Journal of Luminescence 188 (2017) 118–128

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

Spectroscopic account of the point defects related to the sensitization of TL MARK

peaks beyond 220 °C in natural quartz
⁎
Pedro L. Guzzoa, , Leonardo B. Ferreira de Souzab, Vinícius S.M. Barrosc, Helen J. Khouryc
a
Department of Mining Engineering, Federal University of Pernambuco, 50740-530 CDU Recife, PE, Brazil
b
Department of Physics, Catholic University of Pernambuco, 50050-900 Recife, PE, Brazil
c
Department of Nuclear Energy, Federal University of Pernambuco, 50740-540 CDU Recife, PE, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: This study investigates the origin of point defects involved with a strong sensitization of the thermoluminescence
Thermoluminescence (TL) signal of natural quartz between 220 and 400 °C. The sensitization was produced by the combined effect of
Quartz high-dose of γ radiation and heat-treatments at moderate temperatures. The point defects related to silicon and
Radiation-induced defects oxygen vacancies and also with Al, Ge, Li, and OH impurities were assessed by infrared (IR) and electron
EPR spectroscopy
paramagnetic resonance (EPR) spectroscopy in samples prepared from two single crystals with different
Sensitization
sensitivities. The signal intensities of the point defects were measured in as-received, zeroed, γ-irradiated,
Ionic motion
sensitized and also after heat-treatments carried out up to 600 °C. The deconvolution of the TL curves showed
that the major peaks appeared around 240 and 325 °C. The spectroscopic analysis showed the presence of several
point defects identified as E’1, [E’1-GeO4]0, [O23-/Li+]0, [GeO4/Li]0, [AlO4]0, [AlO4/H]0, [BO4/H]0 and Li-
dependent OH centers. The sensitization process was efficient to increase the number of electron traps by means
of a stable coupling (up to 400 °C) between E’1, [GeO4]0 and Li+ ions dislodged from [AlO4/Li]0 centers. It was
concluded that the active electron traps responsible for the TL emission above 220 °C were [GeO4/Li]0 and E’1
centers whereas [AlO4]0 was the main recombination center. The thermal behaviour observed for [E’1-GeO4]0
and [O23-/Li+]0 signals showed that the creation of these centers are connected each other. A sequence of
reactions involving Li+ motion plus electron-hole recombination at localized transitions within ([GeO4/Li]0,
[AlO4]0), (E’1, [AlO4/Li]-) and ([E’1-GeO4]0, [O23-/Li+]0) defect pairs were proposed to explain the TL process in
sensitized samples after the impartment of a given test-dose. The precursors for [E’1-GeO4]0 and [O23-/Li+]0
centers were assumed to compete with the active traps responsible for TL peaks found at 240 and 325 °C peaks.

1. Introduction
The sensitization of the thermoluminescence (TL) signals by ioniz-
ing irradiation followed by heat-treatment is a quite well known
phenomenon in large band-gap materials. Sensitization can be defined
as the change of sensitivity, namely the response to a small test-dose,
caused by a large irradiation dose followed by thermal activation when
heated at a specific temperature [1]. In quartz, this effect was firstly
observed by Fleming and Thompson [2] and then by other authors [3]
for the TL peak at 110 °C. Since its discovery, the sensitization of the
110 °C TL peak, also known as the predose effect, has been used in dating
of archaeological materials such as pottery and burnt pebbles [4,5] as
well as for accident and retrospective dosimetry [6]. Zimmerman [7]
proposed the first phenomenological model to account for the sensitiza-
tion of the 110 °C peak. Her model deals with an active electron-
trapping state, a luminescent center and a non-luminescent “reservoir”
center, with larger cross section to trap holes during irradiation than
the luminescent center. The sensitization of the 110 °C peak by the
thermal transfer of holes from reservoir to luminescence center has
been confirmed by simulating the complete steps related to the predose
technique using a comprehensive kinetic model [8,9]. However,
Zimmerman's model is not able to account for the decrease in the
sensitivity of the 110 °C peak noticed in samples heated above 500 °C.
Thermal deactivation occurs by a mechanism of competition for free
electrons between the active electron traps and the holes trapped at the
luminescent center previously released from non-luminescent centers
[10]. On its turn, the annealing of quartz at temperatures higher than
500 °C leads to a dramatic increase in its optically stimulated lumines-
cence (OSL) sensitivity [11,12]. This sensitivity change was studied by
measuring the luminescence lifetime components using different time-
resolved (TR) OSL set-ups [13,14].
The sensitization of a TL peak occurring between 200 and 220 °C

⁎
Corresponding author.
E-mail address: pguzzo@ufpe.br (P.L. Guzzo).

