J Mater Sci: Mater Electron (2017) 28:13565–13578

DOI 10.1007/s10854-017-7196-8

TL glow curve analysis and kinetics of UV, β and γ irradiated

­YBO3:Eu3+ and ­Y2O3:Eu3+ phosphors
Vikas Dubey1 · Neha V. Dubey2 · S. J. Dhoble3 · Hendrik C. Swart4

Received: 27 March 2017 / Accepted: 22 May 2017 / Published online: 31 May 2017
© Springer Science+Business Media New York 2017

Abstract This paper reports on the thermoluminescence trapping parameters. The trapping parameters such as acti-
(TL) properties of E­ u3+ doped in two different host matrix vation energy, order of kinetics and frequency factor were
phosphors ­(Y2O3 and ­YBO3). The phosphors were prepared calculated by the peak shape method using the computer-
by a high temperature solid state reaction method. The ized glow curve deconvolution technique. Here most of the
method is suitable for a large scale production. The samples peak showed second order of kinetics. The effect of γ, β
were characterized by X-ray diffraction and Rietveld refine- and UV dose exposure on the TL studies was also exam-
ment. The different concentration of ­Eu3+ samples were ined and it showed a linear response with dose which indi-
also examined by TL glow curve analysis for UV, β and γ cated that the samples might be useful for TL dosimetry.
irradiation. The Y
­ 2O3 samples showed well resolved broad The possible mechanics and information about traps forma-
peaks that covered the temperature range from 50 to 350 °C tion are presented in detail.
and the peak temperature was found at 157 °C for the γ irra-
diation. For the UV irradiated samples a well resolved peak
at 121 °C was found for the ­Y2O3:Eu3+ doped phosphors. 1 Introduction
The β irradiated samples showed a resolved peak at 182 °C.
A different behaviour was observed for the Y ­ BO3:Eu3+ Rare earth ortho-borates have been an attractive subject
doped phosphors which showed both higher temperature in the last decades due to their interesting crystal struc-
peaks and lower temperature peaks for UV, β and γ irradia- tures and extraordinary optical properties. Depending on
tion. Here UV irradiated sample showed the formation of the size of the lanthanide cation, their orthoborates are
shallow trap (surface trapping) and the γ irradiated sample generally crystallized into the aragonite-type (La–Nd),
showed the formation of deep trapping. The estimation of vaterite-type (Sm–Yb), or calcite-type (Lu) structure
the trap formation was evaluated by the calculation of the [1–3]. However, some lanthanide borates demonstrate
alterable crystal structures with different crystallized con-
ditions. As far as “vaterite-type” borates are concerned,
* Vikas Dubey their structures are not coincided with the vaterite-type
[email protected]
­CaCO3 despite their similar chemical formula [4–10].
Hendrik C. Swart Rare earth orthoborates show excellent versatile charac-
[email protected]
ters upon highly vacuum ultraviolet transparency, large
1
Department of Physics, Bhilai Institute of Technology, electronic band gaps, chemical and environment stability,
Raipur 493661, India exceptional optical damage threshold, and etc [11–17].
2
Department of Physics, Govt. V.Y.T.PG. Autonomous Over the last few years, much attention has been paid to
College, Durg 491001, India the synthesis and luminescent properties of ­Eu3+-doped
3
Department of Physics, Rashatrasant Tukadoji Maharaj rare-earth orthoborates ­(REBO3) due to their desirable
Nagpur University, Nagpur 440033, India properties as ideal vacuum ultraviolet phosphors, whose
4
Department of Physics, University of the Free State, progress is key to the development of plasma display pan-
Bloemfontein ZA9300, South Africa els (PDPs) [1]. Various synthesis techniques have been

