(b). This red-shift of the absorbance spectra (decrease in
the band gap) with doping may be induced due to a sub-band-
gap transition corresponding to the excitation of 3d electrons of
the Fe ions to the TiO2 conduction band.36 The decrease in the
band gap with the incorporation of TM ions into the TiO2 has
Fig. 8 Room temperature photoluminescence spectra of Ti1xFexO2
been found by other researchers also.54
(0.00 r x r 0.05) samples. Inset represents the intensity variation of the
peaks at 485 nm and 530 nm with the Fe-concentration.
3.6. Photoluminescence study
Photoluminescence (PL) spectroscopy is an eective tool to
study the lattice defects in the samples. Fig. 8 shows the room The UV emission band can be explained by a near-band-edge
temperature photoluminescence (PL) spectra of the undoped (NBE) transition originating from the recombination of carriers
and all the Fe-doped samples excited at 320 nm. From the bound within excitons.56 The violet-blue emission peak at
figure, it is evident that all the samples show mainly four broad around 423 nm originates from the charge recombination on
peaks in the PL spectra. The peaks are broad possibly because shallow trap surface states. The blue-green band (B485 nm)
of the presence of several recombination sites and defects. The emission is from the de-excitation from lower vibronic levels in
peak in the UV region around 375 nm may be attributed to the Ti4+ 3d states of the TiO2 lattice to the deep acceptor levels
the near-band-edge excitonic emission (NBE), because the due to surface defects. The green band (B530 nm) emission is
energy corresponding to this peak is close to the band-gap due to the defect-oriented oxygen vacancies. Since the charge
energy (3.17 eV) of TiO2 (estimated by UV-vis measurements).55 state of the dopant and host are not the same, doping with the

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Journal of Materials Chemistry C
Fe ions causes the generation of oxygen vacancies to maintain
the charge neutrality.16,57 When Fe3+ ions substitute the Ti4+
sites, the energy level corresponding to the defect-oriented
oxygen vacancies may be the deepest for the band gap of
TiO2.58 Therefore, the green emission peak around 530 nm is
due to de-excitation from lower vibronic levels in the oxygen
vacancies of the TiO2 lattice to the ground state.59 It can be
observed from the inset of Fig. 8 that the green band at 530 nm
becomes intense [normalized PL intensity increases linearly]
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with increasing Fe-doping, which signifies that the oxygen
vacancies (OV) increase with the increasing Fe concentration.
Due to the enhancement in the density of oxygen vacancies (OV)
with increasing Fe-doping, the density of surface dangling bonds
increases. This increase in dangling bonds increases the prob-
ability of visible (green) emission by decreasing the probability of
UV emission. This seems to be the main cause behind the
enhanced green emission with increasing Fe-doping. Moreover,
oxygen vacancies (OV) are mainly responsible for the ferro-
magnetism at room temperature (as discussed later).
3.7. Magnetic measurements
Despite many eorts, there is still a lack of understanding of
the origin of ferromagnetism at room temperature (RTFM) in
oxide-based DMS materials. There is no definite conclusion
whether RTFM is an intrinsic property caused by direct or
indirect interactions, or is indeed an extrinsic eect due to
direct interaction between the local moments in magnetic
impurity clusters. The experimental results reported by various
groups are quite conflicting, in particular for TiO2-based DMS.
The MH curve obtained from the superconducting quantum
interface devices (SQUIDs) at room temperature for the samples
Fe0, Fe2, and Fe5 are shown in Fig. 9. It can be clearly seen
from the inset of Fig. 9 that all the samples (Fe0, Fe2, and Fe5)
exhibit weak ferromagnetism at room temperature. The Fe-doping
in TiO2 causes an increment in the remnant magnetization
(the Mr-value) from 8.56  104 to 26.58  104 emu g1, while
a decrement from 442.53 Oe to 137.834 Oe in coercivity (the
Hc-value). The obtained hysteresis at room temperature supports
the fact that the sample is weakly ferromagnetic. One of the
reasons behind the occurrence of ferromagnetism in TiO2 is the
Fig. 9 SQIUD-derived room temperature hysteresis loop (MH curve).
The inset represents the magnified portion in the center of the histogram.
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oxygen vacancy-induced lattice distortion in undoped TiO2.60 The
present samples also show a strong presence of oxygen vacancies
(OV defects) in undoped as well as in Fe-doped TiO2 as evidenced
from the PL study (Fig. 8). Therefore, RTFM is thought to be an
intrinsic property in homogeneously doped samples and is
related to the defects. Furthermore, Ti1xFexO2 powders are able
to retain their anatase nature up to 5%-Fe-doping, and neither
second metallic phases nor metal clusters were observed from
the XRD, HRTEM, and Raman results. Therefore, we believe that
the observed RTFM in the present samples are intrinsic and
induced by the defects, particularly due to the oxygen vacancies
in the samples.
3.8. Resistivity measurements
The electrical resistivity (r) of the Fe-doped samples was
measured as a function of temperature to see the eect of
Fe-doping on the electrical conductivity. Electrical resistance
measurements were carried out using the two-probe technique
in the temperature range of 220300 K. At room temperature,
the resistivity of the Fe0 and Fe5 samples were 2.10  106 to
2.7  105 Ohm-meter respectively. The decrease in resistivity
with the increasing Fe concentration in the present samples
can be explained by the splitting of the d state (into eg and t2g)
of the transition metal ions under the influence of a crystal
field in TiO2. Therefore, with the incorporation of a dopant, the
donor level is shifted toward the conduction band, and then a
very small increase in temperature may cause the transition of
electrons from the donor level to the conduction level. In
general, we can say that the increase in the concentration of
metal (Fe) into the host site leads to the gain of some additional
electrons, which increases the electrical conductivity. Fig. 10
displays the temperature dependencies of the electrical resistivity
r(T), measured without and with Fe-dopant. The main feature
that can be observed is that the resistivity r(T) decreases exponen-
tially with the increase in temperature. This reveals that pristine
as well as 5%-Fe-doped TiO2 preserves the semiconducting
nature. The plots of ln r vs. 1000/T (Fig. 11 for Fe0 and Fig. 12
for Fe5) show two different slopes, one in the high-temperature
region and another in the low-temperature region. These two
different slopes signify two different conduction mechanisms,
Fig. 10 Temperature-dependence of the electrical resistivity for samples
Fe0 and Fe5.
J. Mater. Chem. C
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Paper Journal of Materials Chemistry C

