Radiation Measurements xxx (2014) 1e4

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Radiation Measurements
journal homepage: www.elsevier.com/locate/radmeas

Correlation of optically and thermally stimulated luminescence

of natural fluorite pellets
F.A. Ferreira Jr. *, E.M. Yoshimura, N.K. Umisedo, R.P. do Nascimento
Instituto de Física, Universidade de São Paulo, P.O. Box 66318, CEP 05314-970 São Paulo, SP, Brazil

h i g h l i g h t s

CaF2:NaCl pellets are extremelly useful as dosimetric materials.

Only part of the defects responsible for the TL signal from fluorite is optically active.

NaCl signals affects the TL and OSL signals from the pellets.

NaCl OSL signal can be avoided with a pre-heat or after about 1 h waiting time.

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

Article history: Natural fluorite (CaF2), a dosimetric material of large usage, presents Thermoluminescence (TL) and
Received 2 December 2013 Optically Stimulated Luminescence (OSL). This study examined the behavior of TL and OSL (stimulated
Received in revised form with Blue LEDs) signals from the Brazilian natural fluorite pellets with NaCl as binding agent, as well as
23 January 2014
their correlations, in order to study and optimize the dosimetric process with this material. A series of
Accepted 20 February 2014
experiments were conducted, basically with thermal treatments before OSL acquisition, and optical
bleaching before TL readout. The role of NaCl in the TL and OSL emission was investigated. It was
Keywords:
observed that natural CaF2 TL signal is still ample to be used in dosimetric applications, as dose re-
Optically stimulated luminescence
Thermoluminescence
assessment in personal dosimetry after an OSL measurement. Also it was verified that the fluorite OSL
Natural fluorite signal is extinguished by a 350  C heating and that NaCl has no contribution to the stable part of the OSL
signal.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Both natural and synthetic calcium fluoride are widely used as
dosimetric TL material mainly due to their high sensitivity. In
particular, the use of natural fluorite has extended to many places
because of its abundance and low cost. In Brazil we have developed
a solid dosimeter, based on natural calcium fluoride and sodium
chloride powders pressed together (CaF2:NaCl) (Okuno et al., 1977;
Trzeniak et al., 1990) for dosimetric applications. These pellets are
extremely useful as dosimetric materials because they can provide
information on dose and radiation energy with the use of appro-
priated filters (Guimarães and Okuno, 2003). Recently, it has been
observed that both Indian (Sunta, 1970; Chougaonkar and Bhatt,
2004) and Brazilian (Yoshimura and Yukihara, 2006) fluorite also
* Corresponding author. Tel.: þ55 (0)11 30910849.
E-mail address: felis@if.usp.br (F.A. Ferreira).
emit OSL when blue light is used for stimulation, and that the
emitted light is related to the absorbed dose. In this paper we
explore the OSL and TL properties of the fluorite pellets in order to
verify the possibility of expanding the dosimetric capabilities with
the use of combined OSL and TL emissions. Studies of correlation of
OSL and TL signals in fluorite are rare (Polymeris et al., 2006;
Chougaonkar and Bhatt, 2004; Bakshi et al., 2009). They show
that not all the traps related to TL peaks are optically active and that
both photo and thermal transfer processes may be present. The
addition of NaCl and the production of pressed pellets with CaF2
powder may affect the correlation of OSL and TL signals. This occurs
because the NaCl is itself a luminescent material and the pellet
thickness (1 mm in average) may prevent uniform illumination or
homogeneous deposition of radiation energy in the pellet (Moralles
et al., 2005). Thus, this work aims to investigate the influence of TL
readouts on the OSL response and the effect of blue illumination in
the TL intensity of natural CaF2:NaCl pellet dosimeters. Thus, it is
expected that a better performance of this dosimeter will be
achieved.

http://dx.doi.org/10.1016/j.radmeas.2014.02.020
1350-4487/Ó 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Ferreira, Jr., F.A., et al., Correlation of optically and thermally stimulated luminescence of natural fluorite
pellets, Radiation Measurements (2014), http://dx.doi.org/10.1016/j.radmeas.2014.02.020
2 F.A. Ferreira Jr. et al. / Radiation Measurements xxx (2014) 1e4

