Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21

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Nuclear Instruments and Methods in Physics Research B

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Defect studies in quartz: Composite nature of the blue and UV emissions

Marco Martini a,b,⇑, Mauro Fasoli a, Irene Villa a
a
Dipartimento di Scienza dei Materiali, Università degli Studi di Milano Bicocca, via R. Cozzi 55, I-20125 Milano, Italy
b
INFN, Sezione di Milano Bicocca, Piazza della Scienza 1, I-20126 Milano, Italy

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

Article history: Quartz is an extremely diffused natural luminescence dosimeter. Thanks to the presence of traps and
Received 1 July 2013 luminescence centres, its TSL and OSL (Thermally and Optically Stimulated Luminescence) properties
Received in revised form 24 September have been extensively exploited. Quartz is then used for archaeological and geological dating and is
2013
one of the most useful materials for accident dosimetry.
Available online 8 February 2014
Many luminescence emissions are known to be present in the OSL and TSL of quartz. Three main
emission bands are always reported, as the red, blue and UV bands, centred at around 650, 470, and
Keywords:
360–380 nm, respectively.
Quartz
Radioluminescence
Although the assignment of the luminescence emissions to specific defect centres in quartz is still
Dating undefined, a thorough analysis of the radioluminescence emissions and their response to irradiation
and thermal treatments turned out to be very useful in understanding many features. Specifically, the
presence of the same emission bands in natural and synthetic quartz and their dependence on the pres-
ence of extrinsic impurities is a common characteristic. The main impurities involve Al ions substituting
Si ones and charge compensated by nearby either alkali ions, H+, or a hole. The emission spectra dynamics
evidenced in our experiment confirm the role of Al-related centres in the luminescence properties of
quartz.
From the measurements presented in this paper the composite nature of the ‘‘blue’’ emission is con-
firmed. Two bands labelled as A at 2.5 eV and B at 2.8 eV contribute to the emission in this region, their
behaviour being different as a function of irradiation.
More complex is the picture in the UV region, where, besides the already detected C and D bands at
3.4 eV and 3.9 eV, respectively, two further emissions have been detected at 3.1 eV and 3.7 eV. Despite
both the 3.4 eV and the 3.7 eV bands are shown to be affected by thermal treatments, the annealing tem-
perature dependence of their intensity is markedly different. In fact, whereas the C band intensity, at
3.4 eV, increases after annealing at 500 °C followed by a decrease at higher temperatures, the 3.7 eV
intensity is strongly enhanced by annealing at temperature above 700 °C and reaches its highest value
after annealing at around 1000 °C.
In the light of these results a number of already known features of quartz emissions should be
reconsidered.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction applications. Quartz is one of the most abundant minerals in the

The defect structure of an insulating material is an essential
requirement to understand its dosimetric properties. In fact, intrin-
sic and extrinsic defects act as trapping and recombination centres,
giving origin to the so-called delayed luminescence, a property that
characterizes luminescence dosimetry. Quartz is an efficient
natural dosimeter [1] and is extensively exploited in dosimetric
⇑ Corresponding author at: Dipartimento di Scienza dei Materiali, Università degli
Studi di Milano Bicocca, via R. Cozzi 55, I-20125 Milano, Italy. Tel.: +39 02 64485
166; fax: +39 02 64485 400.
E-mail address: m.martini@unimib.it (M. Martini).
continental crust of the Earth and can be used to detect the amount
of absorbed energy due to natural or man-made exposure to ioniz-
ing radiation, i.e. the absorbed radiation dose. On this measure-
ment are based some luminescence dating techniques, the best
known being thermoluminescence dating [2]. Furthermore quartz
is applied in accident dosimetry, in that a composite material
exposed to unwanted irradiation can record the amount of
absorbed dose if it contains enough quantity of some natural
dosimeter, typically quartz [3]. It has been possible to determine
the dose distribution around some accident zones, like Hiroshima
[4] and Chernobyl [5], through the measurement of the thermolu-
minescence of quartz inclusions in bricks and other artifacts.

http://dx.doi.org/10.1016/j.nimb.2013.09.048
0168-583X/Ó 2014 Elsevier B.V. All rights reserved.
16 M. Martini et al. / Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21

