Radiation Measurements 77 (2015) 18e25

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Radiation Measurements
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Synthesis and TLeOSL studies in Cu activated lithium silicate

R.A. Barve a, *, R.R. Patil a, S.V. Moharil b, B.C. Bhatt c, M.S. Kulkarni d
a
Govt. Institute of Science, Nagpur, India
b
R.T.M Nagpur University, Nagpur, India
c
Bhabha Atomic Research Centre, Mumbai, India
d
Radiological Protection and Advisory Division, BARC, Mumbai, India

h i g h l i g h t s

X-rd analysis confirms the formation of mixed phases of Li4SiO4 and Li2SiO3.

Relative contribution of the phases changes with the change in heating atmosphere.

Luminescent properties are found to be affected due to change in heating atmosphere.

Intense OSL is observed in the samples heated under vacuum.

The CW-OSL sensitivity is comparable to that of the commercial Alumina.

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

Article history: Cu doped Lithium silicate was synthesized by reacting the corresponding salts under acidic medium. The
Received 1 December 2014 XRD analysis confirms the formation of mixed phase compound of (Li4SiO4)1xe(Li2SiO3)x. The sample
Received in revised form heated in air with NH4F as a flux is rich in the orthosilicate phase whereas the sample heated in vacuum
19 April 2015
is rich in the metasilicate phase. The relative contribution of these two phases was found to be altered
Accepted 20 April 2015
Available online 23 April 2015
with the change in heating atmosphere and thus affects the luminescent properties significantly. The
sample rich in the Li4SiO4 phase shows Cuþ emission whereas no emission is observed in the metasilicate
phase. Intense OSL (optically stimulated luminescence) was observed in the Cu doped vacuum heated
Keywords:
Lithium silicate
sample. The sensitivity was found to be 85% of that of the commercial Alumina. Hence it can be explored
Co-precipitation further as an OSL phosphor for the dosimetric applications.
OSL © 2015 Elsevier Ltd. All rights reserved.
Luminescence
Radiation dosimetry

1. Introduction
Silicates are the class of materials which are being widely used
as an ionic conductor thin film (Furusawa et al., 2008, 2009) in
fabrication of solid state electrolyte and as anode electrode material
for Li ion batteries (Tomita et al., 2004; Abe et al., 2007) for the
fabrication of gas sensors (Fergus, 2008). Amongst various silicates,
lithium silicates are in huge demand for its use as a concrete
hardener because it deeply penetrates and seals the existing
hardened floors. Li4SiO4 has also been fabricated as a ceramic
membrane (Nair et al., 2009) and other forms (Escobedo Bretado
et al., 2005; Gauer and Heschel, 2006) for carbon dioxide
* Corresponding author. Present address: Radiological Safety Division, IGCAR,
Kalpakkam, Tamil Nadu, India.
E-mail address: rujuta_barve2003@yahoo.com (R.A. Barve).
absorbent. Li4SiO4 can absorb CO2 up to 1/3rd of its weight which is
of special value for the fossil fuel industries. Substituting Si4þ by an
aliovalent species like P4þ Li4SiO4 enhances the ionic conductivity
to be used for high temperature battery applications (Robertson
et al., 1997). Li2SiO3 and Li4SiO4 are being widely used because of
good tritium solubility and due to the adequate thermo-physical,
chemical and mechanical stability at high temperatures (Peiffer
et al., 1998; Raffray et al., 1995). They have been investigated as
breeder materials for nuclear fusion reactors; in addition to other
more well-known applications such as in low thermal expansion
glass-ceramics used in ceramic hobs (Klix et al., 2005; Wen et al.,
2007; Yamaguchi et al., 2007; Essaki et al., 2006).
The detailed study on the thermal stability of these lithium
silicates is well reported by Cruz et al. (2006). Li2SiO3 crystallizes
into orthorhombic structure having space group Cmc21(36) with
lattice parameters a ¼ 9.392 Å (2), b ¼ 5.397 Å (2), C ¼ 4.660 Å (1).
The lithium atom is tetrahedrally coordinated with a mean Li e O

