Effect of annealing temperature on thermoluminescence glow ...

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Effect of annealing temperature on thermoluminescence glow curve for UV and gamma ray induced ZrO2:Ti phosphor Raunak Kumar Tamrakar a,* , Neha Tiwari b , R.K. Kuraria b , D.P. Bisen c , Vikas Dubey d , Kanchan Upadhyay e a Department of Applied Physics, Bhilai Institute of Technology (Seth Balkrishan Memorial), Near Bhilai House, Durg (C.G.) 491001, India b Department of Physics, Govt. Autonomous Science College, Jabalpur, India c School of Studies in Physics and Astrophysics, Pt. RavishankarShukla University, Raipur (C.G.) 492010, India d Department of Applied Physics, Bhilai Institute of Technology (Seth Balkrishan Memorial), Kendri, Raipur, Pin 492010, India e Department of Chemistry, Shri Shanakaracharya Vidhyalaya, Amdi Nagar, Hudco, Bhilai 490006, India article info Article history: Received 26 September 2014 Received in revised form 10 October 2014 Accepted 22 October 2014 Available online 11 November 2014 Keywords: Thermoluminescence ZrO 2 :Ti Combustion synthesis CGCD Effect of annealing Various heating rate method abstract The present paper reports the thermoluminescence (TL) properties of combustion syn- thesized Ti doped ZrO 2 nanophosphors the effect of annealing on TL glow curve was also studied. The structural characterizations were done by X-ray diffraction technique (XRD), composition by Fourier transformation infrared spectroscopy and surface morphology was determined by field emission gun scanning electron microscopy (FEGSEM) technique. The prepared phosphor annealed at 600 C, 700 C, 800 C and 900 C and its thermolumines- cence glow curve were recorded. The heating rate effect, the thermal quenching as well as the annealing temperature of the material were optimized for the TL glow curve of the sample. The TL glow curves for different UV, gamma doses and for Ti concentration were studied. The TL glow curve of prepared samples have glow peak at 173 C. The kinetic parameters was calculated by Computerized glow curve convolution technique (CGCD) technique. Fading and reusability studies of the nanophosphor further confirmed the phosphor's suitability for radiation dosimetry. The main conclusion is that Solution Combustion Synthesis is one of the appropriate method for synthesis of Ti doped ZrO 2 nanophosphors, which is suitable for temperature sensing applications, the post-synthesis annealing regime being one of the parameters that can affect the intensity and other parameters. Copyright © 2015, The Egyptian Society of Radiation Sciences and Applications. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). * Corresponding author. Tel.: þ91 9827850113 (mobile). E-mail addresses: [email protected], [email protected] (R.K. Tamrakar). Peer review under responsibility of The Egyptian Society of Radiation Sciences and Applications. HOSTED BY Available online at www.sciencedirect.com ScienceDirect Journal of Radiation Research and Applied Sciences journal homepage: http://www.elsevier.com/locate/jrras Journal of Radiation Research and Applied Sciences 8 (2015) 1 e10 http://dx.doi.org/10.1016/j.jrras.2014.10.005 1687-8507/Copyright © 2015, The Egyptian Society of Radiation Sciences and Applications. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). brought to you by CORE View metadata, citation and similar papers at core.ac.uk provided by Elsevier - Publisher Connector
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Effect of annealing temperature on thermoluminescence glow curve for UV and gamma ray induced ZrO2:Ti phosphorw.sciencedirect.com
J o u r n a l o f R a d i a t i o n R e s e a r c h a nd A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 0
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ScienceDirect Journal of Radiation Research and Applied
Sciences journal homepage: http : / /www.elsevier .com/locate/ j r ras
Effect of annealing temperature on thermoluminescence glow curve for UV and gamma ray induced ZrO2:Ti phosphor
Raunak Kumar Tamrakar a,*, Neha Tiwari b, R.K. Kuraria b, D.P. Bisen c, Vikas Dubey d, Kanchan Upadhyay e
a Department of Applied Physics, Bhilai Institute of Technology (Seth Balkrishan Memorial), Near Bhilai House,
