Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Low temperature synthesis of pure cubic ZrO2 nanopowder: Structural

and luminescence studies
D. Prakashbabu a,f,⇑, R. Hari Krishna b,⇑, B.M. Nagabhushana b, H. Nagabhushana c, C. Shivakumara d,
R.P.S. Chakradar e, H.B. Ramalingam f, S.C. Sharma g, R. Chandramohan h
a
Bharathiar University, Coimbatore 641 046, India
b
Department of Chemistry, M.S. Ramaiah Institute of Technology, Bangalore 560 054, India
c
C.N.R. Rao Center for Nano Research, Tumkur University, Tumkur 572 103, India
d
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
e
National Aerospace Laboratory (CSIR), Bangalore 560 017, India
f
Department of Physics, Government Arts College, Udumalpet 642 126, India
g
Department of Mechanical Engineering, B.M.S. Institute of Technology, Bangalore 560 064, India
h
Department of Physics, Sevugan Annamalai College, Devakottai 630 303, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 We present preparation of pure cubic

zirconia (ZrO2) using one step
solution combustion synthesis.
 We have achieved pure cubic phase
devoid of any additional phases
without calcination.
 PL and TL properties are studied and
the relation between defects and
emission behavior is explored.
 TL kinetic parameters have been
calculated and correlated with the
different traps created.
 ZrO2 show linear TL response and do
not saturate even at high c-dose of
5 KGy.

a r t i c l e i n f o a b s t r a c t

Article history: Pure cubic zirconia (ZrO2) nanopowder is prepared for the first time by simple low temperature solution
Received 10 August 2013 combustion method without calcination. The product is characterized by Powder X-ray Diffraction
Received in revised form 28 October 2013 (PXRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform
Accepted 10 November 2013
Infra Red spectroscopy (FTIR) and Ultraviolet–Visible spectroscopy (UV–Vis). The PXRD showed the forma-
Available online 16 November 2013
tion of pure stable cubic ZrO2 nanopowders with average crystallite size ranging from 6 to 12 nm. The lat-
tice parameters were calculated from Rietveld refinement method. SEM micrograph shows fluffy,
Keywords:
mesoporous, agglomerated particles with large number of voids. TEM micrograph shows honey comb like
Cubic zirconia
Combustion synthesis
arrangement of particles with particle size 10 nm. The PL emission spectrum excited at 210 nm and
Photoluminescence 240 nm consists of intense bands centered at 365 and 390 nm. Both the samples show shoulder peak
Thermoluminescence at 420 nm, along with four weak emission bands at 484, 528, 614 and 726 nm. TL studies were
Kinetic parameters carried out pre-irradiating samples with c-rays ranging from 1 to 5 KGy at room temperature. A well
resolved glow peak at 377 °C is recorded which can be ascribed to deep traps. With increase in c radiation
there is linear increase in TL intensity which shows the possible use of ZrO2 as dosimetric material.
Ó 2013 Elsevier B.V. All rights reserved.

⇑ Corresponding authors. Address: Bharathiar University, Coimbatore 641 046,

India (D. Prakashbabu). Tel.: +91 9916322600 (R. Hari Krishna).
E-mail addresses: prakashdebabu@gmail.com (D. Prakashbabu), rhk.chem@
gmail.com (R. Hari Krishna).