http://dx.doi.org/10.1016/j.radmeas.2015.04.016
1350-4487/© 2015 Elsevier Ltd. All rights reserved.
 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25
distance of 2 Å (Hesse, 1977). Lithium orthosilicate (Li4SiO4) exists
in two stable phases: below 665  C it exists in the monoclinic
phase; above 665  C it exists in the quasi-orthorhombic phase.
However, the transformation at 665  C is displacive, with very little
volume change, and is not a restriction on the adoption of Li4SiO4 as
a blanket material. The crystal structure of Li4SiO4 at room tem-
perature is monoclinic; with a space group P2/m and lattice pa-
rameters a ¼ 11.546 Å, b ¼ 6.090 Å, c ¼ 16.645 Å (Cha-Yang et al.,
1989).
Moreover, silicates are also regarded as an excellent host for
luminescent ions due to their high chemical and thermal stability.
More recently, Li2SiO3 is found to be a good candidate for lumi-
nescent devices (Naik et al., 2009; Morimoto et al., 2008). Ma et al.
(2012) has reported the electronic as well as luminescent proper-
ties of RE (rare earth) doped LiSON which acts as a potential
phosphor for UV based white LEDs. Attempts were also made by
researchers to develop Li based orthosilicates. Zhang et al. (2008)
have studied the photoluminescence properties of Li2SrSiO4:
Eu2þ, Ce3þ which exhibits blueeyellow emission and hence can act
as a potential white light emitting phosphors for UV-LEDs. Recently,
Rao et al. (2011) synthesized a new red phosphor Li2SrSiO4: Pr3þ
which is also found to be a potential candidate as a blue light
converter in the fabrication of white LEDs. Mohapatra et al. (2009)
and Alagu Raju et al. (2009) have reported the luminescent prop-
erties of some rare earth doped lithium meta-silicates in order to
develop this material as a potential OSL phosphor. Li2SiO3
(Zeff ¼ 10.5) and Li4SiO4 (Zeff ¼ 9.04) being a low Z material may
find application in the field of radiation dosimetry.
In the earlier studies lithium silicates have been synthesized
using different techniques like solegel (Klein, 1998; Li et al., 1995,
2011), combustion synthesis (Cruz and Bulbulian, 2003), solid
state (Tao et al., 2010) etc. Mondrago n Gutíerrez et al. (2008) have
reported the synthesis of Li2SiO3 using different Li:Si ratios carried
out at low temperature in the presence of urea solution. Recently,
Ortiz-Landeros et al. (2011) made an attempt to synthesize nano-
crystalline Li2SiO3 using hydrothermal method in the presence of
various surfactants. Herein, we report the luminescent properties
of Cu doped lithium silicate synthesized using a co-precipitation
technique which is one of the simplest and most cost effective
techniques. Thermo-luminescence (TL) and OSL (optically stimu-
lated luminescence) properties studied in this material are also
presented in this work.
2. Experimental
Lithium silicate was synthesized by reacting lithium sulphate
and sodium metasilicate under an acidic medium. The obtained
precipitate was filtered and washed thoroughly with double-
distilled water. It was then allowed to dry under the drying lamp
for several hours to remove excess water. The desired amount of
dried powder was taken and a CuCl2 solution along with NH4F
powder was added to it. The excess amount of water was removed
by allowing the wet mixture to dry for several hours under the
drying lamp. This processed sample was then heated at 700  C for
2 h and immediately quenched at room temperature. Several
samples with varying concentration of Cu in the range
0.01e0.5 mol% were prepared. However, the sample with 0.05 mol%
Cu impurity concentration yielded the maximum photo-
luminescence. Hence this concentration is referred to as the opti-
mized concentration and samples with this concentration were
chosen for further study. In a similar way the concentration of NH4F
used as a flux was optimized to 60 mol%. The effect of co-doping of
trivalent and pentavalent impurities (in the form of Al and P
respectively) on the Cu luminescence was also studied. Like Cu,
several samples with varying concentration of Al and P in the range
19
0.1e2 mol% were prepared. Out of several samples, the best prop-
erties were obtained for 1 mol% of Al and P respectively and hence