Although a large number of studies has been published on the

luminescence properties of crystalline quartz [6,1 and references
therein], a comprehensive description of the light emissions under
different stimulation is still far from being clear. The relationships
between each luminescence emission and the corresponding
responsible defects are generally rather tentative and the assign-
ments given by different studies are often in contrast with one
another.
Even the reported energies of the emission peaks can differ also
because it is emerging that many emission bands are composite
[7,8], possibly by components uncorrelated with each other, which
implies that, in the same energy region, one or the other compo-
nent can alternatively be detected (or an overlapping of the two
components), giving as a result a band at a slightly different
energy.
Many defects are present both in the crystalline and in the
amorphous forms of SiO2, quartz and silica respectively, and are often
reviewed together [9] even if their production and response to
irradiation and thermal treatments are often quite different.
Besides, there are defects occurring in glassy silica that are not
found in quartz and vice versa [10]. As a consequence, the lumines-
cence emissions of quartz and silica are not so similar.
In this paper, firstly, a short review of recent results from radio-
luminescence measurements of natural and synthetic quartz will
be given, showing the effect of Al-related centres on the lumines-
cence properties of quartz. Then, new results on thermal treat-
ments in different atmospheres will be shown, evidencing a role
of Oxygen in inducing emission bands. The dependence of lumines-
cence emissions on the temperature of annealing has also been
studied and two distinct UV bands turned out to have different
behaviour as a function of annealing temperature.

2. Defects in quartz and luminescence emissions

In order to understand the role of the various defects in produc-

ing the different luminescence emissions in quartz, it would be
necessary to correlate the defects detected by specific spectro-
scopic techniques to the corresponding luminescence emissions,
following their behaviour as a function of irradiation and/or other
treatments, typically heat treatments.
A number of defects have been definitely identified in crystal-
line quartz by Electron Spin Resonance (ESR) [11] and it is widely
agreed that two types of centres are certainly essential in the
dynamics of radiative recombination: Oxygen vacancies and Al
centres. The simplest type of O vacancy is the diamagnetic centre
resulting from the removal of an O atom from the otherwise
perfect a-quartz, leaving a direct bond between two Si atoms. This
‘‘neutral O vacancy’’ is often considered as the precursor of the
paramagnetic E01 centre, which is the most recurrent intrinsic
defect in quartz and can be described as a hole trapped at a neutral
O vacancy. The resulting defect features an unpaired electron on
one of the two Si atoms, while the other Si ion, being positively
charged, moves away from the vacancy into a nearby plane config-
uration [12]. Al3+ ion is the main ubiquitous impurity in quartz
whom many defects are associated to. It is present as a substitu-
tional ion for Si4+ and is charge compensated by an alkali ion
(M+) or by an H+ ion, giving rise to [AlO4/M+]0, [AlO4/H+]0, respec-
tively. When neither M+ nor H+ is present near a substitutional
Al3+ ion, this centre can be charge compensated by a hole, giving
rise to the [AlO4]0 centre [13]. Such a defect has been reported
as responsible for a recurrent luminescence emission at
365–380 nm [14], detected in many types of luminescence, in
thermoluminescence (TL) below [15] and above room temperature
(RT) [16], in Optically Stimulated Luminescence (OSL) [8], and in
radio-luminescence (RL) [17,18].
Fig. 1. Deconvolution into Gaussian components of the radioluminescence emis-
sion spectra of (a) pegmatitic quartz (K-2-00) and (b) unswept synthetic one (G0).
From Ref. [7].
Some results have been recently obtained through the analysis
of RL. In Fig. 1 the RL curves of a natural and a synthetic quartz
sample are reported, from [7]. It is noteworthy that the curves
can be de-convoluted in the same four components: Martini
et al. [7] concluded that two components participate in the blue
emission, at 440 nm (2.8 eV) and at 490 nm (2.5 eV) and two emis-
sions are present in the UV, at 360 nm (3.4 eV) and at 310 nm
(3.9 eV). A contribution by a further band at 395 nm (3.1 eV) can
be hypothesized to account for some discrepancies in the curve
fitting.
With the aim of investigating how Al centres are involved in
luminescence dynamics, it is possible to compare the luminescence
of quartzes containing highly different concentrations of alkali
ions. By a high temperature electro-diffusion, the so called ‘‘sweep-
ing’’ procedure, the concentration of alkali ions, that are the main
charges present et al. sites in untreated quartz, can be strongly
reduced and [AlO4]0, [AlO4/H+]0 centres are created. This technique
allows the removal (sweep out), or the introduction (sweep in), of
the ions compensating the Al centre (H+ or alkali ions) by applying
a high electric field (typically 1500–2000 V/cm at 500–600 °C)
along the channels running parallel to the c axis of quartz crystals
[Ref. 19]. Correspondingly, evident modifications in the lumines-
cence properties are detected. In Fig. 2 the radio-luminescence of
two untreated and a swept out quartz samples are compared (from
Ref. [18]). There is evidence of luminescence emissions in the blue
 M. Martini et al. / Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21 17