http://dx.doi.org/10.1016/j.jlumin.2017.04.009
Received 5 November 2016; Received in revised form 5 March 2017; Accepted 5 April 2017
Available online 08 April 2017
0022-2313/ © 2017 Elsevier B.V. All rights reserved.
P.L. Guzzo et al.
has also been reported for quartz and porcelain. It was noticed that
quartz grains separated from tiles from Hiroshima and bricks affected
by Chernobyl accident exhibit a sensitization of the 210 °C peak when
subjected to a series of irradiation and heat-treatments [15,16]. Benny
and Bhatt [17] found a factor of sensitization equal to 35 for the 220 °C
peak occurring in quartz grains separated from sludge sand when they
coupled 2.5 kGy of γ radiation with heat-treatment at 400 °C. The
predose effect of the 110 and 210 °C peaks occurring in TL curves of
porcelain was employed in retrospective dosimetry and dating of
ancient objects [18]. The kinetic analysis of these peaks in single
crystals of synthetic quartz thermally activated at different atmospheres
showed that the change in TL sensitivity is more likely to be the result
of an excitation-induced ionic process than merely delocalized transi-
tions of electrons and holes between trapping states [19,20]. It was also
suggested that the dependence of the 110 °C peak on annealing atmo-
sphere was an indication that oxygen-related rather than impurity-
related defects plays an important role in the degree of sensitization of
synthetic quartz.
The ionic process involving point defects to account for the predose
effect in quartz was proposed by Itoh et al. [21]. These authors
provided a model based on the creation of electron-hole pairs resultant
from the rearrangement of [AlO4/M]0 and [XO4/M]0 (M: Li, Na; X: Ti,
Ge) centers controlled by alkali diffusion throughout the crystal lattice.
This model considered point defects previously identified in quartz of
different origins [22–26]. The structure of the point defects and its
importance to explain the characteristics of the luminescence process of
natural quartz was extensively reviewed by Preusser et al. [27]. Itoh
et al. [21] assumed that the increase in the sensitivity of the 110 °C
peak occurs by the increase in the number of [GeO4/M]0 centers caused
by the heating of pre-irradiated samples around 500 °C. However, it is
well accepted that [GeO4/M]0 is created during irradiation at room
temperature by the migration of M+ ions from [AlO4/M]0 center
[22,24]. Until now, there is no experimental evidence supporting the
assumption that [GeO4/M]0 is formed during heating above room
temperature. The modifications in point defect distribution into the
quartz lattice caused by radiation at different temperatures were also
reviewed and updated by Preusser et al. [27]. In addition, the model
proposed by Itoh et al. [21] did not consider the presence of oxygen
vacancies such as E’ centers and peroxy centers that are frequently seen
into the quartz lattice [28,29]. Thus, the origin of point defects related
to the predose peak as well as the whole mechanism of TL in quartz is a
question that is far to be answered and further investigations are
required in this direction.
The sensitization of quartz glow peaks occurring above 220 °C was
much less reported in the literature. As far as we know, the sensitization
of a peak near 280 °C was firstly reported by Khoury et al. [30] who
showed that the degree of sensitization in single crystal specimens was
closely related to quartz provenance. The dose response of a batch of
single crystals prepared from a specimen with high sensitivity showed
that irradiation with γ doses like 25 kGy followed by heating at 400 °C
increased the intensity of the 280 °C peak more than 1000 times [31].
In the sequence, it was shown that the intensity of the 280 °C peak
increased with the increasing of the Li/Al and Li/OH impurity content
ratios in quartz specimens of different origins sensitized in similar
conditions [32]. TL readings following ultraviolet-visible (UV–Vis) and
infrared (IR) spectroscopy carried out at different steps of sensitization
suggested that the intensity of the sensitized peak was directly related
to the creation of [AlO4]0 centers but it was inversely related to the
concentration of OH-related defects [32,33]. Later, it was observed that
the sensitization process combining γ irradiation (25 kGy) and heat-
treatments at 400 °C was also responsible for the sensitization of the so-
called ultrafast OSL components of quartz single crystals [34]. In the
meantime, the sensitization of high-temperature peaks was also noticed
by other authors. Combining a sequence of irradiations (20 Gy) and TL
measurements up to 500 °C in powdered aliquots of natural quartz,
Martini et al. [35] observed the increase of a broad composite structure
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Journal of Luminescence 188 (2017) 118–128
of TL signals in the 200–400 °C range.
Compared to the standard predose effect, the dose of γ rays used to
sensitize high-temperature peaks is, at least, one order of magnitude
higher. Since the structure of point defects in crystalline quartz is
extremely sensitive to ionizing radiation, it is reasonable to think that
the sensitization with tens of kGy creates substantial changes in the
configuration of point defects. Until now, the structure of point defects
in quartz sensitized according to the procedure used by Khoury et al.
[31] was not investigated by EPR spectroscopy, which is by far the most
sensitive technique to inspect point defects in quartz [36,37]. In
addition, it has been observed that such process of sensitization can
be used to distinguish TL and OSL signals of quartz issued from different
origins after imparting test-doses of few Gy [32,34]. Finally, it is also
important to note that the sensitization procedure using high-γ dose
and moderate heat-treatments is different than the thermal sensitization
of the OSL signals above 500 °C that caused a decrease in the lifetime
components of quartz [13,14].
The above mentioned reports suggest that luminescence sensitivity
changes in quartz are governed by ionic motion and electron-hole
recombination in point defects acting as localized levels during the
redistribution of electronic charges. This idea was developed by Itoh
et al. [38] to account for the TL mechanism related to 110 and 325 °C
TL peaks as well as the OSL response of quartz at room temperature.
Recently, the variations in the luminescence lifetimes in TR-OSL
experiments carried out as a function of annealing and stimulation
temperatures [13,14] were interpreted in terms of a model involving
localized electronic transitions between energy states within two
luminescence centers [39,40]. These analytical approaches support
the current importance to investigate the structure of point defects in
quartz in association with TL and OSL measurements. Here, this issue is
further examined in order to understand the mechanism of sensitization
of TL peaks occurring above 220 °C. For this, the configuration of point
defects is followed after each step of sensitization in samples prepared
from two single crystals with different sensitivities. The assessment to
the structure of point defects related to silicon and oxygen vacancies
and Al, Ge, Li and OH impurities was carried out by EPR and IR
spectroscopy. The TL peaks were identified by applying numerical
deconvolutions to experimental glow curves obtained from the same
samples that were used in EPR and IR analysis. The experimental work
was complemented by a sequence of heat-treatments carried out up to
600 °C to desensitize the TL peaks and to clarify the role played by
several point defects during the TL process. The data analysis was
conducted to provide a whole picture of point defects concerned with
the sensitization process and the TL mechanisms involved with high-
temperature glow peaks.
2. Experimental
2.1. Samples: origin, preparation and sensitization
This study was carried out with samples prepared from two colour-
less single crystals taken from Solonópole (Ceará) and Pouso Alegre
(Minas Gerais) districts in Brazil. MC and PA are the acronyms to
identify Solonópole and Pouso Alegre crystals, respectively. MC was a
semi-euhedral specimen weighting 580 g with only two defined pris-
matic (m-) faces. The crystallographic orientation of one of these faces
was confirmed by X ray diffraction. The X ray pattern was obtained
with a Rigaku Ultima diffractometer with Cu-kα radiation (40 kV,
20 mA); goniometer step of 0.017°/s; counting time 1 s and 2θ scanning
from 10° to 60°. PA was an euhedral specimen weighting 230 g with
well defined prismatic (m-) and rhombohedral (r- and z-) faces. Plates
with 2 mm thick parallel to the crystallographic (1010) and (0001)