the properties discussed further are for this concentration of Al and
P.
Photoluminescence studies were carried out on a Hitachi e
4000 Spectrofluorometer. A xenon lamp was used as an excitation
source for the PL studies. OSL and TL response was studied on the
fabricated setup as described elsewhere (Kulkarni et al., 2007). For
studying the TL/OSL response, all the samples were exposed to a
test dose of 100 mGy using 90Sr/90Y beta source with the dose rate
of 20 mGy per min. All the samples were mass normalized and the
measurements were carried out under identical experimental
conditions. Two optical filters viz. UG-1 (across PMT), to prevent
stimulation signal from reaching the PMT (9111B, 25 mm diameter
end window PMT) and GG-435 (across LEDs), to cut-off the stim-
ulation wavelengths below 435 nm, were used in the assembly.
During all the OSL measurements the LED power was kept at
11 mW/cm2 and signal was recorded for 200 s with the acquisition
time 0.1 s. All the thermo-luminescence measurements were taken
at the heating rate 4  C/s. The TL was recorded in air atmosphere
with HA-3 filter used on the PMT side. The details regarding the
uncertainty in the temperature measurement are discussed else-
where (Kulkarni et al., 2007).
3. Results and discussion
3.1. X-ray diffraction analysis
To confirm the formation of the target compound, X-ray
diffraction analysis of the pure sample heated at 700  C for two
hours is performed (Fig. 1a). The X-ray diffraction pattern in-
dicates the formation of a mixed-phase compound having a major
phase of Li2SiO3 (JCPDS File No. 83-1517) with a minor phase of
Li4SiO4 (JCPDS File No. 86-0551). Since only high intensity lines
are observed and low intensity lines are absent, it can be
concluded that the Li4SiO4 phase is present in small amounts. The
occurrence of this phase can be attributed to insufficient reaction
between lithium and silicon compounds at this particular tem-
perature. A Cu doped sample synthesized in this way does not
yield Cuþ emission. Thus to incorporate Cu into the lattice, NH4F is
used as a flux as it is well known that NH4F plays a key role in the
enhancement of luminescence intensity (Guo et al., 2010). Fig. 1b
shows the X-ray diffraction pattern of Cu doped lithium silicate
heated in air. This pattern matches with the pattern reported in
the ICDD database; (JCPDS File No. 86-0551). Heating the sample
with flux at 700  C increases the contribution of Li4SiO4 with
relatively lesser contribution from the minor phase of Li2SiO3. This
is in contrast to what was observed earlier. The observed changes
in the XRD pattern can be due to the incorporation of NH4F which
is also known to affect the structural properties of the host lattice
(Guo et al., 2010). Fig. 1c shows XRD pattern of vacuum heated
sample. Here also lines from both phases are seen. However, the
relative contribution of Li2SiO3 phase is more compared to air
heated sample (Fig. 1b) as can be seen from the comparison of
intensity of diffraction lines. This proves that change in the
heating atmosphere also has significant effect on the different
phase formation. Such changes also have significant effect on
several luminescent properties like Photoluminescence (PL),
Thermoluminescence (TL) and Optically Stimulated Luminescence
(OSL) which are discussed further in detail.
3.2. Photoluminescence properties
Fig. 2 shows the PL spectra of Cu, CuAl and CuP doped
(Li4SiO4)1xe(Li2SiO3)x heated in air with NH4F at 700  C for 2 h.
20 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25
Fig. 1. X-ray diffraction pattern of lithium silicate heated in air and under vacuum at
700  C. (a) Un-doped, (b) Cu-doped heated in air, (c) Cu-doped heated under vacuum.
Since, the addition of NH4F crystallizes lithium silicate in the
Li4SiO4 phase, the observed Cu emission can be attributed to the
Li4SiO4 phase. For the Cu doped sample, the emission is observed
Fig. 2. Photoluminescence spectra of Cu; CuAl and CuP doped (Li4SiO4)1xe(Li2SiO3)x
heated in air. (a) Excitation spectra of Cu-doped (Li4SiO4)1xe(Li2SiO3)x, (b) Excitation
spectra of CuAl doped (Li4SiO4)1xe(Li2SiO3)x, (c) Excitation spectra of CuP doped