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.11.043
 D. Prakashbabu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222
Introduction
In recent years, zirconia (ZrO2) has attracted much attention
owing to widespread practical applications. ZrO2 is an important
engineering material and finds wide applications in various fields
such as thermal barrier phosphors, catalysts, coatings, solid-oxide
fuel cells and gas sensors [1–6]. Further the material exhibit low
thermal conductivity, high melting point, high thermal expansion
coefficient, high stability that enables its use in several other engi-
neering applications. ZrO2 have recently received considerable
attention due to its application as TL dosimeters [7]. ZrO2 exists
in three polymorphs: monoclinic, tetragonal and cubic phases,
m-ZrO2 shows a transition to a tetragonal phase at 1150 °C, above
2300 °C a cubic fluorite type structure is observed [8]. In fact, the
ZrO2 porous nanosolid is a new intermediate state between nano-
powders and nanoceramics. It is a solid constructed of nanoparti-
cles forming pores and channels, thus possessing both the ideal
strength of nanoceramics and the high reactivity of nanoparticles.
Besides, the pores, with the diameter size of several nanometers,
may impose a strong quantum confinement effect on the mole-
cules in it, results in the change of the properties of these mole-
cules [8]. For an extended application, it is required that zirconia
materials should possess higher specific surface area and high crys-
tallinity. Hence, much effort has been attempted to synthesize
mesoporous zirconia materials together with a large surface area
and crystalline pore walls [9].
In the last decade variety of methods have been used for syn-
thesis of ZrO2 namely conventional solid-state reaction, sol–gel,
combustion synthesis, hydrothermal method etc., High tempera-
ture solid-state route is still the most commonly used synthesis
method, that employs temperature more than 1200 °C for a long
time (4 h), which produces large agglomerates and must be
ground or milled to obtain a fine powder. The primary disadvan-
tages associated with this method are high energy consumption
and agglomeration of the final product. To avoid high preparation
temperatures and agglomerations of fine powders, lots of new
methods have been adopted. Realizing that the cost of synthesis,
simplicity and morphological characteristics of nanoparticles to
be important parameters for their use in commercial applications,
it is imperative that a self-propagating combustion route offers
the best choice among other methods [10]. This process involves
the use of organic fuel to initiate decomposition reaction of pre-
cursor metal salts at moderate temperature [11]. Mostly the cubic
phase of zirconia is stabilized by doping with yttrium or some-
times with calcium. In the present work, for the first time to
the best of our knowledge, pure cubic zirconia is synthesized
using zirconyl nitrate and ODH at 400 °C without any stabilizing
agents and thermal treatment. We have also investigated its
luminescence properties (photo and thermoluminescence) and
logically discussed the possible use of ZrO2 as dosimetric
material.
Experimental
The starting materials used for combustion synthesis were ana-
lar grade zirconium nitrate (Zr(NO3)4:99.99%, Sigma Aldrich Ltd.).
Oxlayl di-hydrazide (ODH) is used as fuel which is prepared in
our laboratory. Stoichiometric composition of the redox mixtures
is calculated based on the total oxidizing and reducing valences
of the oxidizer (O) and the fuel (F) keeping the O/F ratio unity
[12]. The aqueous solution containing the redox mixture is taken
in a crystalline dish and introduced in a preheated muffle furnace
maintained at 400 °C.
Assuming the complete combustion the theoretical equation for
the formation of ZrO2 with ODH can be written as follows:
217
ZrOðNO3 Þ2 þ ðCON2 H3 Þ2 ! ZrO2 þ 3N2 þ 2CO2 þ 3H2 O ð1Þ
ð8 moles=mole of ZrO2 Þ
PXRD measurements were made on Philips PW 1050/70 using
Nickel – filtered Cu Ka radiation. The FTIR spectroscopic studies
have been carried out using a Perkin Elmer Spectrometer (Spec-
trum 1000) with KBr pellets. SEM micrograph is recorded using
JEOL (JSM-840A) instrument after coating the samples with gold.
TEM analysis is performed on a Hitachi H-8100 (accelerating volt-
age up to 200 kV, LaB6 Filament) equipped with EDS (Keney Sigma
TM Quasar, USA). UV–Visible spectral study is carried out using
ELICO SL 159 UV–Vis spectrophotometer. The photoluminescence
measurements were performed on a Shimadzu Spectrofluorometer
(Model RF 510) equipped with 150 W xenon lamp as an excitation
source. Thermoluminescence measurements were measured on a
model Nucleonix TL Reader with a heating rate of 5 °C s1 for sam-
ples irradiated with c-rays in the dose range of 1–5 KGy.
Results and discussion
The formation of crystalline phase prepared by solution com-
bustion (SC) method is confirmed by PXRD measurement. Fig. 1
shows the powder X-ray diffraction pattern of ZrO2 and the
observed pattern is in well agreement with the standard JCPDS file
(81-1551). All the diffraction peaks can be assigned to the cubic
phase of ZrO2. No diffraction peaks corresponding to other impuri-
ties were observed. The crystallite size is estimated for the powder
from the full width half maximum (b) of the diffraction peaks,
using Debye–Scherrer’s method [13]. d = kk/b cos h where ‘k’ is the
wavelength of X-ray (1.542 Å) ‘h’ the Bragg angle, ‘k’ is the constant
depends on the grain shape (0.94). The estimated average crystal-
lite size is found to be in the range 6–12 nm.
The lattice parameter of ZrO2 is calculated using Rietveld refine-
ment analysis and is shown in Fig. 2. The analysis is performed
with the FULLPROF program [14], by assuming Fm-3m (No. 225)
space group for a cubic type structure. Pseudo-Voigt function has
been used in order to fit the several parameters to the data point:
one scale factor, one zero shifting, four background, three cell
parameters, five shape and width of the peaks, one global thermal
factor and two asymmetric factors [15]. The experimental and cal-
culated PXRD patterns obtained by the Rietveld refinement of ZrO2
phase is in good agreement with literature [16,17]. The refined
parameters such as occupancy, atomic functional positions for SC
method were determined. Further crystal system, space group, lat-
tice parameter (a), cell volume of ZrO2 prepared by SC method is
obtained by Rietveld software and summarized in Table 1. The
packing diagram corresponding cubic ZrO2 after Rietveld refine-
ment is shown in Fig. 3.
(111)
Intensity (arb. units)
(220)
(311)
(200)
(331)
(222)
(400)
(420)
JCPDS No: 81-1551
10 20 30 40 50 60 70 80 90
2 θ (degree)
Fig. 1. PXRD pattern of ZrO2 nanoparticles prepared by solution combustion.
218 D. Prakashbabu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222