planes were cut from MC and PA, respectively. The plates were squared
into 12×12 mm2 samples and their surfaces were lapped and optically
polished. Four samples were prepared from each crystal. These samples
were used to evaluate the content of the OH-related point defects by
P.L. Guzzo et al.
infrared (IR) spectroscopy and the susceptibility to artificial darkening
by γ irradiation.
Thermoluminescence (TL) and electron paramagnetic resonance
(EPR) were carried out with particulate samples prepared from small
fragments of MC and PA crystals. The fragments came from parent
regions used to cut the oriented plates. After cleaning, the fragments
were carefully crushed using an agate mortar and pestle. The particles
were classified in the size range of 75–150 µm with sieves of stainless
steel.
In order to eliminate the accumulated dose related to natural
irradiation, all samples were heat-treated (zeroed) at 400 °C during
1 h in muffle furnace and then gradually cooled to room temperature.
After that, an amount of each sample was sensitized as follows:
irradiation with 25 kGy with 60Co γ rays in a γ-cell irradiator (dose
rate of 5 kGy h−1); one cycle of heat-treatment at 400 °C for 3 h. The
heat-treatments were performed in a muffle furnace at atmospheric
pressure with heating-rate of 5 °C min−1 and slowly cooled (~
1 °C min−1). In this study, N, Z, 25 kGy and S are the acronyms to
identify samples in natural, zeroed, high-dose irradiated and sensitized
conditions, respectively. In order to better correlate TL response with
EPR and IR signal intensities, several aliquots were heat-treated
isochronically (3 h) at different temperatures from 400 to 600 °C in
steps of 25 °C.
2.2. UV–Vis and IR spectroscopy
Absorption spectra in ultraviolet-visible (UV–Vis) and infrared (IR)
ranges were measured at room-temperature with unpolarized light in
two different plates of each crystal in Z, 25 kGy and S conditions as well
as after heat-treatments carried out above 400 °C. The spectra were
obtained in different regions of each plate by delimiting the beam with
a 3 mm diameter window. The UV–Vis spectra were recorded with a
double beam spectrometer model Perkin Elmer Lambda 35. These
spectra were obtained with a slit of 4 nm from 1100 to 190 nm at
120 nm/min. UV–Vis was employed to evaluate intensity of the smoky
color induced by γ irradiation [41].
IR spectroscopy was used to evaluate the intensity of OH-related
point defects such as the [AlO4/H]0 center [42]. The spectra of natural
quartz in the mid-IR region usually show several sharp bands super-
posed upon a broad band due to OH stretching vibrations [43]. IR
spectra were measured with a FT-IR spectrometer model Perkin Elmer
Spectrum 400. The signals were recorded after 50 scans with a
resolution better than 4 cm−1 from 4000 to 2500 cm−1. IR and UV–Vis
absorbance values were normalized into respect to the sample thick-
ness.
2.3. EPR spectroscopy
Powder EPR spectra were measured with a Bruker EMX 10+
spectrometer operating at X-band frequencies with a cylindrical cavity,
using 100 kHz field modulation and amplitude equal to 0.25, 0.50 and
1.00 G. The measurements were carried out with aliquots of 100 mg
placed in 3 mm I.D. tubes of vitreous silica of high-purity. The
measuring parameters (sweep width, modulation amplitude, power,
time constant, conversion time, number of scans and gain) were
optimized according to the peculiarities of each signal. DPPH was used
as a standard to check g-factor determinations. The EPR signals were
identified by comparing the orthorhombic powder g-values (g1, g2 and
g3) of our spectra with the g-values of point defects previously reported
in literature. At room temperature, it was identified the signals related
to E’1, [GeO4/Li]0 and [E’1-GeO4]0 centers [22,44–46] as well as the
silicon-vacancy center labeled as [O23-/M]0 (M: Li or Na) [47,48]. The
dispersion in g-values readings was better than 0.0001. Additional
measurements carried out at liquid-N2 temperature with a finger Dewar
flask showed the presence of [AlO4]0 center [49–52]. The peak-to-peak
(or peak-to-base) intensities of all signals were measured in non-
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Journal of Luminescence 188 (2017) 118–128
saturated conditions. In order to evaluate the uncertainty related to
EPR signal intensities, the signals of [E’1-GeO4]0, [O23-/M]0 (M: Li or
Na) and [GeO4/Li]0 were measured at four different positions for two
different samples of each crystal. The uncertainties were better than 6%
and 12% for MC and PA samples, respectively.
EPR spectra were undertaken in natural (N), zeroed (Z), irradiated
(25 kGy), sensitized (S) and heat-treated conditions. In addition,
complementary measurements were undertaken when MC and PA
samples in Z and S conditions were subsequently irradiated with a
test-dose of 50 Gy of γ rays. In order to deplete the electronic levels
responsible for the first TL peak (the so-called 110 °C peak) another set
of measurements were carried out when Z and S samples were
preheated at 150 °C during 5 min.
2.4. TL measurements
The TL glow curves were recorded from 50 to 400 °C with a linear
heating rate of 2 °C s−1 using a Harshaw-Bicron 3500 TL reader
equipped with a 9125-B photomultiplier tube without filtering. For
this, aliquots of 10 mg were irradiated in air with γ-rays from a 60Co
source (3.2 Gy h−1) with a test-dose of 50 mGy. TL measurements were
carried out in Z, S and heat-treated samples using three aliquots for
each condition. The spectral dependence of the TL signal was analyzed
with a Hamamatsu C10083CA multichannel spectrometer. The light
signal was transmitted to the spectrometer with an optical fiber Ocean
Optics R400-7-UV–Vis. The emission spectra were measured from 300
to 900 nm by heating aliquots of 20 mg of S particles up to approxi-
mately 350 °C after a test-dose irradiation with 5 kGy of γ-rays.
In order to assess the TL intensity of the sensitized peaks accurately,
the glow curves were deconvoluted by a least-square fitting based on
the first-order kinetics model of Randall and Wilkins with the rearran-
gement of the glow curve function suggested by Kitis et al. [53]. The
glow curves were deconvoluted considering the presence of 8 distinct
peaks between 90 and 480 °C. The figure of merit (FOM) defined by
Balian and Eddy [54] was used as a measure of the “goodness-of-fit”.
The FOM values were always better than 6%. The TL intensities of the
main peaks as well the temperature at peak-maximum (Tmax) and the
activation energy (E) were calculated from the TL glow curves obtained
after each step of heat-treatment.
3. Results
3.1. Darkening by γ-radiation
Fig. 1 shows typical UV–Vis spectra of MC and PA measured for
zeroed (Z), irradiated (25 kGy) and sensitized (S) samples. Zeroed
Fig. 1. UV–Vis spectra of MC and PA (inset plot) quartz crystals in zeroed (Z), γ-irradiated
(25 kGy) and sensitized (S) conditions. The depicted absorption bands are those related to
[AlO4]0 centers.
P.L. Guzzo et al.
Fig. 2. IR spectra of MC (a) and PA (b) quartz crystals in zeroed (Z), γ-irradiated (25 kGy) and sensitized (S) conditions measured at room temperature with unpolarized light. The spectra
were shifted from its original absorbance.
samples show an increase in absorption for wavelength < 220 nm,
which is usually seen in the UV region of quartz. This absorption has
been attributed to electronic transitions inside the valence band energy
levels of the silica structure. Gamma radiation increased the absorption
in this range as well as in the whole visible region of MC and PA
spectra. The net effect of γ irradiation in the visible region is connected
with the creation of absorption bands centered at approximately 630,
480 and 380 nm. These bands are related to the smoky color induced by
[AlO4]0 centers [41,55]. These bands are approximately 9 times higher
for MC compared to PA. These bands were not observed when the
samples were heat-treated at 400 °C during 3 h, i.e., once sensitization
was completed. The UV–Vis spectra of sensitized samples were the same
as those obtained in zeroed condition. This result is in fair agreement
with the thermal stability analysis of the EPR signal of [AlO4]0 centers
in synthetic and natural quartz [24,52,56].
3.2. Point-defects in zeroed and irradiated conditions
Fig. 2 shows typical IR spectra of MC and PA crystals obtained in Z,
25 kGy and S conditions. Absorption bands at 3596, 3484, 3380, 3300
and 3200 cm−1 appear superposed upon a broad band due to funda-
mental O-H stretching vibrations from Si-OH groups and molecular
water aggregates [43]. As assigned by Kats [42], the bands at 3300 and