13
Vol.:(0123456789)
13566 J Mater Sci: Mater Electron (2017) 28:13565–13578

developed to prepare high-quality R ­ EBO3:Eu3+ phos- 2 Experimental

phors, such as solid-state reaction (SR) [7, 18], co-precip-
itation [19, 20], microwave heating [21], spray pyrolysis Y2O3:Eu3+ phosphor was synthesized by the conventional
[6], and sol–gel method [4], but most of them only aimed solid state reaction method. Oxide of rare earth materials
at the enhancement of the photoluminescence (PL). For such as Yttrium Oxide ­(Y2O3), Europium Oxide ­(Eu2O3)
PDP phosphors, both luminescent efficiency and color and ­CaF2 as a flux with high purity (99.99%) from sigma
purity are required. Unfortunately, as a red phosphor, Aldrich were used as precursor materials to prepare E­ u3+
the intensity of the red emission of ­REBO3:Eu3+ is lower doped ­Y2O3 phosphor. In stoichiometric ratios of the
than that of the orange, leading to a poor chromaticity. rare earth ions ­Eu3+ and ­Y2O3 were used to synthesize
Many papers reported on the PL of borate based phos- ­Y2O3:Eu3+ phosphors with different mol% of E ­ u3+ ions.
phors but very few papers gives the information about the These chemicals were weighed and grinded into a fine
thermoluminescence (TL) glow curve analysis and traps powder by using an agate mortar and pestle. The grinded
formation [22]. samples were placed in an alumina crucible and heated
Oxide phosphors are found to be suitable for field at 1000 °C for 2 h followed by dry grinding and further
emission display (FED), vacuum fluorescent display heated at 1300 °C for 3 h in a muffle furnace. The sam-
(VFD), plasma display panel (PDP) and electrolumines- ples were allowed to cool at room temperature in the
cence (EL) devices. Luminescence efficiency is found to same furnace for about 15 h [30–35].
increase as the size of the phosphor particle is decreased Similarly the Y­ BO3 phosphors doped with ­Eu3+ were
and the preparation of phosphor powders becomes very prepared by the solid state reaction method. To prepare
important in technological applications [23]. When TL the ­YBO3:Eu3+doped phosphor with a variable concen-
material is exposed to γ-radiation, it absorbs and stores ­ u3+. ­Y2O3, ­Eu2O3 and ­H3BO3 were used as
trations of E
energy in the form of defects. A part of the stored energy starting material. The reactant mixtures were taken in
is released in the form of visible light when the two quartz boats and heated in the presence of air at 500 °C
types of defect centres are recombined upon warming the for 1 h followed by heating at 1000 °C for 1 h for calcina-
material. tion in a muffle furnace. The mixtures were grinded by
Metal oxide matrix is proved to be an excellent host using an agate mortal and pastle after every heating. The
material for lasing action. The Y ­ 2O3 possesses high mixtures were grounded together to obtain homogene-
refractory properties, a high melting point (~2450 °C) ous powders. After being grounded thoroughly for nearly
and a high thermal conductivity (33 Wm−1 K−1). It is a 45 min, to ensure the best homogeneity and reactivity, the
suitable material for photonic waveguide due to its high powders were transferred to alumina crucibles, and then
band gap (5.72 eV), with a very high refractive index heated in a muffle furnace at 1250 °C for 2 h. The phos-
(~2) and a wide transmission range (280–8000 nm) [14]. phor materials were cooled to room temperature natu-
Numerous techniques are applied on the synthesis of rare rally. All samples were found to be white [22].
earth doped nanocrystalline ­Y2O3 [24–28].
Over the past years, yttrium oxide and borate based Y2 O3 + Eu2 O3 → Y2 O3 :Eu3+
phosphors has been reported as the best host materials
YBO3 + Eu2 O3 → YBO3 :Eu3+
for luminescence emission due to its good chemical and
thermal stability [29]. Keeping this view, TL glow curve The powder XRD pattern of the synthesized phos-
analysis of oxide and borate based UV, β and γ irradiation phors was carried out using a Bruker D8 Advance X-ray
and the calculation of associated kinetic parameters were diffractometer with C ­ uKα radiation (0.154 nm) in the
carried out. range of 10°–90°. The refinement of the XRD pattern
The present paper reports on the TL behaviour of UV, was carried out via the match software. TL glow curves
β and γ irradiated ­Eu3+ doped in different host matrixes were recorded at room temperature by using a TLD
­(Y2O3 and Y ­ BO3). The E ­ u3+ doped samples of ­ Y 2O 3 reader I1009 (Nucleonix Sys. Pvt. Ltd. Hyderabad).
and ­YBO3 were synthesized by the solid state reaction The obtained phosphors under the TL examination were
method. The prepared samples were characterized by exposed to UV radiation using a 254 nm UV source, β
X-ray diffraction (XRD) and TL glow curves. The corre- ­ r90 source and γ irradiation using a
irradiation using a S
60
sponding kinetic parameters were calculated by the peak ­Co source. All of the measurements were performed at
shape method for UV, β and γ irradiated samples. They room temperature [30–37].
were compared to the theoretical and experimental glow
curves by using the computerized glow curve deconvolu-
tion (CGCD) technique and the respected figure of merit
(FOM) was described.

13
J Mater Sci: Mater Electron (2017) 28:13565–13578 13567

3 Results and discussion the COD card No. 96-100-9014. Refinement was done
using Celref version 3 (Collaborative Computational Pro-
3.1 Phase identification and structural refinement ject No. 14 [CCP14] for Single Crystal and Powder Diffrac-
tion Birkbeck University of London and Daresbury Labo-
Figure 1a exhibits the comparison of the observed, cal- ratory, London, UK). The calculated spectra confirmed the
culated XRD pattern of ­ Y2O3:Eu3+ having 2 mol% of presence of cubic ­Y2O3. The calculated lattice parameters
­Eu3+ and the standard (Match!2) XRD pattern of ­Y2O3. are shown in Table 1. They were slightly deferred than val-
Match! v. 2.3.1 was used to match the standard (Crystal- ues obtained in case of the standard COD card. This may
lographic open database) and experimental XRD pattern. ­ u3+ (dopant) ions having greater
be due to the presence of E
3+
It was clearly observed that, the experimental XRD pattern ionic radii than the ­Y ions [38].
matched convincingly with the crystallographic open data- The black solid curve indicated the experimental diffrac-
base (COD) card No. 96-100-9014 with FoM of 0.9446. tion data and the “*” marks represented the simulated dif-
This is the already reported XRD pattern of ­Y2O3 [29]. fraction data. The red line denoted the deviation between
The datasheet provided by match version 2.3.1 expressed the simulated and experimental values (Fig. 1b). The
that the prepared sample was cubic with an Ia3̄ (206) space crystal system of the prepared samples was identified as a
group. Table 1 presents the refined lattice parameters of the hexagonal structure. It shows the Powder XRD pattern of
phosphor ­Y2O3:Eu3+ having a 2 mol% of ­Eu3+. The values ­YBO3:Eu3+. The peaks were found to be in agreement with
of the lattice parameters of the phosphor was obtained from the JCPDS card No. 16–0277 [39] reference corresponding