Fig. 2. Reitveld refinement of cubic ZrO2 nanoparticles prepared by solution

combustion.

The strain and crystallite size produces broadening of peak in

the diffraction pattern. The crystallite and strain effect have to be
differentiated in the diffraction pattern. Both effects are indepen-
dent and can be distinguished by W–H plots. Williamson and Hall Fig. 3. Packing diagram of cubic ZrO2 prepared by solution combustion.
(W–H) have suggested a method [18] combining the domain size
and lattice microstrain effects on line broadening, when both are
operative. The W–H approach considers the case when the domain
effect and lattice deformation are both simultaneously operative
0.7
and their combined effects give the final line broadening FWHM
(b = b1 + b2), which is the sum of b1 (grain size) and b2 (lattice
distortion). This relation assumes a negligibly small instrumental
contribution compared to the sample-dependent broadening.
W–H equation may be expressed in the form: 0.6
β cosθ

Kk
b cos h ¼ eð4 sin hÞ þ
D
where b (FWHM in radian) is measured for different XRD lines cor-
responding to different planes, K is the shape factor, e is the strain
developed and D is the grain size. The equation represents a straight
line between 4 sin h (X-axis) and B cos h (Y-axis) (Fig. 4). The slope of
line gives the strain (e) and intercept (k/D) of this line on the Y-axis
gives grain size (D). It is observed that the grain size determined
from W–H formula (6 nm) is slightly lesser than those calculated
using Debye–Scherer’s formula (9 nm). The small variation in the
values is due to the fact that in Debye–Scherer’s formula strain
component is assumed to be zero and observed broadening of dif-
fraction peak is considered as a result of reducing grain size only.
Further, the strain is found to be 2.308  104.
The FTIR spectra (Fig. 5) of ZrO2 nanocrystals were recorded in
the range of 300–4000 cm1. The dominant absorption band cen-
tered at 446 cm1 is due to the deformation mode of Zr –O–Zr bond
[16]. The peaks centered at 1130 cm1 and 1380 cm1 can be asso-
ciated to stretching vibrations of Zr–O terminal groups (O mean-
ing non-bridging atom) [19]. weak band centered at 1591 cm1
assigned to symmetric bending of H2O [20] and the band at
2370 cm1 is due to stretching vibrations of C–O in adsorbed CO2
ð2Þ
0.5
0.4
1.0 1.2 1.4 1.6 1.8 2.0
4 sinθ
Fig. 4. WH plot of ZrO2 nanoparticles prepared by solution combustion.
from atmosphere. The wide band centered at 3410 cm1 is
ascribed to the stretching of O–H group of water.
The SEM micrograph of the ZrO2, Fig. 6a shows porous, agglom-
erated, irregular shaped particles. The voids observed can be ascer-
tained due to the evolution of gases formed at the process of
smoldering combustion. Transmission electron micrograph of the
as-formed cubic-zirconia is shown in Fig. 6b. The micrograph
shows honey comb structure with particles almost spherical in
shape and with uniform size about 6–12 nm. Fig. 6c shows selec-
tive area electron diffraction pattern which proves the high crystal-

Table 1
Structural parameters obtained from Rietveld refinement of ZrO2.

Compound/crystal system Atoms Oxidation state Wyckoff notation X Y Z B Occupancy

ZrO2 Cubic Zr +4 4a 0.0000 0.0000 0.0000 0.50 1
O 2 8c 0.2500 0.2500 0.2500 0.50 1