Fig. 4. Sequence of 40 RL emission spectra of a pegmatitic quartz (K-2-00) collected

under continuous X-ray irradiation. For better readability only some of the spectra
Fig. 2. Radioluminescence emission spectra of synthetic quartz samples either
are shown. From Ref. [7].
untreated (G0 and G12) or ‘‘swept out’’ (GS12). From Ref. [18].

350–450 °C. There is agreement in the interpretation of the effect

as being due to an increase in the concentration of the hole recom-
bination centres, which should emit at 3.4 eV, as seen in Fig. 5.
These have been proposed to be [H3O4]0 [21] or [AlO4]0 [14]. It is
interesting to note that also in this two-step process there should
be the involvement of M+ ions, because the effect is seen only in
unswept quartz [22].

3. Materials and methods

Our investigation was carried out on several crystals of different

origin. For the annealing in controlled atmosphere, a crystal of nat-
ural quartz, named in the text as K-2-00, was considered. The
quartz comes from the Black Hills, South Dakota and formed in
the last pegmatitic stage (T < 300 °C). The crystal was crushed
and sieved to select grains of 100–200 lm dimension. The powder
was divided into four parts, put in quartz crucibles and heated in
the oven at 600 °C for 5 h in the following atmospheres:
Fig. 3. Optically Stimulated Luminescence (OSL) shine down curves, at room
temperature, of an untreated and a ‘‘swept out’’ synthetic quartz sample. Stimu-  Air.
lation wavelength: 470 nm, preheat 10 s at 125 °C. Curves are taken from Ref. [19].  Hydrogen: fluxing a gas mixture of N2 (98%) and H2 (2%).
 Oxygen: in a 50 ml/min O2 flux.
and in the UV regions. The most relevant effect of the ‘‘sweeping  Vacuum: under 105 mbar pressure.
out’’ procedure is that the main UV emission only is present after
eliminating the alkali ions, which is interpreted as a fundamental
role of Al-related centres in the radiative recombination. Similarly,
Optically Stimulated Luminescence (OSL) emission is heavily
affected by the ‘‘sweeping out’’ procedure: in Fig. 3, taken from
Ref. [20], a comparison of the room temperature OSL shine down
curves, under 470 nm stimulation, from an untreated and a ‘‘swept
out’’ quartz, is shown, evidently highlighting a difference of three
orders of magnitude in the OSL intensity.
While in Fig. 4 an increase of the 2.5 eV emission is detected,
another band is affected by irradiation followed by heat treat-
ments: in Fig. 5, also taken from Ref. [7], a sequence similar to
the one reported in Fig. 4 is shown. The fundamental difference
is that now a heating up to 500 °C follows each irradiation, in a
sequence similar to what is known as ‘‘pre-dose’’. The result is a
strong increase of the UV 3.4 eV band rather than the blue 2.5 eV
one.
Still unknown electron and hole traps are involved in the so
called pre-dose effect. The effect consists in a strong increase in Fig. 5. Sequence of RL emission spectra of natural pegmatitic quartz (K-2-00)
the efficiency of the 110 °C TSL peak, as a consequence of repeated obtained during X-ray irradiation followed by a heating up to 500 °C at 1 °C/s. From
RT irradiation followed by heating to a temperature in the range Ref. [7].
18 M. Martini et al. / Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21

