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Journal of Luminescence 149 (2014) 176–184

Contents lists available at ScienceDirect

Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Characterization and luminescence studies of Eu doped


Barite nanophosphor
Shaila Bahl a,n, S.P. Lochab b, Anant Pandey c, Vipin Kumar d, V.E. Aleynikov e,
A.G. Molokanov e, Pratik Kumar a
a
Medical Physics Unit, IRCH, AIIMS, New Delhi 110029, India
b
Inter-University Accelerator Center, Aruna Asaf Ali Marg, New Delhi 110067, India
c
Department of Physics, Sri Venkateswara College, University of Delhi, New Delhi 110021, India
d
Department of Physics and Astrophysics, University of Delhi, New Delhi 110007, India
e
Joint Institute for Nuclear Research, Dubna 141980, Russia

art ic l e i nf o a b s t r a c t

Article history: Barite (BaSO4) nanophosphors were successfully prepared by the co-precipitation method. The structural
Received 16 February 2013 analysis of the sample was carried out by analytical techniques such as X-ray diffraction (XRD),
Received in revised form Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and Raman
12 December 2013
spectroscopy. XRD study reveals that the particles exhibit orthorhombic structure and are approximately
Accepted 7 January 2014
Available online 15 January 2014
50 nm in size, while TEM study further confirms the particle size in the range 48–52 nm and depicts oval
shape of the particles. The FTIR spectrum displays the bands centered at 1197 to1077 cm 1 and the
Keywords: shoulder at 982 cm 1 corresponding to the symmetrical vibration of SO42 ion. Moreover, S–O bending
Thermoluminescence and stretching are the Raman signature of barite, which were proven by the Raman spectra, unveiling the
Photoluminescence
various vibrational modes of the compound. Samples were irradiated by gamma rays and proton beams
Nanocrystalline
and their Thermoluminescent (TL) glow curves were plotted and studied. On applying two different
Proton beam
Raman types of irradiations in addition to large energy difference, the sample showed almost a similar TL glow
FTIR curve structure, which is the remarkable feature of this phosphor. Analysis of the glow curve was also
carried out by the glow curve deconvolution method. Photoluminescence (PL) study shows broad
excitation spectra with the main peak at around 250 nm whereas the emission band excited by the
wavelength 250 nm was observed at 374 nm which corresponds to the 4f65d-4f7 (8S7/2) transitions of
Eu2 þ ions. The sample was also examined for its PL response to different exposures of gamma
irradiations where it showed an increase in the PL intensity up to a dose of 800 Gy for both excitation
and emission spectra. The present sample shows good crystal quality along with high TL and PL
sensitivity. Hence our results suggest possible potential applications of nanocrystalline BaSO4:Eu
phosphor in dosimetric study of gamma and proton beams.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction other heavy particles). This ionizing property of these radiations


has been utilized for treatment of heterogeneous class of diseases
Radiation is omnipresent in the environment. It is a form of in which a group of cells display uncontrolled growth, commonly
energy which traverses as electromagnetic waves or high speed known as cancer.
particles. It can further be classified as ionizing and non-ionizing, Both ion beam and photon therapy work on the principle of
differentiating feature being the amount of energy they carry. selective cell destruction but the treatment with energetic ion
Non-ionizing radiation has enough energy to move around the beams has various advantages compared to the conventional
atoms in a molecule or cause them to vibrate, but not enough to irradiation with photons. The chief advantage is its ability to
remove electrons, while ionizing radiation has enough energy to deposit the radiation more precisely due to the phenomena of
break chemical bonds in molecules or remove tightly bound Bragg Peak [1] in which the dose deposition is at the end of its
electrons from atoms, thus creating charged molecules or atoms/ range. Proton therapy is one such type of particle therapy which is
ions (e.g. gamma rays and x-rays, alpha, beta, neutron, proton and gaining importance in this regard. More than 50,000 people have
been treated worldwide. With the enormous success in its
research, the facilities are now emerging in regional treatment
n
Corresponding author. Tel.: þ 91 9582 582987. centers. On interaction, these charged particles damage the DNA of
E-mail address: [email protected] (S. Bahl). cells and interfere with their ability to proliferate, ultimately

0022-2313/$ - see front matter & 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jlumin.2014.01.009
S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184 177