Durg (C.G.) 491001, India b Department of Physics, Govt. Autonomous Science College, Jabalpur, India c School of Studies in Physics and Astrophysics, Pt. RavishankarShukla University, Raipur (C.G.) 492010, India d Department of Applied Physics, Bhilai Institute of Technology (Seth Balkrishan Memorial), Kendri, Raipur,
Pin 492010, India e Department of Chemistry, Shri Shanakaracharya Vidhyalaya, Amdi Nagar, Hudco, Bhilai 490006, India
a r t i c l e i n f o
Article history:
Keywords:
Thermoluminescence
ZrO2:Ti
Peer review under responsibility of The E http://dx.doi.org/10.1016/j.jrras.2014.10.005 1687-8507/Copyright© 2015, The Egyptian Soc open access article under the CC BY-NC-ND l
a b s t r a c t
The present paper reports the thermoluminescence (TL) properties of combustion syn-
thesized Ti doped ZrO2 nanophosphors the effect of annealing on TL glow curve was also
studied. The structural characterizations were done by X-ray diffraction technique (XRD),
composition by Fourier transformation infrared spectroscopy and surface morphology was
determined by field emission gun scanning electron microscopy (FEGSEM) technique. The
prepared phosphor annealed at 600 C, 700 C, 800 C and 900 C and its thermolumines-
cence glow curve were recorded. The heating rate effect, the thermal quenching as well as
the annealing temperature of the material were optimized for the TL glow curve of the
sample. The TL glow curves for different UV, gamma doses and for Ti concentration were
studied. The TL glow curve of prepared samples have glow peak at 173 C. The kinetic
parameters was calculated by Computerized glow curve convolution technique (CGCD)
technique. Fading and reusability studies of the nanophosphor further confirmed the
phosphor's suitability for radiation dosimetry. The main conclusion is that Solution
Combustion Synthesis is one of the appropriate method for synthesis of Ti doped ZrO2
nanophosphors, which is suitable for temperature sensing applications, the post-synthesis
annealing regime being one of the parameters that can affect the intensity and other
parameters.
Copyright © 2015, The Egyptian Society of Radiation Sciences and Applications. Production
and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
gyptian Society of Radiation Sciences and Applications.
iety of Radiation Sciences andApplications. Production and hosting by Elsevier B.V. This is an icense (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction
Thermoluminescence (TL) technique reached at new height in
the field of radiation therapy, space research, geology,
archaeology and other related research areas has attracted
researchers from all over the world. It is an extremely powerful
technique used for estimation of doses of ionizing radiations
as the energy absorbed during irradiation and the following TL
intensity on stimulation is proportional to the radiation doses.
But, one of the main challeng is the limited availability of TL
materials with properties suitable for temperature sensing,
namely a wide range of TL peaks and light insensitivity, among
others (Barth et al., 2003; Bahl et al., 2013; Strehl, 1999).
This work is part of an effort to develop new TL materials
with TL peaks in a wide range of temperatures and insensitive
to light, therefore suitable for temperaturemeasurements.We
have been exploring the Solution Combustion Synthesis (SCS)
method (Chick et al., 1990). ZrO2 is one of the widely studied
oxide materials over the last two decades because of its
excellent electrical and optical properties. It is an attractive
material in both fundamental and application-oriented
research. It is well known for low thermal conductivity, high
melting point, and high thermal andmechanical resistance. It
is used as an ideal medium for fabrication of highly lumi-
nescent material due to its high refractive index, low phonon
energy, high chemical and photochemical stability (Chandra,
2010; Tamrakar, Bisen, Upadhyay, & Tiwari, 2014; Tiwari,
Kuraria, & Tamrakar, 2014).
solution combustion synthesis method and investigated its
thermoluminescence glow curve for the samples annealed at
600 C, 700 C, 800 C and 900 C. Moreover, previous work has
focused on material properties that are important (Tiwari
et al., 2014), the objective of this work was to investigate the
effect of annealing on the TL properties of Ti doped ZrO2
nanophosphors synthesized by Solution Combustion Method.
