ARTICLE IN PRESS

Journal of Quantitative Spectroscopy &

Radiative Transfer 95 (2005) 373–386
www.elsevier.com/locate/jqsrt

Influence of titanium ions on optical properties of

AF–PbO–B2O3 glasses
P. Nageswara Raoa, C. Laxmi Kanthb, D. Krishna Raoa, N. Veeraiahc,
a
Department of Physics, Nagarjuna University, Nagarjuna Nagar-522 510, A.P., India
b
Department of Physics, P G College of Science, Osmania University, Saifabad, Hyderabad 500 004, India
c
Department of Physics, Nagarjuna University P.G. Centre, Nuzvid-521 201, A.P., India

Received 24 June 2004; accepted 16 November 2004

Abstract

AF–PbO–B2 O3 (where A ¼ Li, Na, K) glasses containing different concentrations of TiO2 ranging from
0 to 0.6 mol% were prepared. A variety of spectroscopic studies viz. infrared spectra, optical absorption,
ESR spectra and thermoluminescence have been carried out as a function of titanium ion concentration.
The results of these studies have been analyzed in the light of different oxidation states of titanium ions.
The comparison of the results of three series indicate the lithium series glasses are the better candidates for
the practical applications.
r 2005 Elsevier Ltd. All rights reserved.

Keywords: AF–PbO–B2 O3 glasses; Titanium ions; Spectroscopic studies

1. Introduction

Alkali fluoro borate glasses are well known due to their variety of applications in radiation
dosimetry, phosphorus, solar energy converters and in a number of electronic devices. These
glasses are relatively moisture resistant and possess better mechanical strength when compared
with pure borate glasses. The physical properties of these glasses can however be improved by the
addition of PbO to these glasses, since PbO has the ability to form stable glasses. Extensive studies
Corresponding author. Tel.: +91 86 56 23 5551; fax.: +91 86 56 23 5200.
E-mail address: nrv8@rediffmail.com (N. Veeraiah).

0022-4073/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jqsrt.2004.11.005
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374 P.N. Rao et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 95 (2005) 373–386

on the influence of different transition and rare earth ions on various properties like electrical,
ESR, optical, elastic properties of various alkali borate glasses are available [1–6]. Among various
transition metal-oxide-doped glasses, the titanium-oxide-doped glasses have gained much
importance in recent years due to their possible applications in non-linear optical devices such
as ultrafast switch and power limiter [7–9]. In general, titanium oxide is considered as a nucleating
agent of crystallization in silicate glasses. However, the presence of small quantities of TiO2 in the
other glass matrices is observed to enhance the glass forming ability and chemical durability of the
glasses [10]. Commonly, the ions of titanium, exist in the glass networks in Ti4þ state and
participate in the glass network forming with TiO4 ; TiO6 and some times with TiO5 (comprising
of trigonal bipyramids) structural units [11,12]. However, there are reports suggesting that these
ions may also exist in Ti3þ state in some other glass matrices like fluoroaluminate, zirconium
barium lanthanum sodium (ZBLAN) fluoride, etc. [13,14]. The empty or unfilled d-shells of Ti4þ
ions contribute more strongly to the non-linear polarizabilities. Further, the investigation on the
co-ordinate chemistry of titanium ions in alkali fluoro borate glass networks is of interest in itself,
because, the presence of these ions can have a dramatic effect on physical properties including
colour, chemical durability, mechanical and insulating strengths [15,16]. Thus the objective of the
present study is to investigate the role of titanium ions on the structural aspects of PbO–B2 O3
glasses mixed with three different alkali fluorides (viz. LiF, NaF and KF) by studying their
spectroscopic properties viz., optical absorption, ESR and IR spectra and also thermolumines-
cence studies.

2. Experimental methods

With in the glass-forming region of AF–PbO–B2 O3 : TiO2 glass system, the following particular
compositions with successive increase in the concentration of TiO2 (0 to 0.6 mol%) are chosen for
the present study:
20 AF–10 PbO-ð70  xÞ B2 O3 : x TiO2 (A ¼ Li, Na, K, x ¼ 0; 0.2, 0.4 and 0.6 and the samples
are labeled as AT0 ; AT2 ; AT4 ; and AT6 :
Appropriate amounts of Analar grade reagents of AF, PbO, H3 BO3 and TiO2 were thoroughly
mixed in an agate mortar and melted in a platinum crucible at 950  10 1C for about 1 h until a
bubble-free liquid was formed. The resultant melt was then cast in a brass mould and
subsequently annealed at 300 1C. Powder X-ray diffractometry (XRD) was used to examine all the
as-quenched melts to confirm the amorphous nature of the samples. The instrument used was X-
pert, Panalytical, Philips X-ray diffractometer fitted with copper target and nickel filter, operated
at 40 kV, 30 mA. The differential thermal analysis studies on these samples were carried out for
evaluating the glass transition temperature T g using TA instruments DTA 2010 differential
thermal analysis with a programmed heating rate of 20 1C/min in the temperature range of
30–550 1C to an accuracy  1 1C: The ESR spectra of the fine powders of the samples were
recorded at room temperature on JES SA 200 ðn ¼ 9:234 GHzÞ X-band ESR spectrometer with
100 kHz field modulation; the magnetic field was scanned from 0 to 5000 G. Infrared transmission
spectra for these glasses were recorded using a Perkin-Elmer 1600 Infrared Spectrophotometer in
the wavenumber range 400–4000 cm1 by KBr pellet method. The optical absorption spectra of
the present glasses were recorded at room temperature in the wavelength range 400–900 nm up to
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a resolution of 0.1 nm using Shimadzu-UV–VIS–NIR Spectrophotometer Model 3101. For

