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Article history:
Received 22 December 2013
Received in revised form 6 February 2014
Accepted 14 February 2014
Available online 22 February 2014
Keywords:
Oxide materials
Solgel processes
Exchange and superexchange
Impurities in semiconductors
Luminescence
Magnetic measurements
a b s t r a c t
In this work we have studied the magnetic properties of solgel synthesized Gd doped TiO2 nanoparticles.
The Gd concentration varying from 0.03 to 0.07 mol. Structural, morphological and compositional analyses have been monitored with X-ray diffraction, transmission electron microscope (TEM), Raman spectroscopy and energy dispersive X-ray (EDX) spectroscopy. XPS spectra establish that Gd ions are in the +3
oxidation state. Photoluminescence intensity enhances at 0.03 and 0.05 mol and then quenches at 0.07.
This is likely due to the formation of emission quenching centers. All the samples exhibit paramagnetism
at room temperature as well as at 10 K. It is observed that due to the shielding of 4f shell of Gd3+ ions by
6s5d shell the direct exchange interaction of these Gd3+ ions with other Gd3+ ions is weak. These noninteracting and localized magnetic spins of Gd3+ induce only paramagnetism. The high magnetization
exhibited by the samples at 10 K is due to minimization of the thermal randomization of the magnetic
spins. Antiferromagnetic interaction persists at 0.03 mol and it gets stronger at 0.07 mol. Antiferromagnetism appears due to strong superexchange interaction of Gd3+ ions via O2 ions.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Diluted magnetic semiconductors (DMS) represent a synergetic
collaboration between charge based semiconductors and spin
based magnetism [13]. Following the success of (Ga, Mn) As,
many DMS materials have been discovered which exhibit room
temperature ferromagnetism (RTMF). In particular, theoretical
studies predicted and experiments veried that some wide band
gap semiconductors such as ZnO and TiO2 doped with transition
metals are effective DMS [4]. Magnetism in oxide based DMS are
often inadequate owing to low doping concentration and poor conductivity, both disfavoring the carrier based mechanism [5]. Furthermore, precipitates of doped magnetic elements and
inadvertent contaminations complicate experimental ndings.
TiO2 is a transparent wide band gap semiconductor. Transition
metal doping has been proposed to introduce magnetism in TiO2
nanoparticles [6]. The magnetic properties of doped TiO2 are
strongly sensitive to preparation condition, morphology and presence of defects. Bhattacharya et al. synthesized Mn doped TiO2
nanoparticles by one pot RAPET technique (reaction under autogenic pressure at elevated temperature) and reported ferromagnetic behavior up to 1%. However, with the increase in dopant
concentration up to 5% and 7% the system showed paramagnetic
behavior [7]. Peng et al. observed ferromagnetism in Mn doped
Corresponding author. Tel.: +91 3712267120; fax: +91 371222345.
E-mail address: ajc@tezu.ernet.in (A. Choudhury).
http://dx.doi.org/10.1016/j.jallcom.2014.02.070
0925-8388/ 2014 Elsevier B.V. All rights reserved.
202
GaN [13,14]. Dalpian and Wei reported that the direct coupling between the Gd atoms was antiferromagnetic in nature in Gd doped
GaN [13]. The ferromagnetic phase was stabilized by the electrons
due to the mixing of Gd f with host s states. Liu et al., however, reported that the room temperature ferromagnetism in Gd doped
GaN was due to the interaction of Gd 4f spins via pd coupling
involving holes introduced by the intrinsic defects [14].
In the present study our objective is to investigate the structural, morphological and magnetic properties of TiO2 nanoparticles
due to doping of gadolinium. The structural and morphological
characterizations are done with X-ray diffraction, Raman, HRTEM.
The valence state of Gd in the host matrix is characterized by XPS.
This manuscript describes the magnetism in Gd doped TiO2 nanoparticles. To the best of our knowledge there are no reports on
magnetism in Gd doped TiO2 nanoparticles. Unlike transition metal
doped TiO2 where magnetism is initiated by dopants and oxygen
defects, the similar situation is not encountered in this system.