Fig. 1  a Comparison of

observed, calculated and stand-
ard (matched) XRD pattern of (a)
­Y2O3:Eu3+ phosphor. b Refined
XRD pattern of the ­Eu3+ doped
­YBO3 phosphor. (Color figure
online)

(b)

13
 Table 1  Indexing and refined lattice parameters
13568

Crystal structure
Crystallographic data

13
Space group Ia -3 (206)
Crystal system Cubic
Cell parameters a = 10.6056 Å
Z 16
d [Å] Int h k l Mult.

5.3028 2.7 2 0 0 6
4.3297 119.4 2 1 1 24
3.7496 0.2 2 2 0 12
3.0616 1000.0 2 2 2 8
2.8345 5.2 2 3 1 24
2.6514 253.3 4 0 0 6
2.4998 50.2 4 1 1 24
2.3715 11.1 4 0 2 12
2.2611 55.7 3 2 3 24
2.1649 8.9 4 2 2 24
2.0799 82.1 3 4 1 24
1.9363 25.6 5 1 2 24
1.8748 405.5 4 4 0 12
1.8188 20.9 3 4 3 24
1.7676 4.3 4 2 4 24
1.7205 48.7 3 5 2 24
1.6769 10.7 6 0 2 12
1.6365 38.2 4 5 1 24
1.5989 263.1 6 2 2 24
1.5637 55.9 6 1 3 24
1.5308 43.6 4 4 4 8
1.4999 18.4 4 3 5 24
1.4707 11.3 6 0 4 12
1.4432 28.9 5 2 5 24
1.4172 13.5 4 6 2 24
1.3469 18.4 3 7 2 24
1.3257 37.9 8 0 0 6
1.3055 31.4 4 7 1 24
1.2861 16.7 4 6 4 24
J Mater Sci: Mater Electron (2017) 28:13565–13578
 Table 1  (continued)
d [Å] Int h k l Mult.

1.2676 18.1 5 3 6 24
1.2499 11.3 6 6 0 12
1.2329 28.1 4 7 3 24
1.2165 63.1 6 6 2 24
1.2008 0.7 5 7 2 24
1.1857 40.7 8 0 4 12
1.1712 8.2 8 3 3 24
1.1572 9.2 4 8 2 24
1.1436 18.9 5 6 5 24
1.1306 1.4 6 4 6 24
1.1179 19.3 5 4 7 24
J Mater Sci: Mater Electron (2017) 28:13565–13578

1.0939 20.1 6 7 3 24
1.0824 43.7 8 4 4 24
1.0713 19.8 5 8 3 24
1.0606 12.6 8 0 6 12
1.0501 6.4 7 7 2 24
1.0400 28.5 6 8 2 24
1.0301 7.1 4 9 3 24
1.0205 37.5 6 6 6 8
1.0112 24.9 5 9 2 24

13
13569
13570 J Mater Sci: Mater Electron (2017) 28:13565–13578

to the [002], [100], [101], [102], [004], [110], [104], [112], measurements (Fig. 2). The heating rate used for the TL
[200], [202], [114], [204] and [210] planes. It confirmed measurements was 6.7 °C s−1. The ­YBO3:Eu3+ (2 mol%)
the formation of single phase hexagonal crystalline yttrium doped samples furnished well resolved peaks at (a) 174 and
orthoborate phosphor [39]. 390 °C for the UV irradiation, (b) 143 and 286 °C for the
β irradiation and (c) 149 and 282 °C for the γ irradiation.
3.2 Thermoluminescence study of ­YBO3:Eu3+ doped The corresponding activation energy (E) values were cal-
phosphor culated by the use of the formulas modified by Chen and
others. The shape factor (µ), activation energy (E), and fre-
The TL was studied by giving the samples UV (254 nm quency factor (s) for the prominent glow peaks of the pre-
source), β (­Sr90 source) and γ ­ (Co60 Source) exposure pared phosphors were evaluated and presented in Tables 2,
with different doses prior to the TL recordings, Fig. 2. The 3 and 4 using the CGCD technique. It was found that for
254 nm UV source irradiation measured after 25 min, the the ­YBO3:Eu3+ doped phosphor, the formation of both
β ­(Sr90 source) irradiation after 30 min and the γ ray expo- shallower (lower temperature peak) and deeper (high tem-
sure after a dose of 1 kGy are shown in Fig. 2. Every time perature peak) trapping occurred. The deeper trapped peaks
a 2 mg weighed powdered phosphor was taken for the TL are shown in Fig. 2a–c, which presented the experimentally