recording thermoluminescence emission, the glasses were irradiated with X-rays for 12 h with a
Norelco X-ray unit operated at 35 kV, 10 mA; thermoluminescence output of these glasses was
recorded with a heating rate of 1 1C/s, on a computerized Nucleonix-TL set up (Nucleonix Pvt.,
Ltd., Hyderabad). The glow peak temperature was determined to an accuracy of 1 1C:

3. Results

Various physical parameters such as total titanium (calculated as Ti4þ ions) ion concentration
N i ; mean titanium ion separation Ri ; are evaluated using the measured values of density d and the
calculated average molecular weight M for the present glasses and are presented in Table 1.
Differential thermal analysis traces (recorded between 30 and 550 1C) of AF– PbO–B2 O3 : TiO2
glasses have exhibited an endothermic effect due to glass transition temperature T g ; the values of
T g are evaluated from the point of inflection of this change and its variation with the
concentration of TiO2 is shown in Fig. 1 for all the series of glasses. The curves of all the three
series of glasses have exhibited an upward kink at x ¼ 0:2 mol% for the series of glasses.
The infrared transmission spectra of pure LiF–PbO–B2 O3 glasses recorded at room
temperature (Fig. 2) exhibit two groups of bands: (i) in the region 1200–1600 cm1 ; (ii) in the
region 900–1050 cm1 and an another band at about 715 cm1 : The second group of bands is
attributed to BO4 units where as the first group of bands is identified as being due to the stretching
relaxation of the B–O bond of the trigonal BO3 units and the band at 715 cm1 is due to the
bending of B–O–B linkages in the borate network [17,18]. It may be worth mentioning here that
the earlier studies on the IR spectra of various other glasses containing TiO2 indicate the presence
of a vibrational band at about 720 cm1 due to vibrations of TiO4 groups [19]. Hence, there is a

Table 1
Summary of data on various physical parameters of AF–PbO–B2 O3 : TiO2 glasses

Glass Conc. TiO2 (mol%) Density ðg=cm3 Þ Avg.mol.wt. (M) Conc. Ti ions Inter ionic distance
Ni ð1021 ions/cm3 ) of Ti ions Ri ðA Þ

LT0 0.0 2.561 76.23 — —

LT2 0.2 2.667 76.25 4.21 6.19
LT4 0.4 2.944 76.27 9.29 4.75
LT6 0.6 3.206 76.29 15.18 4.03

NT0 0.0 2.532 79.44 — —

NT2 0.2 2.458 79.46 3.72 6.45
NT4 0.4 2.596 79.48 7.86 5.02
NT6 0.6 2.641 79.50 12.00 4.36

KT0 0.0 2.515 86.27 — —

KT2 0.2 2.391 82.68 3.48 6.59
KT4 0.4 2.554 82.71 7.43 5.12
KT6 0.6 2.574 82.72 11.24 4.46
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450

LT
KT
Tg (°C)

400

NT

350
0 0.2 0.4 0.6
Concentration of TiO2 (mol%)

Fig. 1. Variation of the glass transition temperature T g with the concentration of TiO2 of AF–PbO–B2 O3 glasses.

LT6
410
710
Transimittance (%)

730 618 LT4

410
1064
LT2
626
725 410
LT0
1310 1036 715 638 410
1014 710
1364
1372 1042

1336

1900 1500 1100 700 300

Wavenumber (cm−1)

Fig. 2. IR spectra of LiF–PbO–B2 O3 glasses doped with different concentrations of TiO2 :