spectra. A similar effect is observed for a high energy emission,

Fig. 6. Radioluminescence of a natural pegmatitic quartz (K-2-00) powders
annealed in controlled atmosphere at 600 °C for 5 h. The reported spectra are the
first one out of a sequence of 40 consecutive measurements.
In a second experiment, three different types of quartz were
annealed at different temperatures. Single crystals of a natural col-
ourless quartz, a natural smoky one, and a bar of synthetic (Sawyer
Premium Quality) one, were crushed and grinded. For each quartz,
the fraction of 100–200 lm grain size was selected by sieving and
was divided into ten different batches. Each batch was put in a
quartz crucible and annealed, in air, for 10 min in a preheated
oven. The crucible was then removed from the oven and let cool
to room temperature. A set of nine annealing temperatures, from
300 °C to 1100 °C, in 100 °C step, was considered.
The radio-luminescence (RL) measurements were carried out at
room temperature (RT) using a home-made apparatus featuring, as
detection system, a charge coupled device (CCD) (Jobin–Yvon spec-
trum one 3000) coupled to a spectrograph operating in the 200–
1100 nm range (Jobin–Yvon Triax 180). The data were corrected
for the spectral response of the detection system.
RL excitation was obtained by X-rays irradiation, through a Be
window, using a Philips 2274 X-ray tube with Tungsten target
operated at 20 kV. During each measurement the sample was given
a dose of 10 ± 2 Gy, where the uncertainty is related to the dose
calibration rather than to its repeatability that was quite good
(1%). RL spectra were deconvoluted into Gaussian components
using the least squares method with the Levenberg–Marquardt
algorithm (origin 8.0).
close to 3.9 eV, whose intensity is sensibly higher in the annealed
samples compared to the untreated one. The enhancement of these
two RL emissions is more evidently induced by the annealing in
oxidizing atmosphere (air and Oxygen).
The evolution of the quartz luminescence, under continuous
X-ray irradiation, was monitored on all of the samples through a
sequence of 40 successive RL measurements. The effect of the
irradiation on the RL spectra is similar regardless the annealing
atmosphere. As an example, the results obtained on the quartz
annealed in Oxygen atmosphere are shown in Fig. 7. The blue emis-
sion around 2.7 eV is progressively reduced, at the same time, the
maximum of the emission shifts towards lower energy evidencing
a composite nature of the blue emission. In fact, a second band,
around 2.5 eV, is enhanced by irradiation becoming quickly the
dominant emission. The high energy range of the RL spectrum is
not strongly modified by the X-ray irradiation. In particular, the
emission close to 3.9 eV seems to be stable, whereas in the
3.0–3.5 eV region the RL emission is slightly increased by irradia-
tion but early reaches a saturation level. Finally, an emission band
below 2.0 eV, detected only in annealed samples, is enhanced by
X-ray irradiation. Fig. 8 reports the RL spectra recorded at the
end of the sequence. The most intense emission is peaked around
2.5 eV both in the untreated quartz and in the annealed ones and
the absolute intensity of the band is similar in all of the samples,
regardless the annealing atmosphere.
A numerical analysis of the emission spectra was carried out
following the same approach used in [7,18,24]. The RL spectra were
resolved, using the Levenberg–Marquardt algorithm, into the
Gaussian components reported in Table 1. All the parameters were
allowed to vary within 0.01 eV from the reported value. With
respect to our previous work, two more bands were introduced
in the fitting process: one at 3.1 eV (FWHM 0.89 eV) and one at
3.7 eV (FWHM 0.45 eV) which were labelled as X and M band,
respectively. The presence of the X band was required in order to
obtain a fully satisfactory numerical analysis in the range between
3.0 eV and 3.5 eV. Indeed, low temperature RL measurements evi-
denced the presence of a band close to 3.1 eV in both natural and
synthetic quartzes. Assuming that the contribution of this band
could account for the discrepancy between the Gaussian fits and
the experimental curve, we tentatively added it to the deconvolu-
tion analysis. The M band was necessary only to deconvolve the
spectra of the samples annealed at temperature higher than
600 °C (see the next section).

4. Results

High temperature annealing is known to strongly affect the

luminescence characteristics of quartz [23]. We used RL measure-
ments to systematically investigate the effect of both annealing
atmosphere and temperature on the emission bands of quartz.