(a) (b)

(c)

Fig. 2  TL glow curves of the a UV, b β and c γ irradiated ­YBO3:Eu3+ (2 mol %) doped phosphor

­ BO3:Eu3+ (2 mol%) doped phosphor after 25 min UV ray

Table 2  Corresponding kinetic parameters calculation from CGCD curve for the Y
irradiation
Peaks T1 Tm T2 τ δ ω µ = δ/ω b E (eV) S ­(s−1)

Peak 1 161 208 263 47 55 102 0.53 2.13 0.644 5 × 107

Peak 2 305 339 371 34 32 66 0.48 1.69 1.425 7 × 1012

13
J Mater Sci: Mater Electron (2017) 28:13565–13578 13571

observed peaks for the UV, β and γ irradiation (higher in Fig. 5b. It also showed a linear relation with the γ expo-
temperature). sure (Fig. 5b). Hence this behaviour of the sample might be
TL glow curve analysis of the ­YBO3:Eu3+ doped phos- very useful for γ dosimetry applications [30].
phor for varying UV dose up to 25 min, shows that the TL
glow curve intensities increased with a UV dose and hav- 3.3 Computerized glow curve deconvolution of ­YBO3
ing a near linear response with dose means the prepared and ­Y2O3:Eu3+ phosphor for UV, β and γ induced
phosphor may be useful for UV dosimetry (Fig. 3a, b). phosphor
The TL glow curve peak analysis were focused on the high
temperature peak which were due to the deeper trapping The recorded glow curves of the prepared phosphors
phenomenon. exposed to UV, β and γ exposure with different doses seem
TL glow curve analysis of ­YBO3:Eu3+ (2 mol %) doped to be composite in nature as they exhibit a broad peak. So,
phosphor for varying β dose shows the TL glow curve CGCD method was used to deconvolute and calculate the
intensity increased with β dose and having a linear response kinetic parameters. This computer programme (Glowfit) is
with dose and may be useful for β dosimetry (Fig. 4a, b). based on Halperin and Barner equations which describe the
Figure 5a shows the TL glow curves of the ­YBO3:Eu flow of the charges between the various energy levels dur-
(2 mol%) γ irradiated for doses of 0.5 kGy up to 2 kGy. ing a trap emptying by thermal heating. The kinetic param-
These TL glow curves showed two prominent well resolved eters of trap levels were determined for each deconvoluted
TL glow peaks at 146 and 282 °C, respectively. The results peak by this programme [29, 37, 38, 40–42].
indicated the creation of trapping centres that increased The fitted TL glow curves are shown in Fig. 6a–c for
with an increasing γ-ray exposure. The TL intensity of the ­YBO3:Eu3+ and Figs. 7d, 8b and 9c for Y ­ 2O3:Eu3+ and
282 °C glow peak as a function of irradiated dose is shown the values of trap depths and frequency factors of trapped

Table 3  Corresponding kinetic parameters calculation for CGCD curve for ­YBO3:Eu3+ (2 mol%) doped phosphor after 30 min β irradiation
Peaks T1 Tm T2 τ δ ω µ = δ/ω b E (eV) S ­(s−1)

Peak 1 130 169 210 39 41 80 0.51 1.89 0.649 3 × 108

Peak 2 253 281 311 28 30 58 0.51 1.89 1.427 1 × 1014

Table 4  Corresponding kinetic Peaks T1 Tm T2 τ δ ω µ = δ/ω b E (eV) S ­(s−1)

parameters calculated from
CGCD curve for the ­YBO3:Eu3+ Peak 1 75 101 118 348 17 43 0.395 1 0.681 2 × 1010
(2 mol%) doped phosphor after
Peak 2 94 129 159 367 30 65 0.462 2 0.589 3 × 108
2 kGy γ radiation
Peak 3 162 215 254 435 39 92 0.424 2 0.563 5 × 106
Peak 4 235 273 305 508 32 70 0.457 2 1.005 2 × 1010

(a) (b)

Fig. 3  a TL glow graphs of the ­YBO3:Eu3+ (2 mol %) doped phosphor with the variation of UV exposure time focused on the high temperature
peak. b Dose versus intensity plot with the variation of UV exposure time. (Color figure online)

13
13572 J Mater Sci: Mater Electron (2017) 28:13565–13578

(a) (b)

Fig. 4  a TL glow curve of the Y ­ BO3:Eu3+ doped phosphor with the variation of β exposure time focused on the high temperature peak. b Dose
versus intensity plot with the variation of β exposure time. (Color figure online)

(a) (b)