(Li4SiO4)1xe(Li2SiO3)x, (d) Emission spectra of Cu-doped (Li4SiO4)1xe(Li2SiO3)x, (e)
Emission spectra of CuAl doped (Li4SiO4)1xe(Li2SiO3)x, (f) Emission spectra of CuP
doped (Li4SiO4)1xe(Li2SiO3)x.
around 358 nm (Fig. 2d) with the excitation at 254 nm (Fig. 2a).
When 1 mol% Al was co-doped with Cu, the PL intensity is found to
be reduced having emission (Fig. 2e) and excitation (Fig. 2b) at the
same position. Similar effect was observed on the Cu luminescence
when 1 mol% P was co-doped with Cu (Fig. 2f,c). The size of Cuþ
(0.1 Å) is nearly the same as Liþ and therefore it is expected to
occupy Liþ site without creating any change in the lattice structure.
However, a decrease in Cuþ fluorescence with Al3þ indicates that
Al3þ occupies the Si4þ site forcing Cuþ to change to Cu2þ.
The samples heated under vacuum do not exhibit Cu lumines-
cence. This suggests that Li2SiO3 phase is responsible for quenching
of Cu luminescence as the contribution of this phase is more in the
vacuum heated sample.
3.3. CW-OSL (continuous wave-OSL) and TL properties
Fig. 3 shows the CW-OSL response of Cu, CuAl and CuP doped
(Li4SiO4)1xe(Li2SiO3)x heated in air. The wavelength of stimulation
light source was 470 nm. The OSL signal of Cu doped sample decays
in 1 s (Fig. 3a). Addition of Al and P has no significant effect on the
OSL decay however, it influences the OSL sensitivity. The OSL signal
from the CuAl and CuP doped sample decays in 1.2 s and 1.5 s
(Fig. 3b,c) respectively. On the basis of an area integration method;
integrated over the time period of the initial 3 s, the OSL sensitivity
of the CuAl and CuP doped samples is found to be 1.1 and 2.4 times
the OSL sensitivity of the Cu doped sample.
Heating the samples under vacuum has profound effect on the
OSL decay as well as the sensitivity. Fig. 4 shows the OSL response of
Cu, CuAl and CuP doped (Li4SiO4)1xe(Li2SiO3)x heated under
vacuum. The OSL signal of the Cu doped sample decays in 3 s
(Fig. 4a). Addition of Al and P further slower the decay. The com-
plete signal decays in 6 s and 2.5 s (Fig. 4b,c) respectively. Unlike the
air heated Al and P co-doped samples, significant reduction in the
OSL sensitivity is observed in the case of vacuum heated samples.
On the basis of an area integration method; integrated over the
initial 3 s, the OSL sensitivity of the CuAl and CuP doped samples is
found to be 0.67 and 0.78 times the OSL sensitivity of the Cu doped
sample.
The sensitivities of these samples are also compared with
Al2O3:C from Landauer, Inc. Since the decay of the two phosphors is
different, the comparison is done on the basis of an area integration
method; integrated over the initial 3 s (Yukihara et al., 2004). Fig. 5
shows the OSL response of Cu doped (Li4SiO4)1xe(Li2SiO3)x heated
under vacuum. Inset shows the OSL response of Al2O3:C. Table 1
summarizes the CW-OSL comparison of various
(Li4SiO4)1xe(Li2SiO3)x samples with Al2O3:C.
From Table 1 it can be observed that the OSL sensitivity of the
vacuum heated samples is more than that of the samples heated in
air. Increase in the sensitivity of the vacuum heated samples can be
attributed to the increase in the relative contribution of Li2SiO3
phase which acts as a trapping centre imparting better OSL sensi-
tivity to the phosphor. Also, in case of samples heated in air,
incorporation of Al and P increases the number of defects respon-
sible for OSL increasing the OSL sensitivity. However, in the case of
vacuum heated samples incorporation of Al and P reduces the
number of defects responsible for OSL resulting in a decrease in the
OSL sensitivity. Thus, as observed in PL, change in the heating at-
mosphere also has significant effect on the CW-OSL properties of
the phosphor.
The minimum detectable dose of Cu and CuP doped vacuum
heated samples is also calculated. For the measurement, a 20 mGy
dose is given to the sample and the OSL of the sample is recorded
for the time period of 200 s. After bleaching the sample under blue
light, the background of the sample is recorded for 10 times for the
time period of 200 s. The minimum detectable dose (3s) in the case
 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25 21