4.1. Effect of annealing atmosphere

In a first experiment a set of K-2-00 powders (100–200 lm)

were annealed at 600 °C for 5 h in different controlled atmosphere
as described in the previous section. In Fig. 6 the RL spectra of the
annealed samples are reported as a function of energy. The spec-
trum of the unannealed sample is also shown as a reference.
Regardless the annealing atmosphere, the RL spectra are character-
ized by a composite emission. Two main components are found to
be enhanced by the thermal treatments: an emission with an Fig. 7. Sequence of 40 consecutive radioluminescence measurements on a natural
apparent maximum around 2.7 eV, and not detected in the unan- pegmatitic quartz (K-2-00) powders annealed in Oxygen atmosphere at 600 °C for
nealed sample, dominates the blue region of the annealed quartzes 5 h. For readability sake only three spectra are reported.
 M. Martini et al. / Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21 19

Fig. 8. Radioluminescence of a natural pegmatitic quartz (K-2-00) powders

annealed in controlled atmosphere at 600 °C for 5 h. The reported spectra are the
Fig. 9. Dose dependence of the A (2.5 eV), B (2.8 eV) and X (3.1 eV) radiolumines-
last one out of a sequence of 40 consecutive measurements.
cence bands intensity in a natural pegmatitic quartz (K-2-00) powder annealed in
Oxygen at 600 °C for 5 h.

A detailed investigation on the irradiation effect on the inten-

The effect of the annealing on the RL spectra of the smoky and
sity of the bands was carried out on the quartz annealed in Oxygen.
colourless natural quartz turned out to be qualitatively similar
Fig. 9 reports the area of three of the Gaussian components
(Fig. 11 reports some of the spectra collected for the annealed
obtained from the numerical analysis as a function of the
accumulated dose. As expected from the RL spectra, the B band batch of smoky quartz). In particular, the samples annealed at tem-
peratures between 400 °C and 600 °C showed a dramatic enhance-
progressively decreases under continuous X-ray irradiation. How-
ever, the numerical deconvolution of the spectra evidences a com- ment of the C band (3.4 eV) which becomes the dominant emission
component. The maximum sensitization was observed for samples
plex dose dependence of the A band intensity. In fact, in the first
irradiation stage (up to 70 Gy approximately), the band intensity annealed at 500 °C since a treatment at higher temperature caused
a reduction of such emission band intensity. The sensitization of
is sensibly reduced. At higher dose the band increases and, above
100 Gy, the growth becomes linear. The 3.1 eV emission (X band) the C band was found to be most effective in the smoky quartz
whereas no effect at all was observed in the synthetic one. For
is enhanced by X-ray irradiation reaching a saturation level at
100 Gy. It is interesting to note that the increase of the A band annealing temperature higher than 700 °C the RL spectra of both
natural samples showed an increase of the emission in the 3.5–
starts as soon as the X band has reached the saturation level. A sim-
ilar correlation between the A and X bands is observed also in the 4.0 eV range. The numerical analyses evidenced that this is due
to a Gaussian component at 3.7 eV (labelled as M band) whose
untreated sample (Fig. 10) where, again, the growth of the A band
becomes linear as soon as the X band intensity has stabilized after intensity reaches its maximum in samples annealed at 1000 °C
and is reduced when the annealing temperature is further in-
an early increase under irradiation. Finally, the remaining compo-
creased. The effect of annealing on the RL spectrum of synthetic
nents, in particular the D band, turned out to be not significantly
quartz is significantly different from the one observed in natural
affected by irradiation.
samples. In particular, no evidence of either C or M band was
found. Moreover no relevant modification of the RL spectrum
4.2. Effect of annealing temperature was detected for annealing temperature below 900 °C whereas,
at higher temperature, an increase of the A, B and D bands was
A second experiment was carried out in order to investigate the
effect of the annealing temperature on the RL spectrum of different
types of quartz. Powders obtained from single crystals of a natural
colourless quartz, a natural smoky one, and a synthetic (Sawyer
Premium Quality) one were considered. For each quartz type,
different batches were annealed at different temperatures as
described in the Materials and Methods section. A RL spectrum
was then collected for each annealed sample and deconvolved into
Gaussian components.

Table 1
Parameter of the Gaussian components used in the numerical deconvolution of the
radioluminescence spectra of quartz samples.

Band Wavelength (nm) Energy (eV) FWHM (eV)