The heating rate that affects the thermal quenching as well as
the annealing temperature of thematerial was optimized. The
kinetic parameters were calculated by Computerized glow
curve convolution technique technique. Fading and reus-
ability studies of the nanophosphor further confirmed the
phosphor's suitability for radiation dosimetry.
1.1. Synthesis of ZrO2:Ti nanophosphor
The raw materials, zirconium (IV) oxynitrate hydrate
(ZrO(NO3)3 $ 6H2O: 99.99%, (Sigma Aldrich) and Titanium (IV)
nitrate tetrahydrate (Ti(NO3)4.4H2O Sigma Aldrich) are the
sources of Zr and Ti respectively. Urea was used as fuel.
(Tamrakar, Bisen, & Brahme, 2014a, 2014b).
Scheme 1 e Synthesis o
For the synthesis of ZrO2:Ti (0.2 mol%), required amount of
Urea and aqueous mixture of zirconium (IV) oxynitrate hy-
drate were subsequently added to the titanium nitrate solu-
tion while continuously stirring the mixture to ensure
homogeneous mixing. The mixture was heated on a hot plate
at 60 C for 1.5 h convert these in to gel form. The Petri dish
containing the homogeneous redox mixture introduced into a
muffle furnacemaintained at 600 ± 10 C. Initially the solution
boils and undergoes dehydration. Eventually the mixture un-
dergoes decomposition, which results in the liberation of large
amounts of gases (usually CO2, H2O andN2). This was followed
by a spontaneous ignition which resulted in flame type com-
bustion (Chick et al., 1990; Singanahally & Alexander, 2008;
Tamrakar, Bisen, & Brahme, 2014a, 2014b). The whole pro-
cess completed in less than 5 min and a highly porous ZrO2:Ti
nano powder obtained. Finally, samples annealed in a pre-
heatedmuffle furnace from600 C to 900 C for fixed periods of
time 2 hour (Tamrakar, Bisen, & Brahme, 2014a, 2014b; Tam-
rakar, Bisen, & Ishwer, 2014, Tamrakar, Bisen, Ishwer and
Bramhe, 2014; Tiwari, Kuraria, & Tamrakar, 2014) (Scheme 1).
1.2. Instrumental details
PRO MPD X-ray diffractometer (PXRD) with copper k alpha
anode of wavelength 1.5405 A. The diffraction patterns
recorded at room temperature with nickel filter in the 2q range
15e85 at a slow scan rate. The morphological features and
particle size was studied by scanning electron microscopy
(SEM, Hitachi-3000) (Dubey, Tiwari, Tamrakar, Rathore, &
Chitrakat, 2014; Dubey, Tiwari, Pradhan, et al., 2014;
Tamrakar, 2012; Tamrakar, Bisen, Upadhyay & Bramhe,
2014, Tamrakar, Bisen, & Sahu, 2014). Thermally stimulated
luminescence glow curves were recorded at room tempera-
ture The thermoluminescence studies were carried out using
TLD reader I1009 supplied by Nucleonix Sys. Pvt. Ltd. Hyder-
abad. The sample was irradiated by UV radiation 254 nm. The
heating rate used for TL measurement is 6 C/s. Kinetic
parameter evaluated by Chen's peak shapemethod and graph
plotted by Origin 8.0 programme. For gamma, irradiations a
60Co source was used which produced an exposure rate of
0.69 kGy/h.
The crystal structures and the phase purity of the materials
were obtained for each of the synthesized materials both
f ZrO2:Ti phosphor.
Fig. 1 e X-ray diffraction patterns of fresh and annealed ZrO2:Ti (0.2 mol%).