Although Gd is ferromagnetic, doping of this ion does not initiate
ferromagnetism in TiO2. It is observed that the unpaired spins in
Gd 4f does not undergo direct exchange interaction with nearest
Gd3+ ions nor do they take part in carrier mediated ferromagnetism. We have observed paramagnetism which is due to the presence of localized non-interacting spins present in 4f shell of Gd3+.
2. Experimental methods
2.1. Material synthesis
Gd doped TiO2 nanoparticles with three different nominal concentrations of Gd
(0.03 mol, 0.05 mol and 0.07 mol) were synthesized employing a simple solgel
method. The precursors for dopant and host were taken to be gadolinium nitrate
hexahydrate and titanium iso-propoxide respectively. 5 ml of titanium isopropoxide and 15 ml of 2 propanol were added to a 100 ml conical ask under constant
stirring, followed by the addition of 1 ml of water to initiate the hydrolysis reaction.
To the white sol of titanium isopropoxide, the dopant precursor solution were
added and stirred for 78 h. During such process rst a sol was formed which ultimately transformed into a gel. The gel was then centrifuged in water followed by
ethanol for 4 times. The centrifuged product was dried at 80 C. The resulting product was nally annealed at 450 C to obtain crystalline gadolinium doped anatase
TiO2 nanoparticles.
2.2. Characterization details
The structure of all the samples are determined using RigakuMiniex CD 10041
XRD unit with copper target and k = 0.154 nm at a scanning rate of 1/min and in
the scanning range of 1080. High resolution transmission electron microscope
images for morphology and particle size determination are observed with JEM2100, 200 kV JEOL. The elemental compositions are known from energy dispersive
X-ray analysis (EDX) equipped with a JEOL JSM 6390 LV scanning electron microscope (SEM). Raman spectra of the samples are acquired with Renishaw in via Spectrometer. An Argon-ion laser of 514.5 nm is used as the excitation source. The
oxidation state of the samples are studied with the help of X-ray photoelectron
spectroscopy (XPS) is recorded on KRATOS-AXIS 165 instrument equipped with
dual aluminiummagnesium anodes using the Mg Ka radiation (hm 1253:6 eV)
operated at 5 kV. Photoluminescence (PL) measurements at room temperature
are recorded with Perkin Elmer LS 55 uorescence spectroscopy. Magnetic measurements are carried out in a vibrating sample magnetometer (VSM) using a selection of Varian and Walker electromagnets.
0:9k
bCosh
203
Fig. 2. TEM images of (a) undoped (c) 0.03 mol Gd doped TiO2; high resolution images showing the lattice fringes of (b) undoped and (d) doped TiO2 nanoparticles (e) EDX
analysis of 0.03 mol Gd doped TiO2 the doped sample.
differences in the size calculated from XRD and TEM. The magnitude of the crystallite and particle size compliments each other
in case of stable, monodisperse, single crystals and hard spheres
and deviation from this criteria leads to variation in measured sizes
[18]. A nanoparticle of polycrystalline aggregates compose of
grains of several sizes. Scherrers formula determines the size of
coherently diffracting grain size. Moreover, the size determined
by Scherrer formula is affected by instrumental broadening, crystalline strain, defects, etc. On the other hand TEM provide direct
evidences of the nanoparticle size, shape. Due to the polycrystalline nature containing several grain sizes the crystallite size is
not generally the same as the particle size [19,20]. The compositional analysis is performed with EDX analysis. The spectrum is
marked with the signals obtained from Ti, O, Gd.
Raman spectroscopy is used for characterizing local structure,
defects, crystallinity, etc. Fig. 3 shows the Raman spectra of pure
and Gd doped TiO2 nanoparticles. Group theory calculation predicts that anatase phase contains six active Raman modes (A1g + 2B1g + 3Eg) [21]. Ohsaka reported six allowed Raman active modes
for anatase TiO2 at 144 cm1 (Eg), 197 cm1 (Eg), 399 cm1 (B1g),
513 cm1 (A1g + B1g) and 639 cm1 [22]. From the Raman spectra
204
Fig. 4. Core level X-ray photoelectron spectrum (XPS) of (a) Ti 2p (b) O 1s (c) Gd d3/2 for 0.07 mol Gd doped TiO2.