O 635 1.92 0.39
A 490 2.51 0.46
B 440 2.79 0.46
X 395 3.06 0.89
C 360 3.42 0.58
M 330 3.73 0.45
D 315 3.93 0.49 Fig. 10. Dose dependence of the A (2.5 eV) and X (3.1 eV) radioluminescence bands
intensity in an untreated natural pegmatitic quartz (K-2-00) powder.
20 M. Martini et al. / Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21
Fig. 11. Radioluminescence spectra of a natural smoky quartz powders annealed in
air at different temperatures for 10 min.
observed. The intensity of the 3.4 eV (C band) and 3.7 eV (M band)
bands obtained from the Gaussian deconvolution are reported in
Figs. 12 and 13, respectively, as a function of the annealing
temperature.
5. Discussion
The assignment of a luminescence emission band to a specific
quartz defect has long been the weakest point in the discussion
of many papers found in the literature. The unambiguous identifi-
cation of a defect to a recombination centre (or to a trap) requires
the combined use of different experimental techniques (for exam-
ple thermoluminescence, optical absorption, photoluminescence,
ESR, etc.). Unfortunately, however, matching the experimental data
and obtaining their coherent interpretation is often not as straight-
forward. This often leaves the field to speculations that, in the long
run, can be misleading in further investigations. In the case of
quartz, the identification of defects involved in the luminescence
dynamics is particularly tricky because of the different varieties
of crystals, either natural or synthetic. Quartzes of different origin,
in fact, contain different amounts of intrinsic and extrinsic ions
(Al, alkali ions, and hydrogen in particular). Moreover, the relative
concentration of defects can be altered by radiation and/or thermal
treatment also because of high ion mobility.
Fig. 12. Annealing temperature dependence of the C (3.4 eV) radioluminecence
band for three different types of quartz powders.
Fig. 13. Annealing temperature dependence of the M (3.7 eV) radioluminecence
band for three different types of quartz powders.
From the data reported in this paper and in recent publications
[7,18,24] some conclusions can be drawn, particularly thanks to a
better defined picture of radioluminescence mechanisms. The first
important result is that it has been demonstrated that all RL spec-
tra, both in natural and in synthetic quartz, are composed of the
same luminescence emissions, as shown in Fig. 1 (from Ref. [18]).
Most papers in the literature report a blue emission as the main
recombination centre in the TSL glow curves. We found always a
blue luminescence in the RL spectra of unswept synthetic and nat-
ural quartz and clearly demonstrated that two bands, labelled as A
and B, at 2.5 eV and 2.8 eV respectively, contribute to this emis-
sion. A perfect agreement between the growth with irradiation of
the A RL emission and of the 110 °C TL peak has been shown, see
Fig. 4 (from Ref. [7]).
The 110 °C TSL peak is also increased through a procedure sim-
ilar to the so called pre-dose, a series of irradiation followed by
heat treatments [25,26]. This TL growth has been clearly related
to the growth of a further RL emission band, the C emission at
3.4 eV, see Fig. 5. It is then clear that the same quartz crystal can
alternatively strongly emit, both in RL and TL, in the blue (A band)
or in the UV (C band), depending on the treatments it has been sub-
mitted to. It is not easy to correlate these changes to specific
recombination centres, but an indication of the role of Al-related
centres (charge compensated substitutional Al) comes from some
experimental results. Figs. 2 and 3 summarize the effects due to
the reduction of the concentration of alkali ions (‘‘sweeping’’) on
RL and OSL emissions: it is evident that most RL bands disappear
after a ‘‘sweeping’’ procedure and similarly a reduction in the
intensity of OSL is seen in swept out samples.
As already discussed by Halliburton et al. [13], the modifica-
tions that occur et al. centres are at the basis of most luminescence
emissions. Martini et al. [14], through high temperature treatment,
induced substitutional Al3+ ions to be charge compensated by a
hole, giving rise to the [AlO4]0 centre. This latter has been proposed
as the recombination centre responsible for the main UV emission
in TSL, that has been identified as the C band, at 3.4 eV [7].
Jani et al. [27] reported a correlation between the growth of the
E01 centre and the decay of the [AlO4]0 centre and observed that
sweeping out the alkali ions strongly reduces the intensity of the
E01 ESR signal. Poolton et al. [28] suggested that E01 may act as
non-radiative centre competing in OSL with the [AlO4]0 recombina-
tion centre, while a good correlation between the growth of E01 and
of [AlO4]0 was found by Usami et al. [29]. Then E01 centre has not
been clearly identified in its role in indirectly contributing to the
 M. Martini et al. / Nuclear Instruments and Methods in Physics Research B 327 (2014) 15–21
luminescence processes. Some indications could come from the ef-
fect of high temperature annealing in different atmosphere. Look-
ing at Figs. 6–8 the presence of O is seen to enhance both the blue
and the UV emissions. Specifically, in the blue region, both A and B
bands are induced by the thermal treatments; in the UV region, the
D band at 3.9 eV is mainly enhanced. Furthermore, a confirmation