causing their death. However depending upon the tumor location, reaction:
type and patient specifications, treatment with other beams may EuCl2 ð0:2 mol%Þ þ EtOH
be best for certain therapies, so the ultimate treatment facility BaCl2 þðNH4 Þ2 SO4 - BaSO4 : Eu þ 2NH4 Cl
should offer a range of beams for the treatment options. Thus,
Analytical reagent (AR) grade barium chloride (BaCl2) was dis-
photon therapy causing less damage to the surface tissues, and solved in doubly distilled water. Europium Chloride (EuCl2),
proton therapy causing less damage to tissues beyond the target
0.2 mol% of AR grade was then added to the solution. To control
can be selected as per the requirement. The efficiency of the the size of particles to be produced on precipitation, ethanol was
treatment strongly depends upon the knowledge of the absorbed
then added to the solution with constant stirring. Further, ammo-
dose at the target organ to lower the risk of complications nium sulfate was added drop wise to the solution until the
resulting from incorrect exposure [2,3] which demands an accu-
precipitation was complete. The mixture was centrifuged each
rate calibration of radiotherapy sources, with proper dosimetry.
time so that the precipitate settled at the bottom of the tube and a
In space, there exist many kinds of radiations, such as galactic
clear liquid was seen at the top. The liquid on the top was then
cosmic rays and geomagnetic trapped particles, where protons are
decanted and the precipitate was washed repeatedly in distilled
the main components contributing to radiation dose in space,
water and dried at 363 K for 2 h. The nanocrystalline powder thus
which span a very wide range of energies (keV–GeV). They pose a
obtained was further annealed at 1123 K for 1 h under argon
serious dosimetric problem, particularly high energy particle
atmosphere in a quartz boat in a tube furnace and quenched by
radiation near the low earth orbit, where the components used
taking the boat out of the furnace and placing it on a metal block.
in various subsystems of the space craft get exposed to such
radiation. Due to differences in shielding throughout the habitable
volume of the spacecraft a choice of the detector won't be good
3. Characterization
especially if it is large in size, has a complex geometry and does
not show the cumulative dose.
3.1. Particle size
With small size and easy handling Thermoluminescent Dosi-
meters (TLDs) are one of the preferred choices of detectors which
The average particle (grain) size of the nanoparticles was
could be employed for this purpose. Using TLD's for measuring
estimated from the line broadening of the XRD peaks by using
ionizing radiations doses have been practiced for decades and
an XRD diffractometer, model D8-advance of Bruker (Germany) of
there are a number of commercially available TLD's for the same
Cu K-α radiation, the energy of which was 8.04 keV and the
[4,5]. Most common of them are fluorides which are tissue
wavelength was 1.54 Å. The applied voltage was 40 kV and the
equivalent but have complicated glow curve structures and are
current was 25 mA. Fig. 1 shows the X-Ray Diffraction (XRD)
more susceptible to heat treatments. Next in the category are
pattern of BaSO4:Eu nanoparticles. Broadening in the XRD lines
sulfates which have gained popularity for their use in radiation
is seen when the crystallite size is lesser than approximately
dosimetry. Calcium sulfate (CaSO4) is one of the most sensitive TL
100 nm. This can be used to estimate the average grain size.
phosphors and it was in fact the first one used to measure ionizing
Assuming the particles to be stress-free, the size can be approxi-
radiation as early as 1895 [6]. Since then the material has been
mately calculated from the most prominent peak using Debye
activated by several dopants [7–9] so as to obtain TL phosphors
Scherrer's formula
with greatly improved characteristics. CaSO4:Dy has by far been
reported to be the most sensitive in this series. Another interesting 0:9λ

phosphor in this series is CaSO4:Eu, which too has been widely β cos θ
studied by several workers [10,11]. Barium sulfate (BaSO4) [12,13] where D is the average grain size of the crystallites, λ is the incident
has been yet another sulfate that has been quite popular amongst wavelength of Cu K-α radiation, β is the diffracted full-width at half-
the researchers in this field. When doped with Eu the phosphor maximum (in radians) caused by the crystallites and θ is the Bragg
displays sensitivity even higher than that of CaSO4:Dy [13]. Recent angle. All the studies were performed at Room Temperature (RT).
studies have shown that the available microcrystalline phosphors The diffraction lines were indexed and unit cell configuration was
saturate at higher doses while their corresponding nanocrystalline identified using a computer program package ‘Powder X-ray Data
form has the potential to be used in higher dose ranges. Micro- Analysis System’ which revealed that the compound exhibits an
crystalline and nanocrystalline forms of BaSO4:Eu have been orthorhombic structure. There are considerable broadenings in the
reported to show satisfactory performance for measuring γ-ray
exposures [14,15]. This has prompted us to investigate further the
TL properties of nanocrystalline BaSO4:Eu for proton beams. There
are several studies on this material for its TL [16–22]. However, the
TL response of BaSO4:Eu to proton beam has been rarely reported.
Its synthesis is carried out by the simple co-precipitation method
and is found to be a highly sensitive TL material with a simple
glow curve structure. In this study, irradiation was carried out
using two types of irradiation having different energies, namely,
1.25 MeV Gamma rays and 150 MeV proton beam. TL glow curves
of the irradiated materials were recorded for wide ranges of doses.
The phosphor has also been characterized by other techniques
such as XRD, TEM, FTIR, Raman, PL, etc.

2. Material and methods

Nanocrystalline sample of BaSO4:Eu was prepared by the


chemical co-precipitation method with 0.2 mol% Europium Chlor-
ide (EuCl2) as the dopant taking into account the following Fig. 1. XRD pattern of nanocrystalline BaSO4:Eu.
178 S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184

Fig. 2. TEM image of BaSO4:Eu nanoparticles, (a) shows the cluster view and (b) shows the magnified view.