Space group: Fm-3m (No. 225), Lattice parameters: a = 5.1164 (4) Å, Cell volume = 133.93 (2) Å3, Rp = 3.81, Rwp = 4.89, v2 = 1.54, RBragg = 0.93, RF = 0.79.
 D. Prakashbabu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222 219

emission vanishes. Furthermore, in addition to emission peaks at

390, 420, 484 and 529 nm, a peak centered at 726 nm is observed.
Since Zr4+ itself is non-luminous and the observed luminescence
from ZrO2 samples must be due to non-stoichiometry created by
the oxygen deficiency in the system, which is known to occur
% Transmittance (a.u.)

when ZrO2 forms in carbon rich ambient. The difference in the

1591 1130
2370
3410
4000 3500 3000 2500 2000
Wavenumber (cm-1)
Fig. 5. FTIR spectrum of the as-formed ZrO2 nanoparticles.
linity of the product. The elemental composition is obtained from
EDAX which is shown Fig. 6d. The UV–Vis absorption of ZrO2 is
shown in Fig. 7. The weak absorption in the near UV–Visible region
is ascribed to transitions involving extrinsic states such as surface
traps or defect states (oxygen/zirconia vacancies) [21]. Inset of
Fig. 7 shows the Wood and Tauc plot, from which the direct band
gap is obtained to be 4.96 eV.
Fig. 8a and b shows the photoluminescence emission (PL) spec-
tra obtained from the sample under different excitation wave-
lengths 210 and 240 nm respectively. The sample shows
emission peaks centered at 390, 420, 484, 529 and 609 nm when
excited at 210 nm. However, upon 240 nm excitation, 609 nm
emission behavior of the sample with change in the excitation
wavelength might be due to different kinds of oxygen deficiencies
present in the sample. The result is similar to that of the warm like
zirconia reported by Che et al. [22], which suggests that the oxy-
1380
gen-vacancy defects in ZrO2 crystal lattices are responsible for
the photoluminescence emission of zirconia nanowires under UV
excitation. However, the emission intensity is almost three times
greater for 210 nm excitation than for 240 nm excitation.
So far, to explain the luminescence mechanism of ZrO2, two dif-
446
ferent mechanisms have been proposed; an impurity luminescence
center model and a structure defect model. The impurity lumines-
1500 1000 500
cence center model ascribes the luminescence of ZrO2 to the traces
of Ti4+ impurity already present in the material, whereas the struc-
ture defect model proposes that the luminescence of ZrO2 to singly
ionized oxygen-vacancy defects [23]. Recently Chen et al. [24],
observed violet emission at 391 nm from mesoporous ZrO2 and
assumed that it results from Zr–O–P lumophores. Here ZrO2 nano-
powders were synthesized by solution combustion technique and
are free from Ti4+ and phosphorous (P), confirmed from PXRD,
EDAX and FTIR. Therefore, the emission band of ZrO2 nanopowders
originates purely from oxygen vacancies [25] i.e., structure defect
model. The 365 nm and the 391 nm emission lines are charge
transfer bands. Joy et al. [26], assigns the 391 nm emission partic-
ularly to the capture of electrons by oxygen vacancies from the
conduction band. The violent combustion process leads to the exis-
tence of large amounts of oxygen-vacancy defects in ZrO2 nano-
powders. The narrow blue band with lower emission energy at
420 nm arises from the singly ionized associated oxygen vacancy