3200 cm−1 are due to quartz overtones or to combination bands of Si-O
vibrations. In addition to the band at 3380 cm−1, the bands at 3435 and
3316 cm−1 observed in PA were also assigned to [AlO4/H]0 centers.
These bands were explained as different vibration of that occurring at
3380 cm−1 but with almost the same resonance frequency [42]. Several
electrodiffusion (sweeping) experiments have suggested that the sharp
Fig. 3. EPR spectra of MC and PA quartz samples irradiated with 25 kGy of γ-rays showing the signals of [AlO4]0 (a) and [GeO4/Li]0 (b) centers. The inset plot in (b) shows the hyperfine
multiplet related to 7Li atoms. The principal values of the g-tensor are indicated.
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Journal of Luminescence 188 (2017) 118–128
band observed at 3484 cm−1 correspond to OH-vibration influenced by
Li+ species [42,57–59]. Experimental evidences indicate that the origin
of the defect center responsible for the band at 3596 cm−1 is connected
to B3+ species substituting for Si4+ in the quartz lattice [60–62].
Similarly as [AlO4/H]0, the charge compensation is provided by H-
bonded OH species and this center can be represented as [BO4/H]0.
In accordance with the Beer-Lambert law, which states that
absorbance is proportional with the molar concentration of the
absorbing species, the concentration of OH-related defects is much
lower in MC compared to PA as Fig. 2 shows. Since ionizing irradiation
causes a reduction in Li-dependent OH and an increase in [AlO4/H]0
bands, the change in IR bands due to irradiation with γ rays can be also
explained by the migration of Li+ species from their original sites in Al-
and OH-related centers. As it is well known, ionizing radiation causes
the destruction of [AlO4/Li]0 centers giving rise to [AlO4]0 and [AlO4/
H]0 centers [42,57–59]. Fig. 2 also shows the IR spectra of the
sensitized samples. It is noticed that the heat-treatment adopted to
complete the process of sensitization almost restored back the inten-
sities of the bands related to [AlO4/H]0 and Li-dependent OH centers.
The band assigned to [BO4/H]0 decreased slightly in both crystals.
EPR measurements in natural samples showed the characteristic
signals of the well known E’1 center with g1 =2.0018, g2 =2.0005 and
g3 =2.0003 values at room temperature [28,44]. The E’1 signal was
approximately two times higher in MC compared to PA. At liquid-N2
temperature, MC showed a weak signal related to [AlO4]0 centers
related to the exposure of natural radiation. After heating at 400 °C
(zeroed condition), neither E’1 nor any other paramagnetic center were
noticed. As it can be seen in Fig. 3, the γ irradiation with 25 kGy caused
the creation of [AlO4]0, [GeO4/Li]0 and [E’1-GeO4]0 centers in both
P.L. Guzzo et al.
samples. These signals were identified considering the g-factors of
powdered and quartz single crystals reported elsewhere
[22,45,46,50–52,63].
In Fig. 3(a), the signal intensities of [AlO4]0 center is significantly
higher for MC, which is in agreement with the intensity of the optical
absorption bands shown in Fig. 1. In addition to the typical hyperfine
lines due to the nuclear spins and quadrupole splitting, the EPR
spectrum of MC shows many narrow lines superposed upon the
[AlO4]0 signals around 3380 Gauss. The origin of these lines is
unknown. The peak-to-peak intensity related to the gAl signal of
[AlO4]0 showed that this center was approximately 5 times higher for
MC compared to PA. In turn, the peak-to-base intensities related to the
g3-signal of [GeO4/Li]0 in Fig. 3(b) showed that this center was
approximately 40 times higher for MC. The signal intensity of [E’1-
GeO4]0 cannot be properly evaluated in these spectra because it is
affected by the strong intensity of [GeO4/Li]0 center. The four lines
centered near 3492 G in Fig. 3(b), equidistant from each other by
approximately 0.6 G, are related to the nuclear spin flip satellites
resultant from the interaction of 7Li with Ge unpaired electron [46,64].
3.3. Point defects created by sensitization
The configuration of point defects in MC and PA changed consider-
ably when sensitization was completed with the heat-treatment at
400 °C. In the EPR spectra, [AlO4]0 and [GeO4/Li]0 centers were no
more observed. In the UV–Vis and IR spectra, the optical bands related
to [AlO4]0 were eliminated and the intensities of the Li-dependent OH
bands were restored to values similar as those measured in zeroed
samples.
The new point defects created by sensitization are shown in Fig. 4.
In the spectra recorded with 0.2 mW, the signals identified by
g1=2.0012, g2=1.9951 and g3=1.9943 are closely compared to those
of an E’1 trapped electron center occurring in the vicinity of a
substitutional Ge4+ ion. The structure of this center was established
by Feigl and Anderson [45] and it was labeled as [Ge(III)e-]. In the
present study, this center is denoted as [E’1-GeO4]0. The peak-to-peak
intensity related to the g2-component of this center is approximately 6
times higher for MC than PA. Fig. 4(a) also shows a narrow signal
superposed upon the g1 component of the [E’1-GeO4]0 occurring around
3482 G. The g-value of this signal (~2.0006) correspond to the g2
component of the pure E’1 center, i.e., an electron trapped at an oxygen
vacancy surrounding a silicon atom. In Fig. 4(b), the spectra obtained
with 20 mW show a set of signal components with g1 =2.0497, g2
=2.0074 and g3 =2.0037 that are closely compared to those of a
silicon vacancy hole-center involving an alkali ion as charge compen-
sator. This signal has been labeled as [O23-/M]0 (M: Li or Na) [47,48].
Fig. 4. EPR spectra of MC and PA sensitized samples showing the signals of [E’1-GeO4]0 (a) and [O23-/Li]0 (b) centers measured at room temperature with 0.2 and 20 mW, respectively.
The principal values of the g-tensor are indicated.
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Journal of Luminescence 188 (2017) 118–128
Trace elements analysis in natural quartz issued from hydrothermal and
pegmatite deposits from Brazil have been shown that Li concentration is
often higher than Na [58,65,66]. In this study, it is assumed that the
main charge compensator for [O23-/M]0 centers in MC and PA crystals
is Li. Thus, the silicon vacancy hole-center is denoted here as [O23-/Li]0.
The intensity of the g2 component for this signal is approximately 17
times higher for MC compared to PA.
Fig. 5 shows the EPR spectra obtained at room temperature of
zeroed and sensitized samples of MC irradiated with a test-dose of
50 Gy. The spectrum of the sensitized sample subsequently heat-treated
at 150 °C is also shown. These spectra show that the [E’1-GeO4]0 and
[O23-/Li]0 centers occurs only in sensitized sample. In addition to [E’1-
GeO4]0 signals, Fig. 5(a) also shows the signal components related to
the [GeO4/Li]0 center and those probably related to the E’1 center. The
EPR spectra inserted in Fig. 5(a) were obtained with the experimental
parameters suitable to record [GeO4/Li]0 signals, i.e., with lower power
and smaller amplitude modulation than those used for [E’1-GeO4]0
signals. It is observed that the intensity of the signals related to [GeO4/
Li]0 is lower in the sensitized sample compared with the unsensitized
(zeroed) sample. This feature can be explained by the fact that a
number of Li+ ions were captured by silicon vacancies to create [O23-/
Li]0 centers during sensitization. The spectra of sensitized samples in
Fig. 5 also show that [E’1-GeO4]0 and [O23-/Li]0 centers as well as
[GeO4/Li]0 are not affected by the heat-treatment carried out at 150 °C.
As expected, the EPR spectra recorded at liquid-N2 temperature showed
the presence of the [AlO4]0 center for both of zeroed and sensitized
samples. The ionizing radiation energy related to the test-dose of 50 Gy
was not sufficient to produce any noticeable change in the intensities of
IR bands related to [BO4/H]0, [AlO4/H]0 and Li-dependent OH centers.
Fig. 6 summarizes the effect of heat-treatments performed above
400 °C in the intensities of the point defects measured in sensitized
samples. The relative difference of the signal intensity (ΔI/I0) of [E’1-
GeO4]0 and [O23-/Li]0 centers was calculated in relation to the signal
intensity measured in the sensitized condition (I0). It is observed that
[E’1-GeO4]0 and [O23-/Li]0 centers are both very sensitive with heating
temperature above 400 °C. For MC, the intensities of [E’1-GeO4]0 and
[O23-/Li]0 centers decreased more than 60% after the heat-treatment at
425 °C. Due to this reason, an additional treatment was carried out at
410 °C. The decay patterns of [E’1-GeO4]0 and [O23-/Li]0 centers are
quite similar each other but they vary according to the crystal origin. In
