Characterization and Luminescence Studie
Characterization and Luminescence Studie
Characterization and Luminescence Studie
Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin
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.
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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
D¼
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.
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.
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.
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 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. 10. TL response curves of BaSO4:Eu nanocrystalline samples to 150 MeV proton
beam in a dose range of 0.1–325 Gy.
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.
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