XRD lines, which are due to the reduction in the grain sizes, from
which the average grain size of the concerned phosphor was
calculated to be approximately 50 nm.
Transmission Electron Microscopy (TEM) is a vital tool to
investigate the nanostructure of the material at small length
scales, in particular for analyzing the shape and size of the
particles. Fig. 2(a) shows the cluster view of the nanocrystalline
BaSO4:Eu micrograph and Fig. 2(b) shows its corresponding
zoomed view. The TEM image of the powder sample has been
obtained on an FEI “TECNAI G2”, operated at 200 kV by depositing
the suspension in absolute ethanol, approximately 1 mg powder in
10 ml of ethanol on a carbon coated 200 mesh size copper grid.
It can be clearly seen that the particles are oval in shape and the
size lies within a range of 45–55 nm which is in agreement with
our XRD results.

3.2. FTIR study


Fig. 3. FTIR spectra of nanocrystalline BaSO4:Eu sample at room temperature.

FTIR spectroscopy is another useful technique to characterize


inorganic compounds. Fig. 3 shows the experimentally obtained moisture in the air and this indicates that the prepared sample
FTIR spectrum of nanocrystalline BaSO4:Eu compound, recorded consists of a certain amount of moisture [27,28]. However, these
using a NEXUS-670 FTIR spectrometer. Approximately 2–3 mg of unwanted peaks do not affect the classification of the elements
the compound was mixed with about 95 mg of Potassium Bromide involved in the experiment due to the difference in the absorption
(KBr) to obtain a fine powder. Finally the KBr pellets were obtained peaks of water and the possible product.
using a hydraulic pressure of 7–10 psi. The sulfate group contains
two S ¼O bonds and two S–O with tetrahedral geometry. Accord- 3.3. Raman study
ing to Adler and Kerr, [23], the sulfur-oxygen (S–O) stretching of
inorganic sulfates is found in the region 1179–1083 cm 1. In our Raman spectroscopy is an important spectroscopic technique
results of the FTIR spectrum of the prepared BaSO4, the bands which provides associated vibrational spectrum of molecular
centered at 1197–1077 cm 1 and the shoulder at 982 cm 1 is the spectra within the irradiated scattering volume. It relies on the
symmetrical vibration of SO42 , which is slightly different from principle that when the laser light interacts with molecular
that reported by Ramaswamy et al. [24]. This difference could have vibrations, it results in the energy of the laser photons being
arisen due to different methods of preparation and reduction in shifted up or down. The shift in energy gives information about
size from micro- to nano order, which leads to change in certain the vibrational modes in the system which can be further utilized
other features like high surface to volume ratio and increased band for the investigation of material properties such as lattice defect
gap. Like any other bonds, sulfate bonds can bend, giving rise to identification, crystal orientation and doping concentration. Pellet
one or two bands normally in the 680–610 cm 1 range. This has of approximately 100 mg of the sample was prepared and around
also been reported by Shen et al. [25] and is ascribed as the out-of- 7–10 psi pressure was applied. The Raman spectra were recorded
plane bending vibration of the SO4. In our case these bands are using an InVia Raman microscope from Renishaw, UK using Ar ion
seen in the spectrum near 610 and 630 cm 1. Generally, bending laser with 514.5 nm wavelength and 50 mW power. Fig. 4(a) shows
bands are sharper than the stretching bands. This is commonly the Raman Spectra of the virgin and 1000 Gy gamma irradiated
observed in inorganic infrared spectra and is also confirmed in our nanoparticles of BaSO4:Eu. The Raman signature of barite is
result as well. According to Manam and Das [26], the peaks near dominated by S–O bending and stretching. The wave numbers
2000 cm 1 are overtones and combination bands of the lower observed in the spectra recorded under ambient conditions are in
wave number of sulfur-oxygen stretching and bending vibrations excellent agreement with those reported in the literature [29].
The characteristic bands around 3000 cm 1 and 1600 cm 1 are A slight shift in the frequency is observed which could be due to
ascribed to atmospheric water vapor, since KBr readily absorbs the change in particle scale from micro to nano order. Therefore,
S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184 179

Fig. 4. Curve (a) shows the Raman spectra of virgin and irradiated nanocrystalline BaSO4:Eu sample at room temperature with v1, v2, and v4 modes of barium sulfate. Curves
(b, c and d) are the expanded views of the v2 mode in the spectral region 420–490 cm 1, v3 mode in the spectral region 590–670 cm 1 and v1 mode in the spectral region
950–1020 cm 1 of nanocrystalline BaSO4:Eu.

we can speculate that the confinement of phonon influences the


phonon spectra when the particle size decreases. The band at
987 cm 1 is due to the ν1 mode of the tetrahedral sulfate ion,
considered as the symmetric stretching of the SO4 group. The
bands at 452 and 464 cm 1 correspond to the ν2 mode and 616,
630 and 644 cm 1 as the ν4 modes of barium sulfate. However the
ν3 mode in which bands are observed at 1140 and 1166 cm 1
reported in the literature is absent with other data sets. This could
be due to the high pressure applied on the pellets. The expanded
views of the modes of virgin and irradiated compound are shown
in Fig. 4(b), (c) and (d). It can be clearly seen that there is no shift
in the peak position but a slight decrease in the Raman intensity
compared to the unirradiated sample. The absence of shift can be
in supposition that the modes retained their identity and there is Fig. 5. TL glow curves of BaSO4:Eu nanocrystalline samples irradiated to gamma
no structural phase transition even after irradiation to a dose of rays at different doses. The ordinate is to be multiplied by the numbers at the
curves to get the relative intensities.
1000 Gy.