the inset plot of Fig. 6, it is seen that the absolute intensities of these
centers are roughly correlated with a linear fitting (R2 =0.957; where
R2 is the fitting factor).
The OH-related centers measured by IR spectroscopy were much
less sensitive to the effect of the heat treatments carried out up to
600 °C. Only the intensity of the Li-dependent OH band of MC crystal
P.L. Guzzo et al.
Fig. 5. EPR spectra of MC quartz in the zeroed (Z) and sensitized (S) condition crystal showing the effect of test-dose (50 Gy) and heat-treatment (150 °C; 5 min) on the signal intensities
of [E’1-GeO4]0, [GeO4/Li]0 (a) and [O23-/Li]0 (b) centers. The principal values of the g-tensor are indicated.
Fig. 6. Effect of the temperature of the isochronal annealing (3 h) on the intensities of the
[E’1-GeO4]0 and [O23-/Li]0 centers in MC and PA crystals. EPR intensities were normal-
ized to values measured after sensitization. The inset plot shows the correlation between
the signal intensities of the same centers.
changed. Compared to the sensitized condition, this band decreased
almost 20% with the heat-treatment performed after heating at 425 °C.
For higher temperatures, the intensity remained unchanged. The
relative variations of the other IR bands turned around 10%, which is
lower than the uncertainty related to the evaluation of absorption
bands in the mid IR region.
3.4. TL intensity and TL emission
Typical TL curves of powdered aliquots of MC and PA in zeroed and
sensitized conditions are shown in Figs. 7 and 8, respectively. In the
zeroed condition, the glow curves show the peaks occurring around 110
and 375 °C. The peak at 375 °C is only observed in MC. Although the
110 °C peak is thermally instable at room temperature, the measure-
ments showed that this peak was always higher for MC samples. Fig. 8
illustrates the experimental glow curves of sensitized samples together
with the Gaussian components and the simulated curve resultant from
the deconvolution procedure. Each component was identified by the
respective peak-maximum temperature. It is noticed that the whole TL
intensity and the peak structure forming MC and PA are quite different.
The strongest peaks occurring above 220 °C in MC are centered at 240
and 325 °C. The activation energy (Ea) calculated for these peaks are
(0.93 ± 0.02) eV and (1.09 ± 0.02) eV, respectively. For PA, the peak-
maximum and the activation energy of the main components are 290 °C
(Ea =0.92 ± 0.03 eV) and 330 °C (Ea =1.07 ± 0.01 eV).
The quantitative analysis of the TL signal intensities as a function of
123
Journal of Luminescence 188 (2017) 118–128
Fig. 7. TL glow curves of MC and PA quartz crystals in the zeroed (Z) condition. Test-
dose: 5 Gy; heating rate: 2 °C s−1.
the temperature of the heat-treatments performed between 400 and
600 °C are summarized in Fig. 9. This figure shows the variation of the
sum of the sensitized components occurring between 200 and 400 °C as
well as the variation of the intensities of the strongest components of
MC and PA individually. The analysis of these results shows that the
sensitization of MC is approximately 2.7 times higher than PA. For both
samples almost 50% of the TL intensity was depleted with the heat-
treatment at 450 °C. The decay pattern of the TL intensity for MC is
mainly governed by the decay of the 240 °C component. For PA, it is the
decay of the 330 °C component that plays the major role in the
desensitization process.
The spectral emission of the TL signal shown in Fig. 10 has a broad
emission in 400–700 nm region and rises to a maximum near 480 nm
(2.53 eV). The intensity recorded for MC is much higher than that of
PA. Several studies have suggested that the origin of the blue emission
in 460–500 nm range is attributed to electron-hole recombination at
[AlO4]0 centers [23,67,68]. The spectral dependence occurring in our
samples is quite similar with that observed by Jani et al. [23] in samples
of synthetic quartz where Al centers were mainly compensated by alkali
(Li and Na) ions. Investigating the effect of X-ray irradiation and heat-
treatments on the radio-luminescence of natural and synthetic quartz,
Martini et al. [35] observed that the blue emission is the dominant band
when samples are submitted to several cycles of irradiation with 20 Gy
and heating (150 °C). These authors also noticed that the ultraviolet
emission at 360 nm (3.44 eV) became the dominant band when the
heating temperature was increased to 500 °C.
P.L. Guzzo et al.
Fig. 8. TL glow curves of MC (a) and PA (b) quartz crystals in the sensitized (S) condition and the components resultant from the deconvolution. Test-dose: 50 mGy; heating rate: 2 °C s−1.
Fig. 9. Effect of the isochronal annealing (3 h) on the intensities of TL components of
sensitized MC and PA samples. The inset plot shows the variation of the major TL
components.
Fig. 10. TL emission spectra of sensitized MC and PA crystals obtained from 25 to 350 °C
at ~20 °C s−1. Test-dose: 5 kGy of γ rays.
4. Discussion
After sensitization with 25 kGy of γ-rays plus heat treatment at
400 °C, it was found that [E’1-GeO4]0 and [O23-/Li]0 centers are
thermally stable at room temperature together with [AlO4/Li]0 and
[GeO4]0. These centers can be acting as localized levels capable to trap
charge carriers during excitation with a given test-dose. It is know that
the probability of trapping electrons or holes of each imperfection is
defined in terms of their capture cross sections for electrons and holes.
124
Journal of Luminescence 188 (2017) 118–128
Comparing the g-factor values of these centers with that of the free
electron (ge =2.0023), it is to be noted that [GeO4/Li]0 and [E’1-GeO4]0
have a higher probability of gaining an electron whereas [AlO4]0 and
[O23-/Li]0 have a higher probability of losing an electron, i.e., they are
probably acting as a hole traps. In the Sections 4.1 and 4.2, the
rearrangements in the configuration of point defects and their thermal
stability are analyzed in order to clarify their role during the TL
emission of the sensitized peaks. Additional evidences showing the
creation of E’1 centers in sensitized samples with test-dose excitation is
also considered. In the sequence, the origin of the point defects acting
as diamagnetic precursors for E’1, [E’1-GeO4]0, [GeO4/Li]0, [AlO4]0 and
[O23-/Li]0 centers are further analyzed in the context of previous works.
Finally, a sequence of reactions involving electron-hole recombination
and Li+ migration at different defect pairs are proposed to describe the
whole TL process in sensitized quartz studied here.
4.1. Electron trapping centers
The results of this study showed that [AlO4]0 and [GeO4/Li]0
centers produced by test-dose irradiation are thermally stable up to
150 °C. These centers are no more observable after MC and PA samples
being heat-treated at 400 °C. These results are in fair agreement with
previous data of isochronal annealing performed in single crystals of
synthetic quartz [56] and quartz grains extracted from granitic rocks
[52]. These authors showed that EPR signal of [AlO4]0 was stable up to
approximately 200 °C and was depleted above 300 °C. McKeever et al.
[24] showed that the signal intensities of [AlO4]0 and [GeO4/Li]0
centers were completely removed over 350 °C in a single crystal taken
from Arkansas. Thus, it is possible to assume that [AlO4]0 and [GeO4/
Li]0 are playing the role of trapping levels related to the glow peaks
occurring above 220 °C. The heat treatment preformed at 400 °C caused
the migration of Li+ ions and electrons back to the Al sites, restoring
the configuration of [AlO4/Li]0 and [GeO4]0 structures found before
excitation with the test-dose. On its turn, the decrease in the intensities
of [E’1-GeO4]0 and [O23-/Li]0 signals shown in Fig. 6 occurred only
above 400 °C. Investigating the EPR signal of Ge-doped synthetic quartz
irradiated with X-rays, Feigl and Anderson [45] remarked that the
signal of the [Ge(III)e-] center was observed up to 330 °C and it was
completely removed above 430 °C. According to Botis et al. [48], the
signal of the [O23-/M]0 (M: Li, Na) center in quartz grains extracted
from sediments was present up to 500 °C and was removed when
annealed at 600 °C. Based on these reports, it is possible to conclude
that both [E’1-GeO4]0 and [O23-/Li]0 centers are thermally stable up to
400 °C. Therefore, these defects are not acting as trapping states
responsible for the sensitized peaks shown in Fig. 8.
The EPR spectra shown in Figs. 4(a) and 5(a) suggested the presence
of E’1 center in sensitized samples of MC and PA. Following the
intensity of the signal component occurring at g =2.0006 with heat-
P.L. Guzzo et al. Journal of Luminescence 188 (2017) 118–128