Fig. 5  a TL glow curve of Y­ BO3:Eu3+ (2 mol%) doped phosphor with the variation of γ exposure. b TL intensity vs γ dose plot for Y
­ BO3:Eu
(2 mol%). (Color figure online)

charges calculated by CGCD method are summarized in order of kinetic and frequency factors were also calculated
Tables 2, 3, 4, 5, 6 and 7. using the peak shape method for individual peaks (Table 3).
Figure 6a shows the TL CGCD curve of the ­YBO3:Eu3+ The order of kinetics are same for both peaks (1 and 2) but
(2 mol%) phosphor for the UV ray induced sample after the activation energy is high for higher temperature peak
25 min UV exposure. The corresponding kinetic param- which represents the deeper level trapping in the β irradi-
eters such as activation energy, order of kinetic and fre- ated phosphor (30 min β dose). The optimized concen-
quency factors were also calculated using the peak shape tration of dopant i.e. 2 mol% of E­ u3+ ion also from other
method for the individual peaks. The two peaks fitted for irradiation such as γ and UV irradiated phosphors higher
the ­YBO3:Eu3+ phosphor (2 mol%) showed nearly second temperature peaks having high activation energy (Tables 2,
order of kinetics and the activation energy calculations 3, 4). FoM of all fitted curve found less than or equal 2%
showed the formation of both shallower and deeper traps in which is best fit by CGCD technique.
the prepared sample for the UV irradiation (Table 2). The The TL CGCD of the ­YBO3:Eu3+ phosphor for the fixed
corresponding activation energy was, however, low as com- optimized concentration of ­Eu3+ (2 mol%) with γ exposure
pared to the γ irradiation as pointed out below. of 2 kGy is shown in Fig. 6c. The corresponding kinetic
Figure 6b shows the TL CGCD curve of the Y ­ BO3:Eu3+ parameters such as activation energy, order of kinetic and
(2 mol%) phosphor after a β irradiated of 30 min. The cor- frequency factors were calculated using the peak shape
responding kinetic parameters such as activation energy, method for the individual peaks (Table 4). The four peaks

13
J Mater Sci: Mater Electron (2017) 28:13565–13578 13573

(a) (b)

(c)

­ BO3:Eu3+ (2 mol%) doped phosphor after 10 min UV ray irradiation. b CGCD curve for Y
Fig. 6  a CGCD curve for the Y ­ BO3:Eu3+ (2 mol%)
3+
doped phosphor after 30 min β irradiated. c CGCD curve for the ­YBO3:Eu (2 mol%) doped phosphor with γ exposure of 2 kGy

that were fitted for the ­ YBO3:Eu3+ phosphor (2 mol%) activation energy which is low and it is calculated from the
showed nearly a second order of kinetic and the activation CGCD pattern of the UV irradiated sample (Fig. 7d).
energy was high for the high temperature peak. It pointed TL glow curves recorded for the ­Y2O3:Eu3+ (2 mol%)
towards the formation of deeper traps in the prepared sam- doped phosphor with the variation of the UV exposure
ple during γ ray irradiation. When sample were irradiated time are shown in Fig. 7b. It was found that the TL glow
by the γ rays, which is a high energy source, deep levels curve intensity increased with increasing UV exposure and
were created and the electrons got trapped in the deep lev- it showed a linear response with dose. The linearity of pre-
els and the required energy for escaping one electron is pared phosphor with dose showed the prepared phosphor
high which means the activation energy was high for the γ may be used for TL UV dosimeters (Fig. 7b, c).
irradiated samples. The sample was also irradiated with Sr-90 βsource giv-
Figure 6a–c shows a good FoM nearly 2.05% for UV ing a dose of 10 Gy and the heating rate used for the TL
induced curve, 1.23% for β irradiated curve and 1.86% for γ measurements were 6.7 °C s−1. The samples displayed
irradiated fitted curve. good TL peaks at 182 °C and two shoulder peak at 264 and
327 °C (Fig. 8a). For the β irradiation the intensity was low
3.4 Thermoluminescence study of ­Y2O3:Eu3+ because the 10 Gy dose was a very low energy and the peak
temperature was high as compared to the UV irradiated
Figure 7a shows the TL glow curve of the ­ Y2O3:Eu3+ phosphor. Indicating the formation of shallower trap for
(2 mol%) doped phosphor after 25 min UV exposure time. UV irradiation and deeper trap formation for the β irradi-
The sample shows a well resolved peak at 121 °C. The ated ­Y2O3:Eu3+ (2 mol%) phosphor.
lower temperature peak shows the formation of shallower The CGCD pattern plotted for the Y ­ 2O3:Eu3+ (2 mol%)
trapping (Tables 5, 6, 7). Table 5 shows the corresponding phosphor for the β 10 Gy dose with four fitted peaks having

13
13574 J Mater Sci: Mater Electron (2017) 28:13565–13578

(a) (b)

(c) (d)

Fig. 7  a TL glow curve for ­Y2O3 2 mol% of ­Eu3+ doped phosphor c Dose versus intensity plot with the variation of UV exposure time.
for UV ray induced sample. b TL glow curve analysis of UV induced d CGCD curve for Y ­ 2O3:Eu3+ (2 mol%) doped phosphor UV ray
­Y2O3:Eu3+ doped phosphor with the variation of UV exposure time. induced

(a) (b)