of the effect of irradiation came from the growth of the A band at
2.5 eV clearly seen in Fig. 8: whatever the atmosphere of treat-
ment, after a series of irradiation this band increases of the same
amount.
Despite the assignment of the emission bands detected in RL to
a particular defect remains matter of investigation, some interest-
ing considerations, based on our results, can be done suggesting
possible correlations that can constitute a clue for further studies.
In particular, the evolution of the RL band intensities of both an-
nealed and untreated samples under irradiation show some com-
mon features. The fact that both the A and X bands intensities
evidence a clear change in the cumulative dose dependence after
about 100 Gy suggests some kind of correlation between them.
Unfortunately, until the exact nature of the related defects is iden-
tified, it is not possible to determine whether this correlation is due
to a simple competition in charge capture or if some more complex
interaction or spatial correlation is implied. Whatever the nature of
the correlation between the A and X bands, however, it is interest-
ing to notice that the B band seems not to be involved in it. The B
band intensity in the annealed samples, in fact, is progressively
reduced by irradiation with no evidence of a discontinuity at about
100 Gy of cumulative dose.
If we now consider the RL spectra as a function of the annealing
temperature, our results point out, one more time, the complexity
of the mechanisms involved in quartz luminescence. In fact, not
only the emission spectrum is due to the contribution of several
Gaussian component, but how such bands are affected by the ther-
mal treatments depends on the specific emission. Despite that, the
set of RL measurements carried out on different types of quartz
allowed to highlight the common and most relevant features. Of
particular interest is how the annealing temperature affects the C
band emitting at 3.4 eV. Such band was proven to be detected also
in TSL and to be activated by a heating following an irradiation like
in the pre-dose sequence. The fact that an annealing at 500 °C
could induce the C band only in natural samples is a further indi-
cation of its extrinsic nature, being the concentration of Al and
alkali ions orders of magnitude lower in synthetic quartz.
A further important result is related to the presence of a new
emission band in the UV region, specifically the M band emitting
at 3.7 eV, in samples annealed at temperatures higher than
700 °C. As we have already observed for the so called blue emission
which was found to be composite, the same holds for the UV
quartz emission. At least three emission components, specifically
the C, D and M band contribute to the RL emission in the high
energy range. The UV quartz emission has long been reported in
the literature, however, referring to the high energy emission of
quartz with a not better defined ‘‘UV emission’’, could be mislead-
ing since each of the involved components is related to a different
luminescent centre which is differently affected by irradiation or
thermal treatments. The effect of the annealing temperature on
the RL spectrum of quartz was already reported in [23] and an
overall good agreement with our results is evidenced. The authors,
however, report of a single UV emission centred around 360 nm
whose dependence on the annealing temperature is compatible
with the sum of C and M bands. It is possible that many results
reported insofar on the UV emission in quartz do not always refer
to the same luminescence band due to the strong overlapping of
the emissions. We remind however that a luminescence band
21
detected in RL is not necessarily involved in the TSL mechanism.
Further detailed investigations featuring a deconvolution of TSL
spectra are thus required in order to determine whether the bands
reported in Table 1, beside A and C, are detected in TSL.
6. Conclusions
Although the assignment of the luminescence emissions to spe-
cific defect centres in quartz is still undefined, a thorough analysis
of the RL emissions and their response to irradiation and thermal
treatments turned out to be very useful in understanding many
features. Specifically, the presence of the same emission bands in
natural and synthetic quartz and their dependence on the presence
of extrinsic impurities is a common characteristic which confirms
the role of Al centres in the luminescence properties of quartz.
From the measurements presented in this paper the composite
nature of the ‘‘blue’’ emission is confirmed. Two bands labelled as A
at 2.5 eV and B at 2.8 eV contribute to the emission in this region,
their behaviour being different as a function of irradiation, the A
band featuring a growth with irradiation in perfect agreement with
the growth of the 110 °C TSL peak.
More complex is the picture in the UV region, where besides the
already detected C and D bands at 3.4 eV and 3.9 eV, respectively,
two further emissions have been detected at 3.1 eV and 3.7 eV. This
latter is seen to be strongly enhanced by high temperature treat-
ments, its intensity reaching its highest value after an annealing
at around 1000 °C, while it is seen that the C band increases in
intensity after annealing at around 500 °C, followed by a decrease.
In the light of these results a number of already known features
should be reconsidered.
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