glow curve structure remains invariant with irradiation to low


4. Results and discussion energy gamma as well as high energy proton beams. The changes
in the glow curve structure are attributable to the disorganization
4.1. TL glow curves of TCs/LCs which is commonly observed in many phosphors
reported. This reflects that the atoms retained their lattice position
Fig. 5 shows the TL glow curves of nanocrystalline BaSO4:Eu even after high energy proton irradiations. The presented phos-
exposed to different doses of gamma rays. The TL glow curve of the phor has a simple glow curve structure with prominent glow
BaSO4:Eu sample exposed to the proton beam is also shown peaks at 458 K and 498 K in the case of the gamma irradiated
(Fig. 6). As seen in Figs. 5 and 6, the glow curves of BaSO4:Eu sample while a slight shift is observed with peaks at 460 K and
exposed to proton beams are similar to that of the gamma 495 K in case of the proton irradiated sample. However, there is a
irradiated sample. On applying two different types of irradiations small variation in the relative intensities of the two peaks which
(proton and gamma), the sample shows almost similar TL glow could be attributed to the change in the population of the
curves, which is the remarkable feature of this phosphor that the luminescent/trapping centers. The low and high temperature
180 S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184

The form factor μg is found to be practically independent of the


activation energy, E, and strongly depends on the order of kinetics.
To determine the general order of kinetics (other than first or
second order), the correlation between the order of kinetics
(b) and the form factor (μg) given by Chen was used [32]. The
peak was then generated theoretically using these parameters and
was separated from the main experimental glow curve. The trap
depth or the thermal activation energy (E) needed to free the
trapped electrons was calculated using a set of equations {Eq. (2)}.
This procedure was repeated for all the TL peaks till a theoretical
glow curve was obtained by their convolution to overlap on the
experimental one.
GCD functions for the general order are given by the following
equation:
Fig. 6. TL glow curves of BaSO4:Eu nanocrystalline samples irradiated with
150 MeV proton beam at different doses. The ordinate is to be multiplied by the
T2
 " !
E T Tm
 
numbers at the curves to get the relative intensities. b=b 1
IðTÞ ¼ I m ðbÞ exp 1 þ X ðb 1Þ 2
KT Tm Tm
b=b 1
E T Tm
   
exp P þZ m ð1Þ
KT Tm
peaks are due to the creation of shallow and deep traps formed.
No appreciable shift in Tmax has been observed with the variation where I(T) is the TL intensity at temperature T (K), Im is the
in doses. This indicates that the sample may follow first order maximum peak intensity, E is the activation energy (eV) (calcu-
kinetics as reported by Sunta et al. [30]. Moreover, the increase in lated from Chen's formulae {Eq. (2)}, and k is the Boltzmann
the heights of the glow peaks with an increase of irradiation dose constant (8.6  10 5 eV K 1):
can be understood by the fact that more and more traps respon-
sible for these glow peaks were getting filled with the increase of P¼1 2Δ þ 6Δ2 24Δ3
irradiation dose and subsequently these traps release the charge Q ¼1 2Δm þ 6Δ2m 24Δ3m
carriers on thermal stimulation to finally recombine with their
Zm ¼ b ðb 1ÞQ
counterparts, thus giving rise to different glow peaks.
Δ ¼ 2kT=E and Δm ¼ 2kT m =E:

4.2. Analysis of TL glow curve and calculations E, the trap depth or the thermal energy needed to release the
of trapping parameters trapped electrons, is calculated using the following set of equa-
tions independent of the kinetic order:
The routine application of TLDs for estimating doses in various
Eα ¼ cα ðkT 2m =αÞ bα ð2kT m Þ ð2Þ
fields has encouraged the study of its kinetic parameters such as
form factor for determining the order of kinetics, activation energy with α ¼ τ; δ; ω;

τ ¼ Tm T1 ; δ ¼ T2 Tm ; ω ¼ T2 T1 ;
cτ ¼ 1:51 þ 3:0ðμg 0:42Þ; cδ ¼ 0:976 þ 7:3ðμg 0:42Þ; cω ¼ 2:52 þ 10:2ðμg 0:42Þ
bτ ¼ 1:58 þ 4:2ðμg 0:42Þ; bδ ¼ 0; bω ¼ 1;