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possibility for the formation of single boron–oxygen–titanium framework in the glass network.
With the introduction of TiO2 (0.2 mol%) in to the AF–PbO–B2 O3 glass network, the intensity of
vibrations of BO4 groups is observed to increase with the shifting of meta-centre (from 1060 cm1 )
towards lower wavenumber ð1030 cm1 Þ; where as the intensity of band due to the vibrations of
BO3 groups is observed to decrease with the shifting of the meta-centre towards higher
wavenumber (Table 2). However, when the concentration of TiO2 is increased beyond 0.2 mol%,
the intensity variation of these two bands with the concentration of TiO2 exhibited a reversed
trend. The spectrum of LT2 glass has exhibited a broad band at 725 cm1 (normally identified due
to vibrations of TiO4 groups, in this case it may be assumed due to the vibrations of B–O–Ti
linkages) and another band at 650 cm1 (identified due to Ti–O–Ti symmetric stretching
vibrations of TiO6 structural units [20]. With increase in the concentration of TiO2 from 0.2 to
0.4 mol%, the intensity of band due to B–O–Ti linkages is observed to decrease with shifting of
meta-centre towards higher wavenumber and splitting of the common meta-centre is observed at
about 0.6 mol% of TiO2 : The intensity of band due to TiO6 structural units is observed to increase
gradually when the concentration of TiO2 in the glass matrix is increased from 0.2 to 0.6 mol%
with the shifting of meta-centre towards lower wavenumber. The IR spectra of other two series of
the glasses have exhibited a similar behaviour. However the comparison shows, for a given
concentration of TiO2 ; the NaF modifier glass to possess the highest intensity of the band due to
TiO6 structural units (Fig. 3). Further, the IR spectra of all the glasses exhibited absorption band
at 410 cm1 (assigned to PbO4 structural vibrations [21]).
The ESR spectra, recorded at room temperature for AF–PbO–B2 O3 : TiO2 glasses under
investigation exhibit a weak asymmetric signal with g ¼ 1:932; 1.93 and 1.928, respectively for LT,
NT and KT glasses. The considerable intensity of the signal is observed in all the three series of
glasses only when the concentration of TiO2 is around 0.4 mol%, With further increase in the

Table 2
Summary of data on the positions of various IR bands for AF–PbO–B2 O3 : TiO2 glasses

Glass BO3 units ðcm1 Þ BO4 units TiO4 units B–O–Ti units TiO6 units PbO4 units
ðcm1 Þ ðcm1 Þ ðcm1 Þ ðcm1 Þ ðcm1 Þ

Glass LT0 1336 1042 — 710 — 410

Glass LT2 1372 1014 — 715 648 410
Glass LT4 1364 1036 — 725 640 410
Glass LT6 1310 1064 730 710 618 410

Glass NT0 1352 1089 — 715 — 410

Glass NT2 1406 1060 — 724 630 410
Glass NT4 1383 1078 — 741 625 410
Glass NT6 1330 1125 738 712 613 410

Glass KT0 1344 1055 — 710 — 410

Glass KT2 1391 1026 — 719 640 410
Glass KT4 1372 1040 — 732 630 410
Glass KT6 1321 1077 734 710 615 410
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TiO4

Relative intensity
LT
KT
NT

TiO6
LT
KT
NT
0.1 0.3 0.5

Concentration of TiO2 ( mol%)

Transmittance (%)

NT2
410
712 613
738
1125 410

710 615 KT2

1330 734
1077 410
730 618
132 710 LT2
1064

1310

1850 1450 1050 650 250

Wavenumber (cm−1)

Fig. 3. IR spectra of AF–PbO–B2 O3 glasses doped with 0.2 mol% of TiO2 : Inset shows the variation of the intensity of
TiO4 and TiO6 units with the concentration of TiO2 :

content of TiO2 (0.6 mol%) an increase in the half-width of the signal is observed for all the three
series of glasses. However, among the three series of glasses (for a given concentration of TiO2 )
the weak intensity of the signal is observed for LT2 glasses. Fig. 4 represents ESR spectra of all the
series of glasses containing 0.4 mol% TiO2 :
Fig. 5a shows the optical absorption spectra of LiF–PbO–B2 O3 glasses containing different
concentration of TiO2 recorded at room temperature in the wavelength region 400–800 nm; the
spectrum of LT2 glass has exhibited two absorption bands at about 696 and 692 nm. When the
concentration of TiO2 is increased from 0.2 to 0.6 mol%, there is a considerable increase in the
intensity of these bands. The comparison plot of optical absorption with the concentration of
TiO2 for the three series of the glasses shows the highest intensity of these two bands for NT series
(Fig. 5b). The details of the optical absorption data of these glasses are given in Table 3.
Fig. 6 represents the thermoluminescence (TL) glow curves of LiF–PbO–B2 O3 : TiO2 glasses.
The LT0 glass exhibits a TL peak at 560 K. The doping of titanium oxide (0.2 mol%) caused a
considerable decrease in the TL light output. With further increase the concentration of TiO2
ð40:2Þ a gradual hike in the TL light output with the shifting of peak positions towards higher
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LT4
g = 1.932 KT4 g = 1.93 g = 1.928
NT4
Intensity (rel. units)