Fig. 11. Microwave power dependence of the signal intensities of E’1, [GeO4/Li]0 and
[E’1-GeO4]0 centers measured in sensitized MC sample irradiated with a test-dose of
50 Gy.
treatments performed up to 600 °C, it was seen that this signal
disappeared above 450 °C. It has been reported that the E’1 intensity
rises from 200 °C to a maximum at 300 °C followed by a decrease up to
400–450 °C [52,56,69]. As it is well known, the storage of radiation
energy in insulators is related to a sufficient population of defects
within the crystal structure. E’1 is a typical electron trap and analysis
often revels an insufficient concentration of electron traps to comple-
ment the [AlO4]0 centers that have been considered as hole traps in the
TL process of natural and synthetic quartz [24,32,50].
As well as the thermal dependence, the analysis of the microwave
power dependence can be helpful to distinguish different paramagnetic
centers occurring in the same spectral region. Thus, Fig. 11 shows the
microwave power dependence of signal intensities related to [GeO4/
Li]0 and [E’1-GeO4]0 centers and the signal that has been supposedly
associated with the pure E’1 center. These signals were measured in the
sensitized MC sample irradiated with a test-dose of 50 Gy. This figure
shows that the signal intensity attributed to E’1 saturates around
0.02 mW whereas those assigned to [GeO4/Li]0 and [E’1-GeO4]0 centers
are still increasing in the power level of 1 mW. These findings are in fair
agreement with the literature that report that the signal intensity of the
E’1 center saturates at 0.01 mW whereas the [GeO4/Li]0 and [E’1-
GeO4]0 center saturates at microwave power > 100 mW [70]. To lend
support to the assumption that E’1 was created by test-dose irradiation
in sensitized samples, Table 1 summarizes the signal intensity values of
E’1 and [E’1-GeO4]0 centers prior and after sensitized MC and PA
samples being irradiated with 50 Gy. The values measured in EPR
Table 1
EPR signal intensities of E’1, [E’1-GeO4]0 and [GeO4/Li]0 centers in sensitized (S) samples
of MC and PA following test-dose with 50 Gy and heat-treatment at 150 °C.
spectra obtained after the heat-treatment at 150 °C are also shown. For
both set of samples, it is seen that signal intensities of E’1 increased
around four times when they were irradiated with a test-dose whereas
no significant change occurred in [E’1-GeO4]0 signals. Thus, it is
possible to conclude that additional electrons are being trapped
together with interstitial Li+ ions dislodged from [AlO4/Li]0 centers
in localized levels formed by oxygen vacancies and [GeO4]0 centers.
The analysis of the glow curves shown in Fig. 8 showed that the
whole sensitized signal can be deconvoluted into several components.
The two main components of MC are those related to the temperature
maximum at 240 and 325 °C. For PA, the major component is centered
at 330 °C. The similar dependence of 325 and 330 °C components with
the temperature of the isochronal annealing shown in Fig. 9 suggests
that they are associated with the same electron traps. Table 1 also
shows the signal intensities for the [GeO4/Li]0 center and the intensity
ratios of each class of defect between MC and PA. It is seen that the
intensity ratio for E’1 and [GeO4/Li]0 is much more close to the
sensitization factor found between MC and PA (2.7) than the intensity
ratio found for [E’1-GeO4]0 center. From Fig. 3(b) and Table 1, it is clear
that the concentration of [GeO4/Li]0 centers is much higher in MC than
PA. Previously, Anderson et al. [71] observed that the temperature
decay of [GeO4/M]0 (M: Li, Na) centers occurred around 250 °C in Ge-
doped synthetic quartz. Based on this analysis, it is possible to assume
that the electron traps related to the 240 °C component are [GeO4/Li]0
centers whereas E’1 centers are the active electron traps responsible for
the component occurring at 325 °C.
4.2. The luminescent center
Until now, the assumption that electron-hole recombination beyond
220 °C is occurring at [AlO4]0 centers was only supported by the
relationships between the intensity of the TL peaks with Li/Al and Li/
OH impurity content ratios measured in samples with different
sensitivities [32,33]. Here, this assumption was supported by the
difference in EPR signal intensities and TL emissions observed between
MC and PA shown in Figs. 3 and 10, respectively. However, both EPR
signals and TL emissions were collected after heavy excitation with 25
and 5 kGy, respectively. In order to progress in this analysis, Fig. 12
shows [AlO4]0 signals of zeroed and sensitized samples of MC irradiated
with a test-dose of 50 Gy. In the sensitized condition, the comparison
between MC and PA shows that the number of [AlO4]0 centers available
to electron-hole recombination by thermal excitation are considerably
higher in MC. Thus, this result confirms that [AlO4]0 is the luminescent
center responsible for the 480 nm emission of sensitized peaks in MC
and PA.
The second feature that deserves to be analyzed in the Fig. 12 is the
difference in the [AlO4]0 signals between zeroed and sensitized