1
for studying the trap structure, lifetime of TL peaks, time range The frequency factor, s (in s ), is obtained from the relation
over which it will be useful in the field of dating, etc. Various
techniques have been developed over time to derive these para- βE=kT 2m ¼ s expð E=kT m Þ ½1 þðb 1ÞΔm Š ð3Þ
meters from the glow curves. In the present study, we chose where, β is the linear heating rate. Eq. (3) has also been modified
BaSO4:Eu nanophosphors exposed to 100 Gy dose of gamma according to the general order equation {Eq. (1)}.
radiations as well as to proton beams to determine the trapping Fig. 7 shows the experimental TL glow curve for gamma
parameters. Since both the irradiations have shown an almost irradiated BaSO4 doped Eu nanophosphors at a heating rate of
similar glow curve structure, they have been deconvoluted into 5 K/s, which has been deconvoluted into three peaks using GCD
three peaks. The glow curve convolution deconvolution (GCCD) functions. A similar observation is seen with proton irradiation as
curve fitting in BaSO4:Eu nanocrystalline material was done using well (Fig. 8). The goodness of fit for the theoretical glow curve with
glow curve deconvolution (GCD) functions for general order the experimental one may be given by the Figure of Merit (FOM):
kinetics suggested by Kitis et al. [31] given as Eq. (1). It is applied
to the experimentally obtained glow curve for BaSO4:Eu to isolate ∑ TLExp TLFit j
FOM ¼
each peak in it for both types of irradiations. ∑TLFit
To determine the order of kinetics (b), the form factor μgwhere
FOM turned out to be 0.015 and 0.0026 for gamma and proton
μg ¼ ðT 2 T m Þ=ðT 2 T 1 Þ; irradiation, respectively, which indicates that the experimental
and theoretical fitted curves overlap each other quite well. Table 1
which includes T1 and T2 (temperature corresponding to the half of lists the peak parameters and the kinetic trapping parameters as
the intensities on either side of the maximum and Tm corresponds obtained from the experimental glow curve and deconvoluted
to the temperature at the maximum TL intensity) was calculated peaks for both irradiations. It has been shown earlier using
theoretically. The form factor, ranging between 0.42 and 0.52, is theoretical models [30] that the criterion for terming a glow peak
close to 0.42 for first order kinetics and 0.52 for second order as first order is the peak position remains unaltered with change
kinetics. of dose when the heating rate is kept the same. Of late, many
S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184 181

Fig. 9. TL response curves of BaSO4:Eu nanocrystalline samples to gamma rays in


dose range of 0.1–1000 Gy. The graph in the inset shows the same response on dose
Fig. 7. Comparison between the experimental, E (———) and the theoretically range 0.1–6400 Gy.
fitted, T (-o–o-) glow curves of nanocrystalline BaSO4:Eu exposed with 100 Gy
gamma rays. Deconvoluted single curves a, b and c of the experimental TL glow
curve are also shown.

Fig. 10. TL response curves of BaSO4:Eu nanocrystalline samples to 150 MeV proton
beam in a dose range of 0.1–325 Gy.

Fig. 8. Comparison between the experimental, E (———) and the theoretically


up to a dose of 1000 Gy in BaSO4:Eu prepared by solid state reaction
fitted, T (-o–o-) glow curves of nanocrystalline BaSO4:Eu exposed to 100 Gy of has also been reported recently by Annalakshmi et al. [18]. As the
proton beams. Deconvoluted single curves a, b and c of the experimental TL glow nanophosphor shows a wide linear TL response even at high doses, it
curve are also shown. can be employed as a dosimeter for measuring high doses of γ-rays.
The proton irradiated phosphor is linear almost in the entire range till
Table 1 305 Gy (coefficient of linearity, 0.999) while a slight supralinearity is
Trapping parameters of BaSO4:Eu nanocrystalline powder. observed with further increase in dose to 325 Gy. This behavior of
linearity/supralinearity/saturation can be easily explained by the high
S.no. Radiation Peak Tm Order of Eavg Frequency factor
surface to volume ratio of nanomaterials and the track interaction
type (K) kinetics (eV) (s)
model (TIM) [37,38], a model that is used to explain the behavior of
1 Gamma a 454 1.58 1.35 3.6  1014 TL materials when irradiated to energies in the order of MeV.
b 496 1.46 1.26 5.20  1013 This model suggests that the number of generated traps as a
c 549 1.22 1.03 7.21  108
result of irradiation depends on both the cross-section of the
2 Proton a1 457 1.61 1.32 1.15  1014 tracks and the length of tracks in the matrix. In case of nanocrys-
b1 494 1.67 1.48 3.36  1014 tallites, the length of such tracks will be only of the order of a few
c1 535 1.25 1.22 2.06  1010
tens of nanometers (dimensions of the nanoparticles); so, the
number of trap centers or luminescence centers will be less for
lower doses. However, as the dose increases, more overlapping
experimental reports [33–36] have proved that non first-order tracks occur, which might not give extra TL and saturation occurs.
kinetics may also be the possibility for the negligible shift in the TL But, in the case of nanoparticles, due to the very tiny size of the
glow curves with increase in dose. particles there still exist some particles that would have been
missed while being targeted by the high-energy radiation. Thus on
4.3. TL response curves increasing the dose, these nanoparticles, which had earlier been
left out from the radiation interaction, now generate trapping and
Figs. 9 and 10 correspond to the TL response of nanocrystalline luminescence centers (TC/LC). However, further increase in dose
BaSO4:Eu irradiated to gamma and proton beam. The area under the results in saturation or even a decrease in TL intensity due to the
curve was used to determine the TL intensities. The gamma irradiated same reason of overlapping of tracks. This can be further explained
phosphor shows a linear response up to a dose of 1000 Gy (coefficient in terms of high surface to volume ratio which results in a higher
of linearity, 0.999) after which slight saturation is observed. Linearity surface barrier energy for the nanoparticles. Thus on increasing
182 S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184