Fig. 3. OSL response of Cu; CuAl and CuP doped (Li4SiO4)1xe(Li2SiO3)x heated in air. (a) OSL response of Cu-doped (Li4SiO4)1xe(Li2SiO3)x, (b) OSL response of CuAl doped
(Li4SiO4)1xe(Li2SiO3)x, (c) OSL response of CuP doped (Li4SiO4)1xe(Li2SiO3)x.

of Cu and CuP doped samples is around 0.85 mGy and 0.75 mGy
respectively on the described setup.
The dose response of the Cu and CuP doped samples is studied
in the range 10 mGy to 1 Gy beta doses. For each dose the OSL
measurement was taken at room temperature for 200 s. Plots of
OSL intensities as a function of absorbed dose are given in Fig. 6.
The response for both Cu (Fig. 6a) and CuP doped (Fig. 6b) samples
is found to be linear over the mentioned dose range.
Fig. 7 shows the thermo-luminescence responses of various
(Li4SiO4)1xe(Li2SiO3)x samples heated at 700  C for 2 h in air. The
Cu doped sample shows TL peaks at 90  C and 163  C respectively
with a broad shoulder peak around 340  C (Fig. 7a). With the
addition of Al, TL peaks are found to be shifted to the lower tem-
perature side. The TL peaks are observed at 85  C and 160  C
respectively (Fig. 7b). However, with the addition of P the TL peaks
are found to be shifted to the higher temperature side. Two TL