center condition MC (a.u.) PA (a.u.) MC/PA

ratio

E’1 S 14745 ± 4350a 7910 ± 335 1.86

S; 50 Gy 58556 35481 1.65
S; 50 Gy; 65511 ± 3942 34165 ± 1170 1.92
150 °C

[E’1-GeO4]0 S 56765 8435 6.72

S; 50 Gy 47230 ± 590 8128 ± 248 5.81
S; 50 Gy; 55661 ± 1116 9636 ± 1030 5.78
150 °C

[GeO4/Li]0 S n.o. n.o. –

S; 50 Gy 633802 ± 31176 165753 3.82
S; 50 Gy; 621926 ± 24664 177172 ± 15470 3.51
150 °C
Fig. 12. EPR spectra of [AlO4]0 center in MC (zeroed and sensitized) and PA (sensitized)
a
standard deviation n.o.: not observed. samples irradiated with a test-dose of 50 Gy.

125
P.L. Guzzo et al.
samples. It is noticed that the intensity of the gAl signal is approximately
the same, which suggests that the population of [AlO4]0 centers did not
change significantly with the sensitization process. However, the entire
extension of the [AlO4]0 signal of the sensitized sample is decorated by
narrow lines with line-width smaller than 0.03 G. In the zeroed sample,
these lines are restricted to the spectral region between 3375 and
3382 G. The narrow lines appearing on the typical [AlO4]0 powder
spectrum suggest that the sensitization process is affecting the electro-
nic structure of this center. In the present time, one plausible explana-
tion for the occurrence of the narrow lines is the trap of the hole on one
oxygen ion adjacent to substitutional aluminum. At room temperature,
where the EPR lines of [AlO4]0 center are very broad, the hole is fast
jumping and it can be found in one of the four tetrahedral oxygen. Due
to the difference in the length of the Si-O bonds, the oxygen sites are not
energetically equivalent. At temperatures below 77 K, the hole can be
trapped by one of two equivalent ground oxygen state sites, which can
increase its magnetic interactions with the oxygen ion itself and with
the surrounding Si atoms [51,72]. Schnadt and Schneider [72] showed
that the polarization effects arising from quartz lattice due to imperfec-
tions and the piezoelectric effect are strong enough to induce a
complete localization of the hole at one of the two equivalent ground
state oxygen sites. Recently, to explain the thermal quenching in quartz,
Pagonis et al. [39,40] proposed an analytical model involving two
electronic transitions between energy states competing one each other
within the recombination center. According to this model, the first
transition is a radiative transition resulting in the emission from excited
level to the ground state. The second transition is an indirect thermally
assisted non-radiative transition passing through a higher excited state
of the recombination center. Considering the localization of the hole in
one oxygen site, as the EPR spectrum of the sensitized MC sample
shown in Fig. 12 suggests, it is possible to assume that the sensitization
process is annihilating the higher excited levels of the [AlO4]0 center
and the mechanism of competition between non-radiative and lumines-
cence transition within the recombination center is no more existing.
Further experimental efforts are required to confirm this hypothesis.
As the rate at which electrons and holes created during excitation is
equal, the number of electrons trapped at E’1 and [GeO4/Li]0 centers
should be the same as the number of holes trapped at [AlO4]0 centers.
The isochronal annealing experiments carried out by Jani et al. [56]
and Toyoda and Ikeya [52] showed that the creation of E’1 centers
occurs in the same range of temperature as the thermal decay of
[AlO4]0 centers. Later, Usami et al. [73] confirmed that the growth of
E’1 centers created by irradiation plus annealing (300 °C, 15 min) is
correlated, up to a certain limit, with the concentration of [AlO4]0
centers. In their study about the thermal sensitization of the OSL
components in sedimentary quartz, Poolton et al. [74] reported that the
EPR signal of the [AlO4]0 center was not affected by annealing
temperatures performed up to 1100 °C. These authors explained the
increase in the luminescence signals observed in annealed samples
between 400 and 900 °C by the annihilation of E’ centers which was
assumed to act as non-radiative centers competing in the OSL process.
However, in contrary to all these reports, the results of the present
study show that both E’1 and [AlO4]0 centers are occurring simulta-
neously in sensitized samples irradiated with a given test-dose,
similarly as it has been observed for [GeO4/Li]0 and [AlO4]0 centers.
Thus, it is possible to suggest that the sensitization process described
here is allowing the coexistence of E’1 and [AlO4]0 into the quartz
lattice just after test-dose irradiation.
4.3. Precursors and competitors
The results of the present study show that the migration of Li+ ions
from Al to Ge sites is essential to explain the changes in the configura-
tion of point defects upon γ-irradiation at room-temperature. The
occurrence of [GeO4]0 and the nature of the charge compensator for
Al centers are prerequisites for sensitization, otherwise [GeO4/Li]0
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Journal of Luminescence 188 (2017) 118–128
would not be available as electron trapping centers and the TL peak at
around 240 °C would not exist. Thus, the higher concentration of
[AlO4/Li]0 and [GeO4]0 centers in the zeroed condition explains the
higher TL sensitivity of the MC crystal. The results of the present work
confirms that the precursors for [AlO4]0 and [GeO4/Li]0 centers in MC
and PA crystals are [AlO4/Li]0 and [GeO4]0 centers, respectively.
It is well recognized that the precursors for E’1 centers are intrinsic
oxygen vacancies filled with two electrons [36,56,73]. The elimination
of the natural E’1 centers after zeroing, suggests that the oxygen
vacancies close to silicon were filled with two electrons during the
heat-treatment at 400 °C. On its turn, E’1 coupled with [GeO4]0 gives
rise to [E’1-GeO4]0 that was not eliminated by the heat-treatment at
400 °C. As stated before, the concentration of Ge in natural quartz is
significantly smaller than Al and Li concentrations. The proximity in the
magnetic resonance energy to produce the spin transitions in E’1,
[GeO4/Li]0 and [E’1-GeO4]0 centers suggests that the energy states
related to them are spatially correlated and it is reasonable to assume
that [GeO4/Li]0 and [E’1-GeO4]0 centers are sharing the same substitu-
tional Ge4+ ions. Although the precursor for [O23-/Li]0 centers is
unknown, it is reasonable to assume that intrinsic silicon vacancies
completely filled with positive charges are occurring into the quartz
lattice in the natural condition. The creation of [O23-/Li]0 centers
during the sensitization process is probably resultant from the migra-
tion of Li+ ions from [AlO4/Li]0 and Li-dependent OH centers to these
intrinsic silicon vacancies.
The similar dependence found for the EPR intensities of [E’1-GeO4]0
and [O23-/Li]0 centers with the temperature of the heat-treatments
(Fig. 6) is another feature that deserves to be analyzed in more detail.
For this, Fig. 13 shows the relationship between the sum of the TL
components (4, 5, 6 and 7) with the intensities for [E’1-GeO4]0 and
[O23-/Li]0 centers measured for MC and PA crystals. It is observed that
the variation of the TL signal with EPR intensity follows a similar path
independently from sample origin. Fig. 13 shows that the thermal
desensitization of TL signals is directly related to the annealing of [E’1-
GeO4]0 and [O23-/Li]0 centers. As shown earlier, [E’1-GeO4]0 and [O23-/
Li]0 centers are not playing the role of electron traps and recombination
centers responsible for the TL mechanism studied here. Thus, the
relationships shown in Figs. 6, 9 and 13 can explains the mechanism
of competition between trapped states related to the precursors for [E’1-
GeO4]0 and [O23-/Li]0 centers and the precursors of the active trapping
centers during the excitation with test-dose in non-sensitized samples.
In sensitized samples, at the moment of irradiation with a test-dose,
[E’1-GeO4]0 and [O23-/Li]0 centers already exist and are not participat-
ing to the TL emissions up to 400 °C. Thus it is possible to explain the
thermal desensitization by an increase in the number of the precursors
Fig. 13. Relationship between the sum of the main TL components (4. 5, 6 and 7) in MC
and PA samples with the EPR intensities of [E’1-GeO4]0 and [O23-/Li]0 centers measured
after the heat-treatments between 400 and 600 °C.
P.L. Guzzo et al. Journal of Luminescence 188 (2017) 118–128