Fig. 11. PL excitation and emission spectra of nano-sized BaSO4:Eu for excitation
wavelength 250 nm. The excitation spectrum taken at the wavelength 374 nm
contains a main peak at 250 nm (Peak a) along with two shoulders at around
270 nm (Peak b) and 320 nm (Peak c).

the dose, the energy density crosses the barrier and a large
number of defects are produced in the nanoparticles which
ultimately keep on increasing with the dose till saturation is
achieved. Several applications can be linked with the presented
nanomaterial such as in the “area of radiation processing of
food products”, i.e. sprout inhibition in bulbs and tubers
(0.03–0.15 kGy), delay in fruit ripening (0.25–0.75 kGy), insect
disinfestations including quarantine treatment and elimination
of food-borne parasites (0.07–1.00 kGy), etc. However, proton
beams dosimetry finds its usage in the area of space explorations
as well as in proton beam therapy.

5. Photoluminescence study Fig. 12. (a) PL emission spectra for gamma irradiated BaSO4:Eu nanocrystalline
irradiated to different doses at an excitation wavelength of 250 nm. The inset
Photoluminescence spectroscopy is a powerful tool to probe shows the PL emission response as a function of dose. (b) PL excitation spectra for
gamma irradiated BaSO4:Eu nanocrystalline irradiated to different doses at an
the electronic structure of materials. It is a contactless, nondes-
emission wavelength of 374 nm. The inset shows the PL excitation response as a
tructive technique to study the defect detection, recombination function of dose.
mechanism, band gap determination, etc. Fig. 11 shows the room
temperature PL excitation and emission spectra of nanocrystalline intensity increases up to a dose of 800 Gy after which a decrease in
BaSO4:Eu for a virgin sample with an excitation wavelength of the PL intensity was found. A similar result is seen with the
250 nm. The emission spectrum consists of a simple and an excitation spectra along with an absence of shift in the excitation
intense peak at 374 nm which is the characteristic emission of wavelength, Fig. 12(b). This characteristic emission peak gives us
Eu2 þ ions. The main emission peak at 374 nm may be ascribed to an insight into the PL mechanism that the major channel of
the transitions between the lowest band of the 4f65d configuration excitation is the direct excitation of dopant levels lying within
and the ground state 8S7/2 of the 4f7 configuration of Eu2þ ion [39–41]. the band gap of the host material. The increase in the PL intensity
The strong violet-blue emission exhibited by the Eu2þ ions can further with increase in gamma radiation dose in case of BaSO4:Eu is an
be exploited for display applications. It is well known that the interesting observation. Similar increase in PL with radiation has
wavelength position of the emission band of Eu2 þ strongly depends been observed in SrS:Ce nanostructures with Ag9 þ ion [42],
on the host lattice. In the crystal structure of Barite, it can be porous silicon with helium ion [43] and β-SiC with carbon ion
interpreted that each Ba2 þ atom is coordinated with four oxygen implantation dose [44]. The first paper [42] attributes the increase
atoms. Moreover, Eu2þ ions are expected to occupy the Ba2 þ lattice in PL intensity to the increase in crystallinity while the last one [44]
sites. The excitation spectrum on the other hand taken at wavelength explains this on the basis of the quantum confinement model.
374 nm extends over a wide range of wavelengths from 220 to 350 nm In case of BaSO4:Eu, we observed a decrease in the PL intensity
with a strong peak at 250 nm (Peak a, Fig. 11), along with two above 800 Gy gamma irradiation dose. Similar decrease in PL
shoulders at around 270 nm (Peak b, Fig. 11) and 320 nm (Peak c, intensity at high doses of radiation has been observed by others
Fig. 11). The strong excitation that peaked around 250 nm may have [43,45]. Some have attributed this decrease in PL to the high defect
originated from the excitation of the host lattice as well as the doped density due to the high radiation dose. If the defect density is high
material. The two excitation bands (b and c) are ascribed to the eg–t2g enough it may lead to non-radiative recombination which, in turn,
sublevels of 4f65d. quenches the radiative recombination, resulting in reduced lumi-
Furthermore, the samples were also analyzed for their excita- nescence [45,46]. The present sample shows good crystal quality
tion and emission spectra for different doses of radiation and were and high photoluminescence sensitivity. This indicates that the
also compared with the virgin sample. Fig. 12(a) shows the plot sample BaSO4:Eu, if explored further, can find its possible potential
between the intensity of 374 nm peak as a function of dose and the applications in solid state lighting devices. The enhancement in
inset shows the PL response with dose. It is observed that the PL photoluminescence for irradiated nanoparticles may make it a
S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184 183