Fig. 4. OSL response of Cu; CuAl and CuP doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (a) OSL response of Cu-doped (Li4SiO4)1xe(Li2SiO3)x, (b) OSL response of CuAl doped
(Li4SiO4)1xe(Li2SiO3)x, (c) OSL response of CuP doped (Li4SiO4)1xe(Li2SiO3)x.
22 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25
Fig. 5. OSL response of Cu-doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum and
inset shows the OSL response of commercial Al2O3:C.
peaks at 98  C and 172  C (Fig. 7c) with a small shoulder peak at
150  C are observed. The integral TL area of the CuAl and CuP doped
samples is found to be 1.4 and 1.6 times that of the Cu doped
sample. This suggests that the incorporation of Al and P into the
host lattice introduces more TL sensitive traps resulting into
enhancement of the TL sensitivity.
Fig. 8 shows the thermo-luminescence response of various
(Li4SiO4)1xe(Li2SiO3)x samples heated under vacuum at 700  C for
2 h. Two TL peaks, one around 97  C and another around 381  C
having a shoulder at 288  C are observed in the Cu doped sample
(Fig. 8a, curve (i)). The TL sensitivity is found to be 0.7 times the
sensitivity of air heated sample. The Al co-doped sample shows an
intense TL peak at 100  C having a shoulder at 145  C and another
peak at 285  C (Fig. 8b, curve (i)). The TL sensitivity is found to be
0.32 times the sensitivity of the air heated sample. In the case of the
P co-doped sample, multiple TL peaks around 100  C, 140  C, 285  C
and 357  C are observed (Fig. 8c, curve (i)) and the TL sensitivity is
found to be 0.27 times the sensitivity of the air heated sample.
Unlike OSL, the TL sensitivity of the vacuum heated sample is
found to be reduced when compared with the sensitivity of the air
heated samples. The observed decrease in the TL sensitivity of the
vacuum heated samples can be attributed to a decrease in the
relative contribution of the Li4SiO4 phase which acts as a trapping
centre imparting TL sensitivity to the phosphor.
Fig. 8 also shows the TL response of the samples recorded after
recording OSL. In the case of the Cu doped sample, the TL recorded
after measuring OSL (Fig. 8a, curve (ii)) shows complete depletion
of the low temperature peak whereas the high temperature TL peak
observed at 381  C is found to be shifted to 389  C with the increase
in the peak intensity correlating the low temperature peak to the
observed OSL. The integral area of the high temperature peak is
found to be 1.5 times the integral area of the high temperature peak
of the TL recorded immediately after irradiation (Table 2). The
observed changes in the structure of the high temperature peak
suggest that carriers generated during OSL readout gets re-trapped
at the TL traps responsible for the TL peaks around 250e450  C.
Fig. 9 shows the CW-OSL response of Cu doped
(Li4SiO4)1xe(Li2SiO3)x recorded after thermally removing the low
Table 1
Comparison of CW-OSL sensitivity of various (Li4SiO4)1xe(Li2SiO3)x samples with Al2O3:C (Landauer).
BSL sensitivity of the samples heated in air
(Li4SiO4)1xe(Li2SiO3)x: Cu 0.13 times
(Li4SiO4)1x e(Li2SiO3)x: Cu, Al 0.15 times
(Li4SiO4)1xe(Li2SiO3)x: Cu, P 0.31 times
temperature peak. The integral OSL after depleting the low tem-
perature peak is found to be 91% of the original signal (Fig. 9a,b)
thereby indicating that 9% of the total signal is attributable to the
low temperature traps. Thus, 9% post irradiation fading can be ex-
pected due to these shallow traps. However, the observed, fading in
the sample is found to be 22% over the period of 192 h (Inset of
Fig. 9 (curve c,d)) which is somewhat greater than the expected
value. Fig. 8 also shows the TL taken after thermally removing the
low temperature peak; followed by taking OSL (Fig. 8a, curve (iii)).
The peak is found to be shifted back to 389  C similar to curve (i)
with the sensitivity comparable to that of curve (i).
However, in case of the Al co-doped sample, the TL recorded
after measuring OSL shows complete depletion of the low tem-
perature peak with the high temperature peak observed at 360  C.
The peaks between 150e250  C are found to be partially optically
sensitive; thus correlating all the peaks to the observed OSL (Fig. 8b,
curve (ii)). Fig. 10 shows the CW-OSL response of the Al co-doped
sample recorded after thermally depleting the low temperature
peak. The integral OSL obtained after depleting the low tempera-
ture peak is found to be 96% of the original signal (Fig. 10a,b)
thereby indicating that 4% of the total signal can be attributable to
the low temperature traps below 120  C. Since 4% is from the
shallow traps around 100  C, 4% post irradiation fading can be ex-
pected due to these shallow traps. The observed, fading in Al co-
doped sample is found to be 59% over the period of 192 h (Inset