3.3. PL measurements
PL spectra are obtained by exciting the doped and undoped TiO2
at 320 nm. Fig. 5 shows the emission spectra of pure and Gd doped
TiO2 nanoparticles. The spectra are deconvoluted into ve emission
peaks with the help of Gaussian tting (r2 = 0.998). All the samples
exhibit a UV emission peak at 398 nm, violet emission peak at
429 nm, two blue emission peak at 457 nm and 488 nm and one
green emission peak at 537 nm. The UV emission peak is the band
edge emission of host TiO2 arising from X1b transition to C3 [30].
The 429 nm peak can be attributed to self trapped excitons (STE)
originated by interactions of conduction band electrons localized
on the Ti 3d orbital with holes present in the O 2p orbital of TiO2
[31]. The peaks at 457 nm and 537 nm are due to the oxygen vacancy related defect centers present below the conduction band.
The intrinsic defects in wide band gap semiconductors are expected to introduce deep energy levels inside the band gap
[31,32]. The signature of peak at 488 nm is due to charge transfer
2
transition from Ti3+ to oxygen anion in a TiO6 complex associated
with oxygen vacancy [33]. The emission spectrum does not contain
any Gd3+ related emission peaks and the emission spectra of doped
and undoped TiO2 are alike. It is the intensity of the emission peaks
which are affected on doping. Photoexcitation of Gd doped TiO2 at
320 nm results in above band gap excitation of electrons to the
upper lying band states in conduction band. These electrons rst
jump to the lower of the conduction band in non-radiative way.
From the lowest of the conduction band edge the electrons either
jump directly to the valence band or initially jump to defects or
to intermediate Gd states and then emit light. Non-existence of
Gd emission peak indicates that the Gd 4f levels are possibly at
the same height as that of oxygen defect states. The signicant contribution of Gd is seen in the intensity of the emission peaks. The
emission intensity gradually increases on incorporation of
0.03 mol and 0.05 mol Gd and then there is sudden quenching of
the emission intensity on adding 0.07 mol Gd. The emission intensity of 0.07 mol Gd doped TiO2 is even less than that of pure TiO2.
At lower dopant concentration the interactions between ions are
too weak to have an effect on the energy levels of each dopant
ion. But at higher dopant concentration the distance between ions
and defects decreases. Decrease in the distance increases the interactions between the ions. The emission energy is transferred from
one ion to another ions or defects and the energy is dissipated nonradiatively resulting in the quenching of emission intensity. We
have calculated the average shortest distance (known as the critical distance) between ions at which the emission energy transfer
occurs, using the equation [34].
RC 2
3V
4pxc N
N = Number of Z ions in the unit cell, Rc = the critical transfer distance. Putting the values the critical distance (Rc) for 0.07 mol is calculated to be 0.9731 nm.
3.4. Magnetic measurements
Fig. 6 shows the MH curves of 0.03, 0.05 and 0.07 mol Gd
doped TiO2 nanoparticle in the magnetic eld range of 15 kOe.
The curves show the typical behavior of paramagnetism. There is
a negligible increase in the magnetization with increase in Gd up
to 0.05 mol. The magnetization of 0.07 mol is less than that of
0.05 mol. The observed paramagnetism might be due to the presence of isolated Gd3+ ions, whereas reduction in the magnetization
is most likely due to the presence of antiferromagnetic interaction
in the system. While incorporating Gd into TiO2, room temperature
ferromagnetism with high magnetization was expected in the system. The notion behind this expectation is that Gd is ferromagnetic
in nature with persistence of ferromagnetic ordering up to 289 K
1=3
2
V = volume of the unit cell = a2c = 0.135 nm3, where a = 0.3785 nm;
c = 0.9424 nm. xc = critical concentration of the dopant (= 0.07),
v v0
C
T h
205
Fig. 8. MH curves of 0.03 mol and 0.07 mol Gd doped TiO2 measured at 10 K.
Fig. 7. Susceptibility (v) vs. temperature (T) curves (a) 0.03 mol and (b) 0.07 mol doped TiO2 nanoparticles.
206
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