J o u r n a l o f R a d i a t i o n R e s e a r c h a nd A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 0 3
before and after annealing. Fig. 1 shows the PXRD patterns of
fresh and annealed ZrO2:Ti (0.2mol%), nanophosphors (Tiwari
et al., 2014). In addition, it was clearly seen that with the in-
crease of annealing temperature, the diffraction peak of
samples were unchanged i. e. there is no phase change, peak
shifting and line broadening were found with the increasing
annealing temperature. The sample shows cubic structure
and the particle sizewere calculated by Scherer's formula. The
Scherrer formula is given by: D ¼ 0.9 l/b Cos q, Where, D is the
average particle size perpendicular to the reflecting planes, l
is the X-raywavelength, b is the FWHM, and q is the diffraction
angle (Tamrakar, 2012; Tamrakar, Bisen, Upadhyay& Bramhe,
2014, Tamrakar, Bisen, & Sahu, 2014). The average crystallite
sizes were 54 and 73 nm for the annealing temperatures of 600
and 900 C respectively (Table 1).
2.2. Fourier transformation infrared spectroscope (FTIR) results of ZrO2:Ti (0.2 mol%) nanophosphor
Fig. 2 shows the FTIR spectra of combustion synthesized
ZrO2:Ti (0.2 mol%) phosphor. A strong absorption peak at
Table 1 e Particle size and annealing temperature.
S. No. Annealing temperature Particle size
1. Fresh ZrO2:Ti(.2%) 54
2. 600 C 60
3. 700 C 64
4. 800 C 69
5. 900 C 73
551.68 cm1 corresponds to ZreO vibrational modes of ZrO2
phase (Gao et al. 2009). Moreover, the absorption band centred
atz3341.67 cm1 corresponds to OH stretching vibrations and
peak centred at 1387.11 cm1 corresponds to bending vibra-
tion of OeH in H2O (Tamrakar, Bisen, Robinson, Sahu, &
Brahme, 2014; Tamrakar, 2013; Tiwari et al., 2014). As
increasing the annealing temperature the OeH Band were
completely vanished.We found nomore significant difference
in FTIR spectra. As similar to PXRD results, FT-IR studies show
no other trace or impurity in the final powder and that it is
pure and crystalline.
2.3. Scanning electron microscope results of ZrO2:Ti (0.2 mol%) nanophosphor
The scanning electron micrographs of freshly prepared sam-
ple and samples annealed at 600 and 900 C for 2 h are shown
in Fig. 3aec, respectively. ZrO2:Ti (0.2 mol%) nanophosphor
show the crystallites with irregular shape and contain several
voids and pores because of the escaping gases during com-
bustion synthesis. It was observed that the crystallites are non
uniform in shape and size. The non-uniform distribution of
shape and size of phosphor can be correlated with the tem-
perature andmass flow in the combustion flamewhich results
in formation of porous phosphors. This type of porous
network is a typical characteristic of combustion-synthesized
phosphors. (Tamrakar, Bisen, & Brahme, 2014a, 2014b). With
an increase in annealing temperature, the highly porous
structure was seen in the freshly prepared sample (Fig. 3a),
which changes to flaky aggregates with pores in their
Fig. 2 e FTIR spectra of fresh and annealed ZrO2:Ti (0.2 mol%).
Fig. 3 e Scanning electron microscope image of ZrO2:Ti (0.2 mol%) (a) freshly prepared; (b) annealed at 600 and (c) annealed
at 900.
J o u r n a l o f R a d i a t i o n R e s e a r c h and A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 04
structure at 600 C (Fig. 3b). Further increase in annealing
temperature to 900 C results in agglomeration of primary
particles (Fig. 3c), In this case, the particles fuse together,
resulting in larger crystallite sizes, which is consistent with
PXRD results.
Fig. 5 e Heating rate Vs peak temperature plot for different
heating rate for freshly prepared.