of Fig. 10 (curve c,d)) which is much greater than the expected
value. The observation of significant OSL obtained after depleting
low temperature peak thermally suggests that the major contri-
bution to the total OSL is due to traps beyond 450  C. Fig. 8b also
shows the TL taken after thermally removing the low temperature
peak; followed by taking OSL (Fig. 8b, curve (iii)). This peak is also
found to be shifted at 320  C with the increase in the peak intensity
as compared to that of curve (i).
In the P co-doped sample, the TL recorded after taking OSL
shows the depletion of the low temperature peak whereas the high
temperature peak is found to be to be shifted to 360  C (Fig. 8c
curve (ii)) correlating the low temperature peak to the observed
OSL. The increase in the peak intensity of the high temperature
peak suggests that the carriers generated during optical stimulation
get re-trapped at the TL traps responsible for the TL peak around
360  C.
Fig. 11 shows the CW-OSL response of the P co-doped sample
taken after thermally depleting the low temperature peak. The
integral OSL obtained after depleting the low temperature peak is
found to be greater compared to the original signal (Fig. 11a,b)
thereby indicating that the carriers generated during thermal
stimulation gets partially re-trapped in the deep OSL traps. This
indicates that even if this low temperature peak fades completely
the OSL signal will fade by small amount. Thus negligible post-
irradiation fading could be expected in the sample. The observed,
fading in P co-doped sample is found to be 13% over the period of
192 h (Inset of Fig. 11 (curve c,d)). Fig. 8c also shows the TL taken
after thermally removing the low temperature peak; followed by
taking OSL (Fig. 8c, curve iii). The high temperature peak is
observed at same position as that of curve i but the integral area of
the high temperature peak is found to be 93% of that of the high
temperature peak of curve (i) (Table 2).
BSL sensitivity of the samples heated under vacuum
0.85 times
0.58 times
0.67 times
 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25
Fig. 6. Dose response of Cu and CuP doped (Li4SiO4)1xe(Li2SiO3)x heated under
vacuum. (a) Cu-doped (Li4SiO4)1xe(Li2SiO3)x, (b) CuP doped (Li4SiO4)1xe(Li2SiO3)x.
As discussed above, in the vacuum heated samples, significant
differences are observed in the expected and observed fading fac-
tor. The expected fading factors are calculated by recording the OSL
after heating the irradiated sample up to 120  C. However, some of
the traps beyond 120  C may be unstable and hence more amount
of signal fades away when the irradiated sample is stored at room
temperature for the period of 192 h from the time of irradiation.
Therefore the actual observed fading is even more than the ex-
pected fading as mentioned in the text.
Table 2 shows the integral TL area for various samples heated
under vacuum. In the case of the Al co-doped sample, the TL
Fig. 7. TL response of Cu; CuAl and CuP doped (Li4SiO4)1xe(Li2SiO3)x heated in air. (a)
Cu-doped (Li4SiO4)1xe(Li2SiO3)x, (b) Cu, Al doped (Li4SiO4)1xe(Li2SiO3)x, (c) Cu, P
doped (Li4SiO4)1xe(Li2SiO3)x.
23
Fig. 8. a: TL response of Cu-doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (i) TL
recorded immediately after irradiation, (ii) TL recorded after OSL readout, (iii) TL
recorded after depleting low temperature peak followed by OSL readout. b: TL
response of CuAl doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (i) TL recorded
immediately after irradiation, (ii) TL recorded after OSL readout, (iii) TL recorded after
depleting low temperature peak followed by OSL readout. c: TL response of CuP doped
(Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (i) TL recorded immediately after irra-
diation, (ii) TL recorded after OSL readout, (iii) TL recorded after depleting low tem-
perature peak followed by OSL readout.
integral area of the low temperature peak (0e200  C) is 2.3 times
that of the Cu-doped sample. This suggests that the Al doping in-
troduces more shallow traps resulting in a significant increase in
their contribution to the total TL as well as OSL compared to that in
the Cu doped sample. However, it also eliminates the deep traps
significantly resulting into decrease in the TL sensitivity of the
sample. The total TL integral area is found to be 45% of that of the Cu
doped sample. The enhancement in the low temperature peak in-
dicates the possibility of more fading in the Al co-doped sample
which is indeed observed. Significant reduction in the OSL also
suggests that some of the carriers corresponding to these peaks
which get stimulated during OSL readout either get recombined
non-radiatively or get re-trapped in the available traps responsible
24 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25