in the 450–500 nm range. The electronic and ionic recombination

transitions are localized within the [AlO4]0 center, similar as it was
recently predicted by Pagonis et al. [39,40]. The optical bleaching of
the OSL components in sedimentary quartz thermally sensitized at
700 °C was also explained by a similar mechanism of electronic and
ionic transfer involving [TiO4/H]0, [TiO4/Li]0 and [AlO4]0 centers
acting as donors and acceptor centers, respectively [74]. The further
increase of temperature above 400 °C restores progressively the point
defect configuration occurring in unsensitized (zeroed) condition, i.e.,
[AlO4/Li]0, [GeO4]0 and oxygen and silicon vacancies completely filled
with charge carriers. In Fig. 14, the neutral Si vacancies are represented
as [O24-]0.

5. Conclusion

The results of the present work showed that the mechanism of

sensitization of the TL peaks occurring above 220 °C in quartz can be
explained by the annihilation of competition between deep traps and
Fig. 14. Summary of point defects and the reaction paths taking place during the TL
recombination center followed by the creation of additional electron
processes in natural quartz sensitized by γ-irradiation (25 kGy) and heat-treatments
(400 °C). [O3Si]0 and [O24-]0 represent oxygen and silicon vacancies filled with electrons
traps. The motion of Li+ ions to silicon vacancies giving rise to [O23-/
and holes, respectively. Li]0 centers, the creation of E’1 centers spatially correlated with
substitutional Ge species and the probable localization of the hole in
for [E’1-GeO4]0 and [O23-/Li]0 centers that are competing with the one oxygen site in [AlO4]0 center are the main changes observed in the
precursors for E’1, [GeO4/Li]0 and [AlO4]0 centers. structure of point defects found in the lattice of high sensitivity quartz
such as the MC crystal.
The combined effect of γ irradiation (e.g., 25 kGy) and heat-
4.4. Electronic and ionic transitions within defect pairs
treatments at 400 °C produces [E’1-GeO4]0 and [O23-/Li]0 centers by
electronic and ionic transfer to intrinsic oxygen and silicon vacancies,
The results of the present study show that electronic transfers in
respectively. [E’1-GeO4]0 centers produced during sensitization and
association with Li+ diffusion through trapping states related to Al and
pure E’1 centers created during test-dose irradiation increased the
Ge point defects and the creation of E’1 centers during test-dose
effectiveness to trap electrons in sensitized quartz together with
irradiation should be at the basis for a model to account for the
[GeO4/Li]0 centers. The existence of [O23-/Li]0 centers eliminates the
essential features of the TL process in natural quartz sensitized by high-
competition between silicon vacancies and [AlO4]0 centers during the
dose of γ radiation and heat-treatment at 400 °C. In this section, the
TL process after test-dose irradiation. The migration of Li+ ions from Al
reactions proposed by Itoh et al. [38] are extended to describe the ionic
to Ge sites during irradiation and from Ge to Al sites by thermal
and electronic processes responsible for the TL signals in high sensitiv-
activation is at the basis of the TL process in sensitized quartz together
ity quartz.
with the coexistence of E’1 and [AlO4]0 centers after test-dose irradia-
Fig. 14 summarizes the configuration of the point defects before and
tion. Besides the 110 °C peak, the main components of the sensitized TL
after sensitized samples being irradiated with a given test-dose. The free
curves in MC and PA crystals correspond to glow peaks occurring near
charge carriers (electrons and holes) produced during test-dose irradia-
240 and 325 °C. The different concentrations of point defects noticed in
tion are trapped by shallow traps such as [AlO4]- that are progressively
zeroed and sensitized samples and the different TL sensitivities found
converted into [AlO4]0 centers. Fig. 14 shows the reaction paths related
between these crystals suggest that the trapping centers related to the
to the main peaks occurring at 110, 240 and 325 °C in MC and PA
240 and 325 °C peaks are [GeO4/Li]0 and E’1 centers, respectively. The
crystals. The mechanism responsible for the occurrence of the 110 °C
electron-hole recombination together with of Li+ motion occurs at
peak is based on the assumption that electron and holes are trapped at
[AlO4]0 centers, restoring [AlO4/Li]0 precursors and giving rise to the
shallow traps and the recombination occurs at [AlO4]- centers produced
emission centered near to 480 nm.
by the diffusion of Li+ from [AlO4/Li]0 centers during test-dose
Taking into account the nature of γ radiation and the moderate
irradiation [24,25]. As it was presumed by Itoh et al. [38], the
temperatures involved with Li+ motion into the crystal lattice, it is
recombination should occur at the [AlO4]- centers in order to explain
possible to suggest that ([GeO4/Li]0, [AlO4]0), (E’1, [AlO4/Li]0) and
the short lifetime of this peak and the emission in the 360–380 nm
([E’1-GeO4]0, [O23-/Li+]0) are spatially correlated defects pairs acting
range. This assumption is supported by the close relationship observed
as localized trapping states in the TL process of high sensitivity quartz.
between the TL sensitivity of the 110 °C peak and the RL band emitting
In the sensitized condition, the deep traps are associated with [E’1-
at 360 nm reported by Martini et al. [75]. As the TL measurement
GeO4]0 and [O23-/Li+]0 centers, which are not competing with the
progress, Li+ ions hosted at [GeO4/Li]0 site are thermally activated and
active traps up to 400 °C.
diffuse back to Al centers, which is in the form of [AlO4]0 centers before
being converted to [AlO4/Li]- centers. As shown in Section 4.1, the
electronic trapping states responsible for the TL peaks occurring at 240 Acknowledgments
and 325 °C are related to [GeO4/Li]0 and E’1 centers, respectively. After
a sequence of electron-holes recombinations, [AlO4/Li]- are progres- This study received the financial support of Fundação de Amparo à
sively transformed into stable [AlO4/Li]0 centers with the transference Ciência e Tecnologia do Estado de Pernambuco (FACEPE/APQ-1343-
of negative charge carriers to E’1 centers, filling the oxygen vacancies 3.09/10 and APQ-0648-3.09/14), Conselho Nacional de
with two electrons, which is represented here as [O3Si]0. For synthetic Desenvolvimento Científico e Tecnológico (CNPq/P: 579751/2008-2,
quartz, it was reported that the blue emission measured in TL and RL 303917/2012-1 and 304890/2014-4) and Financiadora de Estudos e
experiments is dominant over UV emission when the main charge Projetos (FINEP/P: 01.06.0666.00/2005). The authors are grateful to
compensator for Al centers is Li+ ions [23,75]. Thus, as shown in Prof. Maria Fernanda Pimentel (Dep. Chemical Engineering, UFPE) for
Fig. 10, the TL emission related to the peaks above 220 °C is occurring providing them with the facilities to carry out IR spectroscopy.

127
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