2.4. Thermoluminescence studies of ZrO2:Ti (0.2 mol%)
2.4.1. Effect at different heating rates for freshly prepared ZrO2:Ti (0.2 mol%)doped phosphors From the TL glow curve with effect of heating rate for opti-
mized concentration (0.2 mol%) of doping ions shows dual TL
glow curve at low and high temperatures (Fig. 4) (Tiwari et al.,
2014). Heating rate varies from 4e8 C and peak shifts towards
higher temperature side when increase the heating rate it
shows a different pattern and valuable information for trap
depth. The temperature of TL glow curve varies from 164 C to
193 C according to the heating rate (Fig. 5). Here from the TL
glow curve of ZrO2:Ti (0.2 mol%) gives the information that TL
glow curve strongly depend upon the heating rate and its
properties varies when heating rate increase. The corre-
sponding kinetic parameters such as activation energy, order
of kinetic and frequency factor calculated by peak shape
method for intense peak of TL glow curve (Table 2). Here from
present table the activation energy as well as frequency factor
is highest for the higher heating rate (8 C s1).
2.4.2. Effect of annealing on ZrO2:Ti (0.2 mol%) doped phosphors Effect of annealing temperature on TL glow curve from
600e900 C was studies. It shows the broad single glow curve
(Fig. 6) and the higher temperature peak eliminated due to the
annealing the sample (Fig. 4). The high temperature peak may
be the impurity peak in TL glow curve and it eliminated when
sample is heated. Also the TL intensity of the prepared sample
increase with increase in annealing temperature and no
change in peak temperature was observed. It is observed that
the optimized temperature for heating sample i.e ZrO2:Ti for
optimized concentration of Ti (0.2 mol%) shows intense and
Fig. 4 e TL spectra at different heating rate for freshly
prepared ZrO2:Ti (0.2 mol%) doped Phosphors for fixed
20 min UV exposure time.
broad TL glow curve and the corresponding kinetic parameter
was high for the optimized temperature (Table 3). The linear
response with heating rate versus TL glow curve intensity is
very interesting result on TL glow curve (Fig. 7).
Here the TL glow curve recorded for fixedUV exposure time
20 min as well as fixed heating rate 6 C for the variation of
600e900 C annealing temperature. The calculation of kinetic
parameters such as activation energy (E) in eV as well as the
frequency factor in s1 was determined by peak shape
method. For the variation of 600e900 C annealing tempera-
ture, the activation energy varies from 0.69 eV to 0.72 eV and
the relative frequency factor found 9.2 1008 to 1.5 1009 s1.
All peaks shows the first order of kinetic because the value of
shape factor m ~ 0.42 or less than o.42 (Table 3) shows the first
order kinetics glow curve.
2.4.3. Effect at different heating rates For the optimized annealing temperature (900 C) as well as
the optimized concentration of Ti (0.2 mol%) in ZrO2 host the
Fig. 6 e TL spectra of ZrO2:Ti (0.2 mol%) doped Phosphors
for 20 min fixed UV exposure of time for different
annealing temperature with heating rate 6 C/s.
Heating rate T1
E in eV Frequency factor
S in s1
4 129 164 189 35 25 60 0.417 0.69 1.1 1009
5 130 169 189 39 20 59 0.339 0.621 2.2 1008
6 129 173 189 44 16 60 0.267 0.549 1.4 1007
7 129 180 190 51 10 61 0.164 0.475 1.4 1006
8 161 193 220 32 27 59 0.458 0.87 3.4 1010
Fig. 7 e Intensity vs annealing temperature of ZrO2:Ti
(0.2 mol%) doped Phosphors for 20 min fixed UV exposure
of time for different annealing temperature with heating
rate 6 C/s.