has been presented. The XRD analysis shows that the nanocrystal-
line BaSO4:Eu are orthorhombic in structure and the average
particle size was 50 nm. The TEM study indicates that BaSO4:Eu
nanoparticles were oval in shape and particle size was in the range
48–52 nm which is in good agreement with XRD analysis. FTIR
study clearly reveals the functional group of BaSO4 nanoparticles.
Raman study on the other hand effectively provides a window to
sneak into the vibrational structure of the sample. Samples in the
form of pellets have been exposed to 1.25 MeV gamma rays as well
as to 150 MeV proton beams for varying doses. A similar TL glow
curve structure is displayed by the sample for both the irradiations
being different in energy as well as type (electromagnetic versus
particulate). The TL structure shows two glow peaks with a main
peak at 458 K and a shoulder at 498 K for gamma irradiation and
at 460 K and 495 K in case of proton irradiation. The nanopho-
sphor exhibits a linear TL response up to 1000 Gy for gamma and
305 Gy for proton doses. The PL spectrum exhibits a broad
Fig. 13. Fading plot of nanocrystalline BaSO4:Eu for gamma (curve a) and proton
beam (curve b) irradiation. emission band with maxima at about 374 nm with consistency
with the excitation spectra with maxima at about 250 nm. This
multi-utility sample exhibits good TL and PL properties and may
better candidate for practical applications such as scintillators and be considered as a promising material to be used in TL dosimetry
optical devices. in estimating the doses of gamma and proton beam in space,
proton therapy as well as in research and the strong violet-blue
emission exhibited by the Eu2 þ ions in the PL spectra could be
6. Fading and reusability further exploited in the area of lamp and display applications.

For a material to be well suited for radiation dosimetry, stability


and reusability are some of the additional features that a dosi- Acknowledgments
meter should be good at. For the stability study it is expected that
the TL of the sample should be stable and should not fade upon This work was funded by the Department of Science and
storage after exposure. The fading of the sample for both radiation Technology (DST) under the Indo-Russian (ILTP) Project with
of gamma and proton was checked. Approximately 50 mg of the project code INT/ILTP/A-2.53 and the authors acknowledge the
sample was irradiated and stored, out of which 5 mg of the sample same. One of the authors (SB) is thankful to the University Grants
was taken every time in order to check the TL intensity for the Commission (UGC), New Delhi, India for the award of research
desired days. Fig. 13 shows the plot of the fading study for both fellowship and to Mr. Akshey Kaushal, AIIMS, New Delhi, for his
radiations. It can be seen in the figure that both the irradiations help in analyzing the TEM images. The authors are also thankful to
show a fading of approximately 4–5% (over the period of 30 days); the Director, IUAC, for permitting the use of research facilities.
however, an important consideration is that, with gamma irradia-
tion, the fading at initial days of storage is less (compared to
proton irradiation) and continues to fade till the 20th day and References
becomes constant thereafter. While with proton irradiation, the
sample loses its sensitivity only in the preliminary days and [1] R. Pazdur, L.D. Wagman, K.A. Camphausen, W.J. Hoskins (Eds.), Cancer
Management: A Multidisciplinary Approach, 11 ed., 2008.
maintains its value till the 30th day. The reason for this behavior
[2] ICRP. Annals of ICRP, 30, ICRP Publication 86, 2000.
could be that proton beam having high energy and mass in [3] J.E. Rogers, Radiat. Meas. 41 (2006) 36.
contrast to gamma rays might have created tracks and deep seated [4] A.M. Noh, Y.M. Amin, R.H. Mahat, D.A. Bradley, Radiat. Phys. Chem. 61 (2001)
497.
permanent defects in the crystal. Hence, the electrons from the
[5] H.S. Nalwa, Handbook of Nanostructured Materials and Nanotechnology, 1–5,
shallower region, near the conduction band, would have escaped Academic, CA, San Diego, 2000.
in the initial days and the deep defects remained unaffected and [6] E. Wiedemann, G.C. Schmidt, Ann. Phys. Chem. 54 (1895) 604.
produced a good amount of luminescence even after 30 days of [7] T. Yamashita, N. Nada, H. Onishi S. Kitamura, in: Proceedings of the 2nd
International Conference on Luminescence Dosirnetry, Gatlinburg, USA, 1968,
fading. p. 4.
In the reusability study, if the sensitivity of a sample does not [8] T. Yamashita, N. Nada, H. Onishi, S. Kitamura, Health Phys. 21 (1971) 295.
change after several cycles of exposures and readouts it is [9] T. Yamashita, in: Proceedings of the 4th International Conference on Lumines-
cence Dosirnetry, Krakow, Poland, 1974, p. 467.
considered to have good reusability features. For this study, the [10] V.N. Bapat, J. Phys. C: Solid State Phys. 10 (1977) L465.
sample was exposed to a dose of 100 Gy, the TL glow curves were [11] S.V. Godbole, J.S. Nagpal, A.G. Page, Radiat. Meas. 32 (2000) 343.
recorded and the sample was annealed at 1123 K. Several such [12] R.L. Dixon, K.E. Ekstrand, Phys. Med. Biol. 19 (1974) 196.
[13] U. Madhusoodan, M.T. Jose, A.R. Lakshmanan, Radiat. Meas. 30 (1999) 65.
exposure/readout cycles were performed and the variation of the [14] R.S. Kher, A.K. Upadhyay, S.K. Gupta, S.J. Dhoble, M.S.K. Khokhar, Radiat. Meas.
TL intensity with the number of cycles was recorded. The reusa- 46 (2011) 1372.
bility study revealed a negligible amount of change in sensitivity [15] N. Salah, S.S. Habib, Z.H. Khan, S.A. Hamedi, S.P. Lochab, J. Lumin. 129 (2009)
192.
(less than 3%), concluding that the present phosphor has good
[16] G. Kitis, N.G. Kiyak, G.S. Polymeris, Appl. Radiat. Isot. 68 (2010) 2409.
reusability features too. Moreover, the glow curve's shape and [17] R.L. Dixon, K.E. Ekstrand, J. Lumin. 8 (1974) 383.
structure also remained the same for the same exposure. [18] O. Annalakhmi, M.T. Jose, U. Madhusoodanan, Radiat. Prot. Dosimetry 150
(2012) 127.
[19] G. Holzapfel, M. Krystel, Phys. Status Solidi A 37 (1976) 303.
7. Conclusion [20] T.K. Gundu Rao, S.S. Shinde, B.C. Bhatt, J.K. Srivastava, K.S.V. Nambi, J. Phys.:
Condens. Matter 7 (1995) 6569.
[21] B.C. Bhatt, S.S. Sanaye, S.S. Shinde, J.K. Srivastava, Radiat. Prot. Dosimetry 105
A TL study of gamma and proton beam irradiated BaSO4 doped (1997) 105.
with Eu nanophosphors prepared by the co-precipitation method [22] J. Azorin, Radiat. Phys. Chem. 51 (1998) 471.
184 S. Bahl et al. / Journal of Luminescence 149 (2014) 176–184