Fig. 8  a TL glow curve of β irradiated ­Y2O3:Eu3+ (2 mol%) phosphor for a 10 Gy dose. b CGCD curve for Y
­ 2O3:Eu3+ (2 mol%) doped phos-
phor β irradiated

a good figure of merit of nearly 1.25% is shown in Fig. 8b. a high dose of 2 kGy and found that the corresponding
kinetic parameters are calculated as indicated in Table 6. activation energy is high. It was fitted by two resolved
For ­Eu3+ (2 mol%) doped Y ­ 2O3 phosphor irradi- peaks in the composed broad TL glow curve. The kinetic
ated by γ ­Co60 source with a dose of 2 kGy shows a TL parameters were calculated for the experimental glow
glow curve peak at 157 °C (Fig. 9a). The TL glow curve curve as well as the fitted glow curve (Table 7) it is
showed the second order of kinetic peak. Figure 9a shows observed that it having a fairly good fit with a FOM of
the CGCD glow curve of γ—irradiated sample with nearly 2.82%.

13
J Mater Sci: Mater Electron (2017) 28:13565–13578 13575

(a) (b)

(c)

Fig. 9  a CGCD curve for Y ­ 2O3:Eu3+ (2 mol%) doped phosphor γ 2 kGy irradiated. b TL glow curve for Y ­ 2O3:Eu3+ (2 mol%) doped phosphor
3+
for variable γ dose 0.5–2 kGy. c Glow peak intensity under 2 kGy γ dose for ­Y2O3:Eu (2 mol%). (Color figure online)

Table 5  Corresponding kinetic Peaks T1 Tm T2 τ δ ω µ = δ/ω b E (eV) S ­(s−1)

parameters calculation for
CGCD curve for ­Y2O3:Eu3+ Peak 1 118 151 183 33 32 65 0.49 1.65 0.703 3 × 109
(2 mol%) doped phosphor UV
Peak 2 129 152 175 23 23 46 0.5 1.69 1.019 2 × 1013
irradiated sample
Peak 3 82 116 153 34 37 71 0.52 2 0.579 4 × 108

Table 6  Corresponding kinetic Peaks T1 Tm T2 τ δ ω µ = δ/ω b E (eV) S ­(s−1)

parameters calculation for
CGCD curve for ­Y2O3:Eu3+ Peak 1 146 179 212 33 33 66 0.5 1.69 0.80 1 × 1010
(2 mol%) doped phosphor β
Peak 2 199 217 232 18 15 33 0.45 1.32 1.72 1 × 1019
irradiated sample
Peak 3 224 263 300 39 37 76 0.48 1.55 0.95 9 × 109
Peak 4 302 320 335 18 15 33 0.45 1.32 2.52 7 × 1022

Table 7  Corresponding kinetic Peaks T1 Tm T2 τ δ ω µ = δ/ω b E (eV) S ­(s−1)

parameters calculation for
CGCD curve for ­Y2O3:Eu3+ Peak 1 106 136 168 30 32 62 0.51 1.89 0.725 1 × 1010
(2 mol%) doped phosphor γ
Peak 2 106 133 160 27 27 54 0.5 1.69 0.791 1 × 1011
irradiated sample
Peak 3 119 168 220 49 52 101 0.51 1.89 0.513 6 × 109

For the different γ dose the recorded TL glow curves the sample was prepared by solid state reaction method
showed a linear response with dose (Fig. 9b, c). The lin- generated some defects in the prepared sample which was
earity with γ dose present good dosimetry phosphor and responsible for the TL glow curve.