Table 4 Variation of the activation energy (Ea) of Ti1xFexO2 (x = 0, 0.05)

S. No. Sample Slope Activation energy Ea (eV)

1 Fe0 6.41752 0.4295
2 Fe5 4.95813 0.5528

r(T) = r0 exp[T0/T]1/4 (4)

where r0 and T0 are constants and are given by

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r0 = {[8pakBT/N(EF)]1/2}/(3e2nph) (5)

and,

T0 = 18a3/[kBN(EF)], (6)
Fig. 11 Variation of ln r as a function of 1000/T for Fe0 nanoparticles.
Inset: ln (rT1/2) vs. T1/4 the linear fit indicates the validity of the two where nph (B1013 s1) is the phonon frequency at Debye
dierent conduction mechanisms, namely the Arrhenius mechanism and
temperature, N(EF) is the density of localized electron states
the variable range hopping conduction mechanism.
at Fermi level, and a is the inverse localization length. Using
eqn (4) and (5), a linear plot is expected from ln(rT1/2) vs.
(1/T)1/4 for VRH conduction. Thus, the linear fit of
 
1 1
2
ln rT vs: T 4 plot (insets of Fig. 11 and 12) clearly

indicates that the VRH is the dominant mechanism of conduc-

tion in the low-temperature region.

3.9. Dielectric measurements

The dielectric constants of the sintered pellet of the Ti1xFexO2
(x = 0, 0.02, and 0.05) samples were measured as a function of
the temperature at dierent frequencies (i.e., 1 kHz, 10 kHz,
100 kHz, and 1 MHz) and are shown in Fig. 13. The room
temperature (300 K) dielectric constant at dierent frequencies
as a function of Fe-ion concentration is summarized in Table 5.
Fig. 12 Variation of ln r as a function of 1000/T for Fe5 nanoparticles.
There are three main factors aecting the values of dielectric
Inset: ln (rT1/2) vs. T1/4 the linear fit indicates the validity of the two constant, namely the temperature, frequency, and Fe concen-
dierent conduction mechanisms, namely the Arrhenius mechanism and tration. It is clear from Fig. 13 that the dispersion in the
the variable range hopping conduction mechanism. dielectric value for the entire sample is weak in the low-
temperature region up to 160 K. Beyond this temperature, it
increases more rapidly in the low-frequency region, while this
namely Arrheniuss mechanism and Motts variable range
hopping (VRH) of polarons,61,62 are being operated in these
two temperature regions. The linear fit of the plot of ln r vs.
1000/T (the slope of which gives the activation energy) shows
that thermally activated band conduction is the dominant
mechanism for the high-temperature region. The thermally
activated resistivity at the high-temperature region follows the
Arrhenius law as:
r(T) = r0 exp[Ea/kBT ] (3)

where, kB is the Boltzmanns constant, r0 represents a constant

contribution due to the defects, and Ea is the activation energy,
which have been estimated using eqn (3) and the values are
given in (Table 4). It was observed that the activation energy
increases with increasing Fe concentration.
A clear deviation in the linear fit of ln r vs. 1000/T plot was
observed in the low-temperature region. The conduction
mechanism at low temperature due to the variable range Fig. 13 Temperature and Fe-concentration dependence of the dielectric
hopping of polarons can be described by Motts equation: constant (e 0 ) at (a) 1 kHz, (b) 10 kHz, (c) 100 kHz, and (d) 1 MHz.