J o u r n a l o f R a d i a t i o n R e s e a r c h and A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 06
recorded TL glow curve with different heating rate (4, 5, 6, 7
and 8 C s1) shows good TL glow curve (Fig. 8). The peak in-
tensity remains constant for every hating rate but the peak
position shifted towards the higher temperature size. The
increase of heating rate in TL glow curve peak temperature
versus heating rate plot shows linear response (Fig. 9). From
these TL glow curve it is very clear that high temperature peak
is more stable as compared to lower temperature peak. The
high stability and less fading in TL glow curve shows the
application of dosimeter in TL glow curve. The reproducibility
of sample was also determined by the higher temperature
peak. Here the peak centred at 164, 172, 180 and 194 C with
variable heating rate. Here the heating rate 8 C s1 is suitable
for TL dosimetric application due to its high stability. This TL
glow curve recorded for 20 min UV exposure and fixed con-
centration of Ti in host lattice ZrO2. It is very interesting that
the UV exposure form the shallow traps which is responsible
Table 3 e Kinetic parameters of ZrO2:Ti (0.2 mol%) doped Phos annealing temperature with heating rate 6 C/s.
Annealing temperature (C)
Fresh 138 173 198 35 25
600 137 173 199 36 26
700 138 173 197 35 24
800 137 173 199 36 26
900 138 173 198 35 25
for TL glow curve and TL glow peak is lower when shallower
traps was formed. But in the case of ZrO2:Ti phosphor the
formation of both traps surface trap (shallower trap) and deep
trapping phenomenon both occurs and the high temperature
peak indicate that the formation of deep trap in prepared
sample (Dubey, Kaur, Agrawal, Suryanarayana, & Murthy,
2014; Dubey, Kaur, & Agrawal, 2013a, 2013b; Dubey et al.
2010; Dubey, Kaur, Agrawal, 2014a, 2014b; Dubey, Kaur,
Agrawal, Suryanarayana, & Murthy, 2014; Kaur, Parganiha,
Dubey, Singh, & Chandrakar, 2014; Tamrakar, Dubey, et al.,
2013). The kinetic parameter for the TL glow peaks were
calculated by peak shape method the activation energy is
highest for the higher heating rate of TL glow curve (Table 4).
2.4.4. Effect at gamma exposure on ZrO2:Ti (0.2 mol%) doped phosphors When we compare the TL glow curve induced by UV exposure
with gamma exposure 0.5, 0.75 and 1 kGy gamma exposure
well resolved peak found at higher temperature 205 C (Fig. 10)
higher than the UV induced sample (173 C). It is concluded
that the gamma induced sample ismore stable and less fading
was found so the suitability of prepared sample for gamma
dosimetry (Tamrakar, Bisen, & Brahme, 2014a, 2014b;
Tamrakar, Bisen, Sahu, & Brahme, 2014a, 2014b).
The sample shows linear response with gamma dose
(Fig. 11) it presents the sample is suitable for dosimetric
application for gamma induced. The ZrO2:Ti (0.2 mol%) for
optimized annealing temperature 900 C has the good TL peak
centred at 205 C and the formation of deep trapping
confirmed from higher temperature peak.
According to experimental the results here described, the
presence of transition metal ions (Ti) changes the TL glow
curve structure either enhancing or quenching the TL effi-
ciency. These changes are a consequence of the crystalline
field perturbation due to the different characteristics of the
dopant ions which supposedly replaces the zirconium sites.
The traps and the glow curve structure are also dependent
phors for 20 min fixed UV exposure of time for different
u m ¼ d/u Activation energy E in eV
Frequency factor S in s1
60 0.417 0.72 1.6 1009
62 0.419 0.699 9.2 1008
59 0.407 0.718 1.5 1009
62 0.419 0.699 9.2 1008
60 0.417 0.72 1.6 1009
different heating rate.
Fig. 9 e Heating rate vs peak temperature of ZrO2:Ti
(0.2 mol%) doped Phosphors for 20 min fixed UV exposure
annealed at 900 C for different heating rate.