Table 2
Integral TL area of various (Li4SiO4)1xe(Li2SiO3)x samples heated in air and under vacuum.

S. no. Area under low Area under high Total integral area
temperature TL peak temperature TL peak

TL glow curves of Cu, CuAl and CuP doped (Li4SiO4)1x e(Li2SiO3)x heated in air
1. TL of Cu doped sample recorded immediately after irradiation 1989 337 2326
2. TL of CuAl doped sample recorded immediately after irradiation 3223 208 3431
3. TL of CuP doped sample recorded immediately after irradiation 3260 348 3608
TL glow curves of Cu doped (Li4SiO4)1x e(Lie2SiO3)x heated under vacuum
1. TL recorded immediately after irradiation 247 1465 1712
2. TL recorded after OSL readout 0 3149 3149
3. TL recorded after depleting low temperature peak; followed by its OSL readout 0 2613 2613
TL glow curves of CuAl doped (Li4SiO4)1x e(Lie2SiO3)x under vacuum
1. TL recorded immediately after irradiation 810 297 1107
2. TL recorded after OSL readout 44 387 431
3. TL recorded after depleting low temperature peak; followed by its OSL readout 31 494 525
TL glow curves of Cu, P doped (Li4SiO4)1x e(Lie2SiO3)x under vacuum
1. TL recorded immediately after irradiation 415 553 968
2. TL recorded after OSL readout 38 1080 1118
3. TL recorded after depleting low temperature peak; followed by its OSL readout 25 516 541

Fig. 9. OSL response of Cu doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (a) OSL Fig. 11. OSL response of CuP doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (a)
recorded immediately after irradiation, (b) OSL recorded after depleting low temper- OSL recorded immediately after irradiation, (b) OSL recorded after depleting low
ature peak, (c) (inset) OSL recorded immediately after irradiation, (d) (inset) OSL temperature peak, (c) (inset) OSL recorded immediately after irradiation, (d) (inset)
recorded after 192 h from the time of irradiation. OSL recorded after 192 h from the time of irradiation.

for TL. The experimental evidence of this fact is the appearance of

Fig. 10. OSL response of CuAl doped (Li4SiO4)1xe(Li2SiO3)x heated under vacuum. (a)
OSL recorded immediately after irradiation, (b) OSL recorded after depleting low
temperature peak, (c) (inset) OSL recorded immediately after irradiation, (d) (inset)
OSL recorded after 192 h from the time of irradiation.
an intense 350  C TL peak after OSL readout (Fig. 8b, curve ii;
Table 2).
In the case of the P co-doped sample, the total TL integral area is
found to be 39% of that of the Cu doped sample. This suggests
significant reduction of TL sensitive traps with the introduction of P
along with Cu. The integral area of the high temperature peak of the
TL recorded after OSL is found to be 1.9 times that of the TL recorded
immediately after irradiation (Table 2). This indicates that the
charge carriers corresponding to the traps beyond 450  C which get
stimulated during OSL readout get re-trapped in these traps. All
these observations suggest that the two types of traps are present
viz. traps amenable to OSL as well as TL; traps amenable to TL signal
which does not yield OSL.
As in the vacuum heated samples, the fading response of Cu,
CuAl and CuP doped lithium silicate samples heated in air is also
studied. However, intense fading is observed in all the three sam-
ples. The corresponding factors are found to be 80%, 95% and 93%
respectively. The presence of intense fading in the air heated
samples can be attributed to the observance of more intense OSL
sensitive low temperature peaks as compared to those observed in
the vacuum heated samples. From Table 2 it can be observed that
the integral area of the low temperature TL peaks of the Cu, CuAl
 R.A. Barve et al. / Radiation Measurements 77 (2015) 18e25
and CuP doped air heated samples is found to be 8.1, 4 and 7.9 times
the integral area of the low temperature TL peaks of the Cu, CuAl
and CuP doped samples heated under vacuum.
4. Conclusion
The study shows that lithium silicate could be synthesized by a
simple co-precipitation method with commonly available chem-
icals. Also, various impurities can be easily incorporated in the host
lattice. Samples prepared without NH4F flux always crystallize in
the metasilicate phase whereas samples prepared with NH4F flux
crystallizes in the orthosilicate phase. Intense OSL is observed in the
samples heated in air and under vacuum which is comparable to
that observed for commercial Al2O3:C. The OSL decay is very fast
and is influenced by Al and P doping. Heating the samples under
vacuum has remarkable effect on the TL/OSL properties. Amongst
the studied phosphors, the Cu-doped sample heated under vacuum
is found to be highly sensitive. Due to the fast decay, high sensi-
tivity, moderate fading and low Z (9.4), Cu doped lithium silicate
can be further explored as an OSL phosphor for the dosimetric
application.
Acknowledgement
The authors are grateful to B.R.N.S. (Sanction No. 2008/37/20)
for funding this work.
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