Fig. 6. (a) Scanning electron micrograph (b) transmission electron micrograph (c) selected area electron diffraction pattern and (d) EDAX analysis of cubic ZrO2 prepared by
solution combustion.
220 D. Prakashbabu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222

0.4 oxygen vacancies [23]. The least intensive peak at 529 nm could
be ascribed to the emission due to near band-edge transitions
[27]. The 614 nm emission peak is due to oxygen position pertur-
0.3 bation into the structure; an imperfect system caused transitions
Absorbance (a.u)

of O2p ? Zr4d type [20]. Such behavior is also observed by

Camagni et al. [28] for yttrium-stabilized zirconia. The red peak

2
α hν) (eVcm-1)
0.2 at 726 nm can be assigned to combination emissions of electrons
and holes in oxygen vacancies in ZrO2 [29].
Thermoluminescence is a versatile technique used for estima-
2

0.1 tion of high-energy ionizing radiations as the energy absorbed dur-

(α

ing irradiation and the TL intensity on thermal stimulation is

2 3 4 5 6 proportional to the radiation fluence (doses). Recent reports on
Eg (eV)
0.0 different luminescent nanomaterials have showed that they have
200 400 600 800 a potential application in dosimetry of ionizing radiations for the
Wavelength (nm) measurements of high doses using the TL technique, whereas the
conventional microcrystalline phosphors saturate at high doses
Fig. 7. UV–Vis absorption spectrum of ZrO2 nanoparticles prepared by solution [30,31]. This saturation occurs due to the ionized zones overlap-
combustion Inset: Wood and Tauc Plot to find band gap. ping each other in the micromaterial at higher doses, with the
use of very tiny particles such as nanosize TL dosimetric material;
this problem can be avoided to a major extent. The TL results of the
reported nanomaterials have revealed very imperative characteris-
1000
390 λExcitation tics such as single glow curve, linear increase in intensity with
Intensity (arb. units)

300
(a) 210 nm dose, simple trap distribution.
210 nm

800 (b) 240 nm Fig. 9 shows TL glow curve of pure cubic ZrO2 nanoparticles
Intensity (arb. units)

250
240 nm

Intensity (arb. units)

irradiated to different doses of gamma rays from (60Co) source in

420
600 200 the dose range 1–5 kGy. The glow curves have a single well
200 220
Wavelength (nm)
240 260
resolved broad peak at 377 °C at a heating rate of 5 °C s1
150 recorded at room temperature. Variation in TL intensity with dif-
400
ferent c exposures is shown in Fig. 9 (Inset). The peak heights were
484