J o u r n a l o f R a d i a t i o n R e s e a r c h a nd A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 0 7
upon the morphology of the surface area which in turn de-
pends on the nanocrystallite size. The nanocrystallite size
depends also on the dopant ion. Furthermore, the obtained
experimental results show that the presence of dopant ions
also modifies the TL recombination efficiency which was
found to be different for each irradiation type (UV and gamma
dose) and the specific exposed material. It is important to
notice that using the right dopant concentration (Ti 0.2 mol%),
Table 4 e Kinetic parameters of ZrO2:Ti (0.2 mol%) doped Phos Different heating rate.
Heating rates T1 (C)
4 128 161 187 33 26 59 0.441
5 130 164 189 34 25 59 0.424
6 129 173 189 44 16 60 0.267
7 129 180 190 51 10 61 0.164
8 161 193 220 32 27 59 0.458
it is possible to maximize the TL efficiency and improve
sensitivity and dose linearity for a specific irradiation type
(Dubey et al., 2014b; Tamrakar & Bisen, 2013; Tamrakar,
Upadhyay, & Bisen, 2014).
Thermoluminescence (TL) phosphors generally exhibit
glow curves with one or more peaks when the charge carriers
are released. The glow curve is characteristic of the different
trap levels that lie in the band gap of the material. The traps
are characterized by certain physical parameters that include
trap depth (E) and frequency factor(s). For many TL applica-
tions, a clear knowledge of these physical parameters is
essential. In the study of relatively deep trapping effect-states
in various solid state materials as well as TL dating, a detailed
analysis of TL glow curves is indispensable.
Chen's method (Chen & Kirsh 1981) was used to determine
the kinetic energy parameters of the glow peak of the TL
materials. This method is mainly based on the temperature
Tm, T1 and T2, where Tm is the peak temperature, while T1 and
T2 are temperatures at half the intensity on the ascending and
descending parts of the glow peak respectively. To determine
the kinetic parameter the following shape parameters are to
be determined: the total half intensity width u ¼ T2 T1. The
high temperature half width d ¼ T2 Tm and the low tem-
perature half width t ¼ Tm T1 the peak shape method is
mainly used to calculate the order of kinetics. Order of kinetic
can be evaluated from the symmetry factor (mg) of the glow
peak. mg is calculated using Eq. (1) from the known peak shape
parameters d andu.
mg ¼ d
Order of kinetics depends on the glow peak shape. The
value of mg for the first order and second order kinetics is 0.42
and 0.52 respectively. Chen has provided a plot which gives of
geometric factor (mg). Another parameter proposed by Balarin
gives the kinetic order as a function of the parameter.
g ¼ d
For the first order kinetics, the Balarin parameter (g) ranges
from 0.7 to 0.8 for the second order kinetics (g) varies from 1.05
to 1.20. Generally in the first order, the process of retrapping is
negligible and the trap should be situated very close to the
luminescent centre. The characteristics of the second order
peak are wider and it is more symmetric than the first order
peak. For a fixed heating rate, in first order kinetics both peak
temperature and shape are independent of the initial trapped
electron concentration but in the second order, the peak
phors for 20 min fixed UV exposure annealed at 900 C for
u Activation energy E in eV Frequency factor S in s1
0.727 3.4 1009
0.713 1.9 1009
0.549 1.4 1007
0.475 1.4 1006
0.87 3.3 1010
phosphor annealed.
Fig. 11 e Gamma dose vs intensity ZrO2:Ti (0.2 mol%)
doped.
Fig. 12 e CGCD curve of experimental TL glow peak of
ZrO2:Ti (0.2%) for fixed 1 kGy with heating rate 6 C/s.
Table 6 e Trapping parameters of a typical glow curve for ZrO2:Ti(.2%) for fixed 1 kGy with heating rate 6 C/s.