2. Materials and methods

The materials used in this work are natural fluorite and sodium
chloride (99% pure). Natural fluorite acquired as-from-the-mine
was transformed into powder as described by Trzeniak et al.
(1990). Sodium chloride was used as binding agent. Aliquots of
pure NaCl or of a mixture containing 60% CaF2 and 40% NaCl were
compressed to make 5 mm diameter  1 mm thickness (w45 mg
mass) pellets. The dosimeters are protected from humidity with
storage in dry ambient or with plastic enveloping, to avoid influ-
ence of this condition in TL or OSL signals.
Before the first use and between subsequent uses of the same
sample in a experiment, the sample was heated at 5  C/s up to
450  C, as in a TL acquisition, to empty the traps and erase the TL
and OSL signal. The variation of NaCl and CaF2:NaCl pellets sensi-
tivity to repeated irradiation-readout (TL/OSL) cycles was tested
over 100 cycles and the statistical dispersion is compatible with the
uncertainties presented, without trends.
Two groups of ten samples each were selected in accordance
with the signal intensity after the same irradiation time under the Fig. 1. TL glow curves of CaF2:NaCl pellets obtained after different optical stimulation
beta source. One group of pellets was made of pure NaCl and the times. The lines connecting points are just guides for the eyes. The insert shows the TL
signal of a NaCl pellet, freshly irradiated to the same dose, and after blue light stim-
other of CaF2:NaCl (60:40); each group of selected pellets presented
ulation during 5 s.
3.0% standard deviation of the mean OSL signal. The experimental
data that are shown in this work are the mean value from these
group measurements with their respective uncertainties. are necessary to remove these peaks from the glow curve. As far as
OSL and TL measurements were carried out using a commercial the fluorite TL dosimetric peak is concerned, the effect of optical
automated TL/OSL reader produced by Risø National Laboratory stimulation is to bleach the low temperature part of the peak
(model DA-20). Luminescence was stimulated using blue light leaving a very stable signal, centered near 350  C. In fact, after 500 s
emitting diodes (470 nm, FWHM ¼ 20 nm) delivering 80 mW/cm2 of illumination, a TL peak centered at 310  C, usually a part of the
at the sample position. The TL/OSL signals were detected with a bi- main peak, is completely bleached out. A satellite peak at 350  C
alkali photomultiplier tube (PMT) behind an UV transmitting survives the bleaching. Polymeris et al. (2006) have seen a similar
broad-band glass filter (Hoya U-340, 7.5 mm thick  45 mm effect in the study of natural fluorite, and have predicted the exis-
diameter) to block the stimulation light while transmitting part of tence of such a peak through the deconvolution of the whole TL
the OSL signal from the samples. Irradiations were performed at glow curve. Here we identify its presence by the bleaching out of
room temperature using the built-in 90Sr/90Y beta source of the TL/ the TL signal.
OSL reader (dose rate of 11 mGy/s). A better correlation of TL and OSL signals can be seen in Fig. 3
The stimulation time for OSL measurements was 100 s. Inte- where the relative integrated TL signal of the fluorite pellets, from
grated OSL signals were calculated as first 50 s counts considering room temperature to Tstop is compared to the relative residual OSL
the last 50 s as background. TL glow curves were obtained using a signal after a preheating till Tstop. Again it is possible to observe that
heating rate of 5  C/s. the NaCl contribution to the OSL signal is connected with shallow
traps. Also, we see that the fluorite shallow traps concentrate the
3. Results and discussions

The experiments described below involve a series of irradiation-

readout cycles. Some types of NaCl have shown vulnerability to
these cycles, as shown by Polymeris et al. (2011). However, the TL
glow curves from the NaCl samples used on this work show no
peaks at temperatures higher than 300  C, as can be seen in Fig. 1.
These TL glow curves are more similar to those presented by
Ekendahl and Judas (2011) than by Polymeris et al. (2011) and may
explain that no change of sensitivity of NaCl pellets to irradiation-
readout cycles was observed in our work.
Fig. 1 shows residual TL glow curves for CaF2:NaCl pellets after
CW-OSL with different illumination times. The results for a NaCl
pellet are in the insert, and we see that the TL signal is restricted to
the low temperature region, and is completely extinguished after a
light stimulation of just 5 s. Almost all the signal of the fluorite
pellet comes from fluorite, and part of the TL is bleached by the
optical stimulus.
For a more complete analysis, we show in Fig. 2 the difference
between the TL glow curve from a non-illuminated sample and TL
glow curves after different illumination times. With this data it is
possible to conclude that the shallow traps responsible for the low Fig. 2. Differences between the TL glow curve obtained without optical bleach and the
temperature part of the glow curve (below 150  C) are easily TL glow curves after different stimulation times. The lines connecting points are just
bleached out during the OSL readout e less than 5 s of illumination guides for the eyes.