13
13576 J Mater Sci: Mater Electron (2017) 28:13565–13578

3.5 Decay characteristics ­Y2O3 and ­YBO3: ­Eu3+ structure of insulators, and to the presence of imperfection
(2 mol%) samples after γ irradiation in its lattice. The process can be described, in a simplified
way, recurring to the energy band representation of insula-
For the investigation of the decay process of the ­YBO3:Eu3+ tors and assuming the presence of two kinds of imperfec-
and ­Y2O3:Eu3+ phosphors, a 2 kGy γ—dose was given and tion in the crystal, as shown in Fig. 11.
then the TL glow curves were measured after different We present a model to explain the TL behaviour of
delay times; 24, 48, 72 and 96 h, respectively (Fig. 10a, b). ­YBO3:Eu3+ and Y ­ 2O3:Eu3+ to UV, β and γ radiation. In
Figure 10a represents the decay in the TL glow curves of existing models, irradiation of a sample with an electron
the ­YBO3:Eu3+ and Fig. 10b shows the decay curve of the beam creates two types of trap, one shallower and the other
­Y2O3:Eu3+ doped phosphor, both consists of an exponential deeper, in the forbidden band gap of the material (Fig. 11).
nature. The respective emission decay observed to follow When a sample is irradiated with UV, it forms shallower
the second order exponential function given below: traps, as confirmed by the lower temperature peak of the
glow curve. Upon heating of the UV-irradiated material,
I = A1 exp(−t∕t1 ) + A2 exp(−t∕t2 )
the charge carriers trapped during irradiation are released
where I is the fluorescence intensity, A
­ 1, ­A2 are constants, t and transition to the conduction band. The electrons that
is time, τ1 and τ2 are decay times for the exponential com- transition from the conduction band are either be re-trapped
ponents Fig. 10a, b. It was concluded that from the TL at the trap level or defect centre or at the hole trap or lumi-
decay study that both have a low fading rate and good sta- nescence centre, where they recombine with holes, giving
bility which are useful for dosimetry applications. rise to luminescence or the glow peak. Trapped charge car-
riers are found inside the forbidden band gap, as confirmed
3.6 TL model for UV, β and γ irradiated traps by the calculated trap parameters. Similarly for β and γ
formation in the ­Y2O3:Eu3+ and ­YBO3: irradiated ­YBO3:Eu3+ and Y ­ 2O3:Eu3+ deeper traps were
­Eu3+phosphor formed and higher temperature peaks having high activa-
tion energy as compared to UV irradiated phosphor con-
TL is the emission of light observed during the heating of firmed the formation of deep trapping phenomenon.
insulating or semiconductor materials, provided that they
have been previously exposed to ionising radiation [43–46].
The irradiation may take place in the laboratory or 4 Conclusion
a radiative environment. Another possibility, which is
exploited in dating applications, is when a naturally occur- ­ BO3:Eu3+ and Y
In this work, Y ­ 2O3:Eu3+ were synthesized
ring material is irradiated by the radiation field of its nat- by the solid state reaction method. The TL emission meas-
ural surroundings. The exposure to radiation perturbs the urements upon excitation with ultraviolet, β-irradiation and
initial stable configuration of the material and the heating γ-irradiation showed very good TL glow curve response
allows the release of the accumulated energy. The existence for both phosphors. It was found that the deep trapping
of thermoluminescence is linked to the internal ordered phenomenon occurred for both γ-irradiated samples and

(a) (b)

Fig. 10  a TL peak intensity of the TL glow curves maximum plotted against delay time and fitted curve for the Y ­ BO3:Eu3+ (2 mol%). b TL
peak intensity of the TL glow curves maximum plotted against the delay time and fitted curve for ­theY2O3:Eu3+ (2 mol %) doped phosphor

13
J Mater Sci: Mater Electron (2017) 28:13565–13578 13577

Fig. 11  Traps level in UV, β

and γ irradiated phosphors

β-irradiated ­YBO3:Eu3+ and Y ­ 2O3:Eu3+ phosphors. All 13. J.P. Chaminade, O. Viraphong, F. Guillen, C. Fouassier, B. Czirr,
results revealed the possibility of using the ­YBO3:Eu3+ IEEE Trans. Nucl. Sci. 48, 1158 (2001)
3+ 14. I.-E. Kwon, B.-Y. Yu, H. Bae, Y.-J. Hwang, T.-W. Kwon, Ch.-H.
and ­Y2O3:Eu phosphors in TL dosimetry and ionizing Kim, Ch.-H. Pyun, S.-J. Kim, J. Lumin. 87–89, 1039 (2000)
radiations. It may be useful for personal and environmen- 15. J.W. Kolis, H.G. Giesber, Patent No. US 2005022720 (USA)
tal monitoring. The suitable mechanism of the TL trapping (2005)
parameters was explained in detail and it shows very good 16. M. Knitel, New Inorganic Scintillators and Storage Phosphors
for Detection of Thermal Neutrons. (Delft University Press,
response for TL applications. Delft, 1998)
17. Y. Miyasaki, M. Aoki, K. Sugimoto, T. Horikawa, J. Hibino, Y.
Tanaka, H. Setoguchi, O. Toyota, Patent No. JP 2005183246
(Japan) (2005)
References 18. X.Y. Wu, G.Y. Hong, X.Q. Zeng, H.P. You, C.H. Kim, C.H.
Pyun, H.S. Bal, B.Y. Yu, I.E. Kwon, C.H. Park, Chem. J. Chin.
1. M. Blaise, P. Porcher, J. Solid State Chem. 97, 74 (1992) U 21, 1658 (2000)
2. D.A. Keszler, H. Sun, Acta Crystallogr. C44, 1505 (1988) 19. K.N. Kim, H.K. Jung, H.D. Park, D. Kim, J. Mater. Res. 17, 907
3. Y. Laureiro, M.L. Veiga, F. Fernandez, R. Saez Puche, A. Jerez, (2002)
J. C. Pico, Less Com. Metals 157, 335 (1990) 20. D. Boyer, G. Bertrand-Chadeyron, R. Mahiou, C. Caperaa, J.C.
4. E.M. Levin, R.S. Roth, J.B. Martin, Am. Mineral 46, 1030 Cousseins, J. Mater. Chem. 9, 211 (1999)
(1961) 21. Y.Y. Li, M.L. Peng, S.H. Feng, Chin. Chem. Lett. 7, 387 (1996)
5. G. Chadeyron, M. El-Ghozzi, R. Mahiou, A. Arbus, J.C. Cous- 22. V. Dubey, J. Kaur, S. Agrawal, N.S. Suryanarayana, K.V.R. Mur-
seins, J. Solid State Chem. 128, 261 (1997) thy, Superlatt. Microstruct. 67, 156 (2014)
6. G. Corbel, M. Leblanc, E. Antic-Fidancev, M. Lema_ıtre-Blaise, 23. S. Erdei, R. Roy, G. Harshe, H. Juwhari, D. Agarwal, F.W.
J.C. Krupa, J. Alloys Compd. 287, 71 (1999) Ainger, W.B. White, Mater. Res. Bull. 30, 745 (1995)
7. M. Ren, J.H. Lin, Y. Dong, L.Q. Yang, M.Z. Su, L.P. You, Chem. 24. X.J. Wang, L.D. Zhang, J.P. Zhang, G. He, M. Liu, L.Q. Zhu,
Mater. 11, 1576 (1999) Mater. Lett. 62, 4235 (2008)
8. H.J. Meyer, Naturwissenschaften 59, 215 (1972) 25. H. Eilers, B.M. Tissue, Chem. Phys. Lett. 251, 74–78 (1996)
9. R. Boehlhoff, H.U. Bambauer, W.Z. Hoffmann, Kristallogr. 26. M. Kottaisamy, D. Jeyakumar, R. Jagannathan, M. Mohan Rao,
Kristallgeom. Kristallphys. Kristallchem. 133, 386 (1971) Mater. Res. Bull 31, 1013 (1996)
10. S. Lemanceau, G. Bertrand-Chadeyron, R. Mahiou, M. El- 27. B. Bihari, H. Eilers, B.M. Tissue, J. Lumin. 75, 1 (1997)
Ghozzi, J.C. Cousseins, P. Conflant, R.N. Vannier, J. Solid State 28. Y. Tao, Z. Guiwen, Z. Weiping, X. Shangda, Mater. Res. Bull.
Chem. 148, 229 (1999) 32, 501 (1997)
11. L. Lou, D. Boyer, G. Bertrand-Chadeyron, E. Bernstein, R. 29. I.R. Singh, R.S. Ningthoujam, V. Sudarsan, I. Shrivastav, S.D.
Mahiou, J. Mugnier, Opt. Mater. 15, 1 (2000) Singh, G.K. Dey, S.K. Kulshreshtha, Nano Tech. 19, 1 (2008)
12. Z.G. Wei, L.D. Sun, X.C. Jiang, C.S. Liao, C.H. Yan, Y. Tao, J. 30. V. Dubey, J. Kaur, S. Agrawal, Res. Chem. Intermed. 41, 401
Zhang, T.D. Hu, Y.N. Xie, Chem. Mater. 15, 3011 (2003) (2015)