Peaks T1 (K) Tm (K) T2 (K) mg b E (eV) S (s1)
Peak 1 448 477 505 0.49 1.9 1.05 7.62 1011
Peak 2 469 511 551 0.48 1.7 0.801 7.7 1008
J o u r n a l o f R a d i a t i o n R e s e a r c h and A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 08
temperature and shape are strongly dependent on initial
trapped charge concentration.
The activation energy (E) can be calculated by the general
expressions formulated by Chen and is given by
E ¼ Ca
Where k is Boltzmann constant. Tm is peak temperature. The
constant Ca and bawere also calculated by the Chen's equation (Chen, 1969). The activation energy and the frequency factor
were seen in Table 5. The activation energy is found in be-
tween 0.48 and 0.53 eV and the frequency factor is range of
1.5 1009 to 1.7 1011 for UV irradiated phosphor.
Table 5 e Kinetic parameters of ZrO2:Ti (0.2 mol%) doped Phos
Dose in kGy T1 Tm T2 t d u m ¼ d/
.5 167 205 241 38 36 74 0.486
.75 174 205 238 31 33 64 0.516
1 174 205 240 31 35 66 0.53
2.4.5. CGCD curve fitting techniques for ZrO2 Ti(0.2%) phosphor The comparison between theoretical and experimental TL
glow curve was presented by computerized glow curve deco-
volution (CGCD) technique (Fig. 12). The curve is fitted by
origin 8 programme and the experimental glow peak shows
good TL glow peak centred at 476 K. Other two peaks are
prominent for the study of area under the glow curve and the
corresponding kinetic parameters are calculated by peak
shape method (Table 6). The peaks shows second order of
kinetic for the CGCD peaks as well as the activation energy is
very high for that (Puchalska & Bilski, 2006).
The kinetic parameters were calculated by (Computerized
glow curve convolution technique) CGCD technique, activa-
tion energy was found in between 1.05 and 0.801, and the
frequency factors are found in the range of 7.7 1008 to
7.62 1011 s1 (Tamrakar, Kowar, Uplop, & Robinson, 2014;
Tamrakar, Upadhyay, & Bisen, 2014; Tamrakar, Upadhyay, &
Bisen, 2014).
2.4.6. Conclusion The samples were prepared by combustion a synthesis tech-
nique and annealed at 600 Ce900 C. There is no any phase
change found due to annealing of the prepared ZrO2:Ti (0.2%)
phosphor. Sample shows cubic structure and the particle size
phor annealed at 900 C for Different gamma dose.
u Activation energy E in eV Frequency factor S in s1
0.774 1.5 1009
0.959 1.7 1011
0.962 1.9 1011
calculated by Scherer's formula ringing form 54 and 73 nm.
The good connectivity with grains and the semi-sphere line
structure was found by SEM. Phosphor was irradiated by UV
254 nm source and optimized the heating rate. Sample shows
well resolved and higher intensity peak at 173 C for 6 C/s. The kinetic parameters were calculated by (Computerized
glow curve convolution technique) CGCD technique, activa-
tion energy is found in between 1.05 eV to 0.801 eV, and the
frequency factors are found in the range of 7.7 1008 to
7.62 1011 s1.
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1. Introduction
1.2. Instrumental details
2.2. Fourier transformation infrared spectroscope (FTIR) results of ZrO2:Ti (0.2 mol%) nanophosphor
2.3. Scanning electron microscope results of ZrO2:Ti (0.2 mol%) nanophosphor
2.4. Thermoluminescence studies of ZrO2:Ti (0.2 mol%)
2.4.1. Effect at different heating rates for freshly prepared ZrO2:Ti (0.2 mol%)doped phosphors
2.4.2. Effect of annealing on ZrO2:Ti (0.2 mol%) doped phosphors
2.4.3. Effect at different heating rates
2.4.4. Effect at gamma exposure on ZrO2:Ti (0.2 mol%) doped phosphors
2.4.5. CGCD curve fitting techniques for ZrO2 Ti(0.2%) phosphor
2.4.6. Conclusion