Please cite this article in press as: Ferreira, Jr., F.A., et al., Correlation of optically and thermally stimulated luminescence of natural fluorite
pellets, Radiation Measurements (2014), http://dx.doi.org/10.1016/j.radmeas.2014.02.020
 F.A. Ferreira Jr. et al. / Radiation Measurements xxx (2014) 1e4
Fig. 3. Residual OSL (R-OSL) signal after thermal bleaching up to Tstop compared with
TL signal integrated from room temperature to Tstop. Values of R-OSL signals are
relative to OSL signal at room temperature and values of TL signals are relative to TL
acquisition up to 400  C. Lines connecting data points have been included as a guide
for the eye.
majority of charge carriers responsible for a large fraction of the OSL
signal. The fluorite OSL signal disappears after a TL readout till
350  C, and the OSL intensity decays very slowly with Tstop varia-
tions from about 100 to 250  C, showing a progressive releasing of
charges from deeper traps, the same that are responsible for the
second and third TL fluorite peaks.
The absolute values of TL and OSL signals, obtained with the
same set of filters and PMT, can be seen in Fig. 4 where OSL signals
for different stimulation times (from 0.01 to 500 s) are compared
with residual TL signal for CaF2:NaCl pellets. The insert shows the
OSL signal as a function of unbleached minus bleached integrated
signal. This curve shows a nonlinear correlation between OSL signal
detected during bleaching and the amount of decline of the TL
signal. The total light intensity available as TL output equals the
very initial OSL signal. The total light emitted as OSL is about 5
times higher than the total TL. Part of the light loss could be due to
Fig. 4. Integrated OSL signal and residual TL (RTL) signal for CaF2:NaCl pellets after
increasing optical stimulation times. The insert shows the OSL signal as a function of
unbleached minus bleached glow-curves (TL-RTL). Lines joining data points have been
included as a guide for the eye.
Please cite this article in press as: Ferreira, Jr., F.A., et al., Correlation of optically and thermally stimulated luminescence of natural fluorite
pellets, Radiation Measurements (2014), http://dx.doi.org/10.1016/j.radmeas.2014.02.020
3
Fig. 5. Comparison between residual OSL signals from NaCl and CaF2:NaCl pellets as a
function of time after irradiation. The data are percentages relative to the measure-
ments obtained just after the irradiation (about 30 s after irradiation). Statistical un-
certainties are smaller than the symbol sizes. Lines connecting data points have been
included as a guide for the eye.
thermal quenching during TL readout, but this hypothesis has been
ruled out by Polymeris et al. (2006). Without further analysis we
can simply conclude that not all the OSL emitted light comes from
the traps responsible for the TL peaks from 50 to 400  C. As this
feature was also observed for another natural CaF2 sample
(Polymeris et al., 2006), it probably has to due with intrinsic defects
of this material, and also with the fact that, as a natural sample, this
mineral has been exposed to natural radiation (soil and cosmic)
since it was formed giving rise to filled-up deep traps.
The fading curves of integrated OSL signals from CaF2:NaCl and
NaCl pellets are shown in Fig. 5. The OSL signal from NaCl pellets is
very unstable, being completely removed approximately 1 h after
the irradiation, with the sample kept in the dark at room temper-
ature. Regarding the OSL signal from the CaF2:NaCl pellets, a frac-
tion of about 25% of the whole signal is still present after 5000 s.
This light intensity is practically as large as the total intensity that
can be collected with a TL readout till 400  C.
4. Conclusions
It was observed that only part of the defects responsible for the
TL signal of fluorite is optically active, and that the defects associ-
ated to the OSL of this material are completely emptied by heating
it to 350  C. This way, it is possible to use the TL of OSL emptied CaF2
pellets to re-assess doses, e.g. in personal dosimetry. It was not
possible to verify the contribution of each TL trap individually to the
OSL signal.
The initial OSL decay of the pellet signals, either in the case of
thermal bleaching or fading, is strongly influenced by the presence
of NaCl in the sample composition. This was proved by performing
the same experiments with pure NaCl pellets. The OSL signal of
NaCl has fast fading after irradiation and its TL signal is almost
completely erased after 5 s of illumination or after 150  C pre-heat.
For this study, the whole glow-curve was included. Even the low
temperature and low intensity TL peaks were considered in order
to better understand the correlation between OSL and TL signals.
However, for practical applications, such as personal dosimetry, it
is usual to consider only the high temperature and high intensity
TL peaks, due to their stability and sensitivity. In the case of
CaF2:NaCl, the complex peak centered at 310e350  C plays this role.
4 F.A. Ferreira Jr. et al. / Radiation Measurements xxx (2014) 1e4
Furthermore, the signal from NaCl has negligible influence on the
intensity of this peak, even without any previous treatment, rein-
forcing the conclusion that the CaF2:NaCl pellet dosimetric capa-
bilities can be expanded with the use of combined OSL and TL
emissions.
The results presented here characterize CaF2:NaCl as a possible
OSL detector for use in personal dosimetry. The knowledge of the
dose response curve and of the best optical zeroing procedure are
important for this application and are under investigation for the
development of technical aspects.
Acknowledgements
The authors would like to thank the Brazilian agencies São Paulo
Research Foundation (FAPESP) (gs1),grants #2010/16437-0 and
#2012/13534-0, National Council for Scientific and Technological
Development (CNPq) (gs2) and National Institute of Science and
Technology - Radiation Metrology in Medicine (INCT) (gs3).
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