609

100
used for measuring the TL intensities. TL intensity increases line-
529

726

200 50 arly with c exposure for tested dose range. Saturation of TL is

(a) (b) not observed even at 5KGy of c dose. This trend in TL intensity with
0 0 c exposure can be explained on the basis of Horowitz’s TIM (track
300 400 500 600 700 800
interaction model) [32,33]. At low exposure time the recombina-
tion of various trapping/luminescent centers (TCs/LCs) occurs
Wavelength (nm)
entirely within the tracks. Electrons escaping the tracks are
Fig. 8. PL emission spectrum of ZrO2 nanoparticles excited at (a) 210 nm and (b)
intercepted by the non-radiative competitive centers (CC) in the
240 nm. (Inset) excitation spectra. intermediate region. The TL signal, therefore, linearly increases
with the irradiation and is simply proportional to the c dose. At
higher levels of dose, the distance between the neighbouring tracks
decreases and the electrons leaving the track can reach the neigh-
defects (AOD+ centers) (i.e., singly ionized two-oxygen-vacancy de- bouring track resulting in the increased recombinations of the
fect association (F–F)+). The band at 484 nm is likely due to extra luminescent centers resulting in greater TL intensity. In the present

5600
ZrO2
5200
4500
TL Intensity (a.u)

TL Intensity (a.u)

4800

4400

4000 3000
3600

3200
1 2 3 4 5
1500
γ-dose (kGy)

o
377 C 5
4
y)

3
G
(k

2
se
do

1 γ-
150 200 250 300 350
o
Temperature ( C)

Fig. 9. TL glow curves of c-irradiated (1–5 kGy) ZrO2 prepared by solution combustion, (inset) Variation of TL intensity of 377 °C peak with dose.
 D. Prakashbabu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222 221

curve structure that does not change with dose shows excellent
4000 Experimental curve
Fitted curve reusability and thus can be used for dosimetric application.
Deconvoluted peaks The following empirical formulae are used to estimate trapping
parameters using the Chen’s peak shape method [35]:
3000
TL Intensity (a.u)

The activation energy (E)

!
Peak 3 KT 2m
Ea ¼ C a  ba ð2KT m Þ ð3Þ
2000 a

Peak 2
where a = s, d, x.
1000 d
Peak 1
d ¼ T2  Tm x ¼ T 2  T 1 s ¼ T m  T 1 lg ¼
x
0 C s ¼ 1:51 þ 3:0ðlg  0:42Þ C d ¼ 0:976 þ 7:3ðlg  0:42Þ ð4Þ
150 200 250 300 350 400
Temperature ( oC) C x ¼ 2:52 þ 10:2ðlg  0:42Þ ð5Þ

Fig. 10. Glow curve deconvolution of nano ZrO2 nanoparticles prepared by solution
combustion exposed to 4 KGy c radiations.
bs ¼ 1:58 þ 4:2ðlg  0:42Þ bd ¼ 0 bx ¼ 1 ð6Þ

Frequency factor (s)

Once E and b are known, frequency factor (s) can be evaluated
 
study as the c exposure increases, the TL intensity increases as still bE E
2
¼ s exp ½1 þ ðb  1ÞDm  ð7Þ
some particles exist that would have been missed while targeted kT m kT m
by the irradiation, owing to the small size of the ZrO2 particles.
So we do not get saturation in present system even at higher where b is the linear heating rate, b is the order of kinetics and
c-exposures (5 KGy). Dm ¼ 2kTE m .
TL characteristization of the material requires extraction of Order of kinetics
information regarding trapping parameters such as activation en- To determine the order of kinetics (b), the form factor or sym-
ergy (E) of the traps, and order of kinetics (b), associated with metry factor
the glow peaks. Here E is a measure of energy required to eject T 2T m
an electron from the defect center to the conduction band, and s lg ¼ ð8Þ
T2  T1
is the rate of electron ejection. The order of kinetics b is a measure
of the probability that a free electron gets re-trapped. This re-trap- Which involves calculation of T1 and T2 (T1 and T2 are the tempera-
ping effect increases with density of empty traps. For estimation of tures corresponding to the half of the maximum intensities on
trapping parameters (s and E), firstly we did deconvolution of the either side of the glow peak maximum temperature (Tm). The nature
TL glow curves using ORIGIN 8.1 software. This is shown in of the kinetics can be found by the form factor. Theoretically the
Fig. 10 for as-prepared ZrO2 by solution combustion. The three value of geometrical form factor (lg), close to 0.42, for first order
curves obtained are needed to account for the observed TL curve. kinetics and value can be 0.52 for second order.
Deconvolution of which reveals three peaks at 326 °C, 351 °C and Frequency factor (s)
384 °C. Salas et al. [34] observed TL peaks of ZrO2 at 130 °C, Once E and b are known, frequency factor (s) can be evaluated
225 °C and 418 °C and they have assigned first two peaks to mono-  
bE E
clinic phase and third peak to tetragonal phase of ZrO2 respec- 2
¼ s exp ½1 þ ðb  1ÞDm  ð9Þ
kT m kT m
tively. However, our PXRD and Rietveld results show that no
traces of monoclinic or tetragonal phases and hence the TL peaks where b is the linear heating rate, b is the order of kinetics and
may be assigned to the cubic phase of zirconia. Further, single glow Dm ¼ 2kTE m .