[23] H.H. Adler, P.F. Kerr, Am. Mineral. 50 (1965) 132. [36] V. Kumar, H.C. Swart, O.M. Ntwaeaborwa, R. Kumar, S.P. Lochab, V. Mishra,
[24] V. Ramaswamy, R.M. Vimalathithan, V. Ponnusamy, Adv. Appl. Sci. Res. 1 (3) N. Singh, Opt. Mater. 32 (2009) 164.
(2010) 197. [37] S. Mahajna, Y.S. Horowtz, J. Phys. D: Appl. Phys. 30 (1997) 2603.
[25] Y. Shen, C. Li, X. Zhu, A. Xie, L. Qiu, J. Zhu, J. Chem. Sci. 119 (2007) 319. [38] Y.S. Horowitz, O. Avila, M.R. Fuerte, Nucl. Instrum. Methods Phys. Res. B 184
[26] J. Manam, S. Das, Indian J. Pure Appl. Phys. 47 (2009) 435. (2001) 85.
[27] B. Smith, Infrared Spectral Interpretation; A Systematic Approach, CRC Press, [39] Z. Pei, Q. Zeng, Q. Su, J. Phys. Chem. Solids 61 (2000) 9.
New York, 1999. [40] T. Matsuzawa, Y. Aoki, N. Takeuchi, Y. Murayama, J. Electrochem. Soc. 143
[28] K. Nagamoto, Infrared Spectra of Inorganic and Coordination Compounds, (1996) 2670.
Wiley Interscience, New York, 1970. [41] C. Chartier, C. Barthou, P. Benalloul, J.M. Frigerio, J. Lumin. 111 (2005) 147.
[29] P.L. Lee, E. Huang, Y.S. Cheng, High Press. Res. 23 (2003) 439. [42] A. Vij, A.K. Chawla, R. Kumar, S.P. Lochab, R. Chandra, N. Singh, Physica B 405
[30] C.M. Sunta, W.E.F. Ayta, J.F.D. Chubaci, S. Watanabe, J. Phys. D: Appl. Phys. 34 (2010) 2573.
(2001) 2690. [43] E.J. Teo, M.B.H. Breese, A.A. Bettiol, F. Champeaux, D.J. Blackwood, Proc. SPIE
[31] G. Kitis, J.M. Gomez-Ros, J.W.N. Tuyn, J. Phys. D: Appl. Phys. 31 (1998) 2636. (2006)618312.
[32] R. Chen, J. Electrochem. Soc. 116 (1969) 1254. [44] Dihu Chen, Z.M. Liao, L. Wang, H.Z. Wang, Fuli Zhao, W.Y. Cheung, S.P. Wong,
[33] S.P. Lochab, P.D. Sahare, R.S. Chauhan, Numan Salah, A. Pandey, J. Phys. D: Opt. Mater. 23 (2003) 65.
Appl. Phys. 39 (2006) 1786. [45] P.G. Kik, Photoluminescence behaviour of erbium implanted in sodium
[34] A. Vij, S.P. Lochab, S. Singh, R. Kumar, N. Singh, J. Alloys Compd. 486 (2009) containing silicate glasses, Master's Thesis, University of Amsterdam, 1994.
554. [46] J.C. Barbour, D. Dimos, T.R. Guilinger, M.J. Kelly, S.S. Tsao, Appl. Phys. Lett. 59
[35] Salah Numan, P.D. Sahare, A.A. Rupasov, J. Lumin. 124 (2007) 357. (1991) 2088.

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