13
13578 J Mater Sci: Mater Electron (2017) 28:13565–13578

31. S. Agrawal, V. Dubey J. Radiat. Res. Appl. Sci. 7(4), 601 (2014) 41. S. Som, M. Chowdhury, S.K. Sharma, Radiat. Phys. Chem 110,
32. V. Dubey, J. Kaur, S. Agrawal, Res. Chem. Intermed. 41, 4727 51 (2015)
(2015) 42. K.S. Chung, H.S. Choe, J.I. Lee, S.Y. Chang, Radiat. Prot.
33. J. Kaur, Y. Parganiha, V. Dubey, D. Singh, D. Chandrakar, Dosim. 115, 136 (2005)
Superlatt. Microstruct. 73, 38 (2014) 43. S.W.S. McKeever, Thermoluminescence of Solids (Cambridge
34. V. Dubey, J. Kaur, S. Agrawal, N.S. Suryanarayana, K.V.R. Mur- University Press, Cambridge, 1985), p. 390
thy, Optik 124, 5585 (2013) 44. M. Martini, F. Meinardi, Thermally stimulated luminescence:
35. V. Dubey, N.S. Suryanarayana, J. Kaur, J. Miner. Mater. Charac. new perspectives in the study of defects in solids. La Rivista del
Eng. 9(12), 1101 (2010) Nuovo Cimento 20–4(8), 1–71 (1997)
36. V. Dubey, J. Kaur, N.S. Suryanarayana, K.V.R. Murthy, Res. 45. R. Chen, S.W.S. McKeever, Theory of Thermoluminescence
Chem. Intermed. 39, 3689 (2013) and Related Phenomenon. (World Scientific, Hong Kong, 1997)
37. V. Dubey, J. Kaur, Y. Parganiha, N.S. Suryanarayana, K.V.R. p. 559
Murthy, Appl. Radiat. Isotop. 110, 16 (2016) 46. S.W.S. McKeever, M. Moscovitch, P.D. Townsend, Thermolu-
38. R. Shrivastava, J. Kaur, V. Dubey, B. Jaykumar, Bull. Mater. Sci. minescence Dosimetry materials: Properties and Uses. (Nuclear
37(4), 925 (2014) Technology Publishing, Ashford, 1995), p. 221
39. V. Dubey, J. Kaur, N.S. Suryanarayana, S. Agrawal, Int. J.
Lumin. Appl. 3(II), 98 (2013)
40. G. Baldinozzi, J.-F. Berar, G. Calvarin G, Mater. Sci. For. 278,
680 (1998)

13