Table 2
Estimated TL kinetic parameters for ZrO2 nanopowders.

c – dose (kGy) Peak Tm (°C) b (lg) Activation energy (eV) Frequency factor (s1)
Es Ed Ex Eave
1 1 330 0.50 0.847 0.935 0.894 0.892 2.1  1008
2 361 0.50 1.808 1.798 1.813 1.806 3.3  1015
3 378 0.51 2.623 2.370 2.514 2.502 3.8  1020
2 1 326 0.49 0.626 0.736 0.682 0.681 2.9  1006
2 350 0.51 1.531 1.538 1.542 1.537 3.5  1013
3 384 0.49 2.446 2.392 2.436 2.425 7.5  1019
3 1 329 0.50 0.753 0.850 0.804 0.803 3.4  1007
2 361 0.50 1.877 1.860 1.879 1.872 1.2  1016
3 381 0.48 2.957 2.768 2.896 2.874 2.3  1021
4 1 326 0.48 1.450 1.483 1.475 1.47 3.0  1013
2 346 0.49 2.767 2.675 2.742 2.728 4.0  1023
3 382 0.49 2.430 2.378 2.421 2.41 6.6  1019
5 1 327 0.49 1.711 1.713 1.722 1.715 4.0  1015
2 351 0.48 2.159 2.033 2.121 2.104 3.3  1018
3 379 0.48 2.681 2.515 2.628 2.608 2.3  1021
222 D. Prakashbabu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 122 (2014) 216–222
The estimated kinetic parameters for ZrO2 are given in Table 2.
From the data, it is observed that considerable amount of
re-trapping is taking place in all the TL second order peaks of the
nanopowder. The activation energy (E) of all those peaks are
formed to be at comparably deeper site within the band gap of
the host, suggesting that the hole traps are more prominent in TL
process. The simple glow curve structure and linear response over
a wide range (1–5 KGy) are some of the good characteristics of this
cubic ZrO2 and may be useful for its application in high energy
radiation dosimetry.
Conclusion
ZrO2 nanopowder has been synthesized successfully by the
solution combustion process. Compared to the solid-state reaction
method, combustion synthesis has outstanding potential for pro-
ducing cubic ZrO2 nanopowder. The powder X-ray diffraction of
as-formed ZrO2 sample shows completely crystalline, cubic phase
with a particle size of about 10 nm. SEM micrographs show that
the primary particles are agglomerated, with porous structure
formed by the escaping gases during combustion. TEM results also
confirm the ZrO2 particles are of nanosize. Upon 210 and 240 nm
excitation the room temperature PL spectra show green and red
emission bands at 484 nm and 614 nm, which corresponds to oxy-
gen defects. A single well resolved thermoluminescent glow peak
at 377 °C is observed for the dose range of 1–5 KGy. The TL inten-
sity is found to increase with increase of gamma dose which is one
of the desired properties of TL dosimeter.
References
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