J. Mater. Chem. C This journal is The Royal Society of Chemistry 2017


Journal of Materials Chemistry C
Table 5 Room temperature (300 K) dielectric constants at dierent
frequencies as a function of the Fe-concentration
Dielectric constant (e 0 ) at room temperature
S. No. Sample 1 kHz 10 kHz 100 kHz 1 MHz
1 Fe0 104.5131 96.41677 82.50211 77.6539
2 Fe2 84.1063 76.61862 62.69731 57.6972
3 Fe5 75.8342 70.09598 60.71319 57.1525
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increase is slower and more stable at higher frequencies. This
may be because at relatively low temperatures, the possible
orientations of the dipoles with respect to the direction of the
applied field are not too good so they deliver a weak contribu-
tion to the polarization and dielectric behavior. When moving
toward the higher temperature region, there must be enough
thermal energy for the dipoles to obey the change in the
external frequency and to more easily contribute to the polar-
ization, leading to an increase in the dielectric constant. It is
observed from Fig. 13 that the dispersion (with temperature) is
rapid at lower frequencies but it is slow and approaches almost
frequency independence at higher frequencies. This is because
at higher frequencies charge carriers are responsible for the
polarization lag behind the applied alternating field and due to
this they cannot follow the changes in the applied field over a
certain frequency limit.63,64 Moreover, the dielectric constant is
largely aected by the Fe-concentration. It can also be explained
on the basis of the fact that polarization is a size-dependent
property. The size-dependent static dielectric constant can be
calculated using the relation:65,66
 
p2 h2 1 1 1:8e2
DE  (7)
2R2 me mh es R
where DE (eV) is the shift in band gap energy (i.e., DE =
Enano  Ebulk), h is the reduced Plank constant, R is the radius
of the cluster (m), me* and mh* are the eective masses of the
electron in the conduction band and of the hole in the valance
band of TiO2, es is the static dielectric constant, and e is the
electronic charge. The values of me* and mh* in terms of free
electron mass range from 5me to 13me for me* and up to 2me for
mh*. For simplicity, the average value 9me (kg) for me* and 2me
(kg) for mh* have been used.67 The crystallite sizes, taken from
the XRD measurements are 17 nm, 11 nm, and 7 nm, respec-
tively. Therefore, with knowledge of the band gap for nano-
particles (Enano) estimated from the UV-vis data and by taking
Ebulk = 3.2 eV,67 the calculated values of es for Fe0, Fe2, and Fe5
are 112.0, 8.0, and 7.6, respectively. This clearly indicates that es
is largely aected by the shift in the band gap energy and/or by
reduction of the grain size. From the XRD data, it can be
observed that the crystallite size decreases from 17 nm (for
Fe0) to 7 nm (for Fe5) with the increase in Fe-ion concentration,
hence decreasing the dielectric constant of the materials.
4. Conclusions
Undoped and Fe-doped TiO2 nanoparticles were synthesized via
the solgel route. The Fe-dopant was successfully incorporated at
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the substitution site of Ti4+ as evidenced by XRD and Raman
spectroscopy. X-ray diffraction study with Rietveld refinement
was utilized to determine the single phase nature, crystallite size,
and lattice parameters of the samples. The crystallite size decreased
exponentially with the increase in the Fe-concentration being due
to the slowing down of the growth rate. The crystallite size as
measured by HRTEM corroborated with the XRD results. The
intensity of the Raman peaks gradually decreased with increasing
the dopant concentration. This result supports the incorporation of
Fe ions into the substitution site of the host lattice. Furthermore,
doping also causes a small broadening in the Raman peaks. The
decrease in the peak intensity and peak broadening might be
related to crystal size effects and/or to an increase in microscopic
structural distortions in the lattice. Different functional groups
present in the samples were identified through FT-IR spectroscopy.
UV-vis measurements showed that the band gap for all the samples
decreased with increasing the Fe-ion concentration. The room
temperature PL studies suggested that more lattice defects and
oxygen vacancies are created due to the Fe3+-ion substitution of Ti4+
ions in the TiO2 lattice and play an important role in the emission
property and ferromagnetism. Ferromagnetism at room tempera-
ture (RTFM) was observed from MH measurements, and it was
found that the magnetization increased with increasing the
Fe-concentration. This may be due to an increase in the defects,
particularly due to the oxygen vacancies in the samples. Resis-
tivity measurements showed the semiconducting nature of the
samples and indicated that a thermally activated Arrhenius
conduction mechanism is valid in the high-temperature region,
whereas Motts variable range hopping (VRH) of polarons
mechanism is valid in the low-temperature region. The activa-
tion energy as a function of Fe concentration was estimated in
the high-temperature region. It was observed that Fe substitu-
tion on Ti site has a considerable effect on the dielectric
behavior of the material. The dielectric constants measured
in the temperature range of 140300 K and a frequency range
of 1 kHz to 1 MHz showed a decrease with the incorporation of
Fe-dopant ions into the host sites of Ti.
Acknowledgements
AKG is thankful to DAE-BRNS, India; CSIR, India; and UGC,
India for financial support (Grant no. 2011/37P/11/BRNS/1038-1,
03(1302)/13/EMR-II, and F: 42-787/2013 (SR) respectively). AKG is
also thankful to DST-FIST program; to UGC-UPE program; to
UGC-CAS program; to the Bio-Physics lab, Dept. of Physics for
FT-IR, PL facilities, and to Prof. Ranjan Kr. Singh for Raman
Spectroscopy facility.
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