200 300 400 500 200 300 400 500 200 300 400 500
H (mT) H (mT) H (mT)

Fig. 4. ESR spectra (recorded at room temperature) of AF–PbO–B2 O3 glasses containing 0.4% concentration of TiO2 :

2 2
2 2 B2g B1g
B2g B1g
2 2
2 2 B2g A1g
B2g A1g
Optical density
Optical density

LT6 NT6
KT6
LT2 LT4 LT6

LT0

400 600 800 400 500 600 700 800 900

(a) Wavelength (nm) (b) Wavelength (nm)

Fig. 5. (a) Optical absorption spectra of LiF–PbO–B2 O3 glasses containing different concentration of TiO2 ; (b) optical
absorption spectra AF–PbO–B2 O3 glasses containing 0.6% concentration of TiO2 :

Table 3
Summary of data on the positions of optical absorption bands of AF–PbO–B2 O3 : TiO2 glasses
2
Glass B2g !2 B1g (nm) 2
B2g !2 A1g (nm)

LT NT KT LT NT KT

Glass T2 496 515 511 692 704 697

Glass T4 510 519 516 698 713 705
Glass T6 515 523 520 710 722 714
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Intensity (rel. units)

1800 NT4
LT6
TL light output (rel. units)

NT

KT LT4

KT4
900
LT
0 200 400
Intensity (rel. units)

LT4
(a) Temp. °C

0
0 0.2 0.4 0.6
LT0
(b) Conc. TiO2 (mol. %) LT2

0 100 200 300 400

Temperature, °C

Fig. 6. TL glow curves of X-ray irradiated LiF–PbO–B2 O3 : TiO2 glasses. Inset (a) presents the glow curves of three
series of glasses containing 0.4 mol% of TiO2 and (b) shows the variation of TL light output with the concntration of
TiO2 for the three series of glasses.

temperatures has been observed; activation energies associated with these glow peaks are
computed using Chen’s formulae [22]:

E t ¼ 1:52ðKT 2M =tÞ  1:58ð2KT M Þ, (1)

E d ¼ 0:976ðKT 2M =dÞ (2)

for the first-order kinetics. In the above equations K is the Boltzmann constant, b is the rate of
heating, t ¼ T M  T 1 ; d ¼ T 2  T M ; where T M is the glow peak temperature and T 1 (rising end)
and T 2 (falling end) are the temperatures at the half widths of the glow peaks. A summary of the
data on thermoluminescence peaks and corresponding trap depth parameters of the present
glasses is furnished in Table 4. The TL light output of the other two series with the concentration
of TiO2 has exhibited a similar behaviour. The inset of the Fig. 6 shows the comparison of TL
light output with the concentration of TiO2 ; the comparison shows the highest TL emission for
NT series for any concentration of TiO2 among the three series of glasses.
It may be noted here that prior to TL measurements we have recorded the optical absorption
spectrum of all the glasses before and after X-ray irradiation. The X-ray irradiation does not
produce any significant changes of the pattern and the intensity of the existing absorption bands
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Table 4
Data on various trap depth parameters of TL glow peak of AF–PbO–B2 O3 : TiO2 glasses

Glass T M (K) t (K) d (K) E t (eV) E d (eV) TL light output

(arb. units)

LT0 560 64 31 0.483 0.839 821

LT2 495 57 35 0.422 0.581 410
LT4 536 62 39 0.455 0.611 581
LT6 599 71 30 0.492 0.992 1095

KT0 588 74 25 0.446 1.147 895

KT2 519 63 30 0.413 0.745 470
KT4 561 70 32 0.43 0.816 725
KT6 628 81 24 0.46 1.363 1265

NT0 618 95 25 0.353 1.267 1083

NT2 539 81 28 0.319 0.861 600
NT4 585 87 31 0.351 0.916 1015
NT6 663 104 22 0.368 1.658 1585

indicating no considerable changes in the concentration of existing oxidation states of titanium

ions in these glasses due to X-ray irradiation.

4. Discussion

It is well known that the effect of introduction of modifiers like AF, PbO into B2 O3 network is
the conversion of sp2 planar BO3 units into more stable sp3 tetrahedral BO4 units and may also
create non-bridging oxygens. Each BO4 unit is linked to two such other units and one oxygen
from each unit with a metal ion and the structure leads to the formation of long-chain
tetrahedron. The presence of such BO4 units in the present glasses is evident from the IR spectral
studies. Earlier NMR investigations by different researchers [23,24] on alkali fluoro borate glasses
indicate that in addition to BO4 units there exist BðO; FÞ4 or ðBO3 FÞ and BO2 F2 units in this type
of systems; the probable linkages between various ions in the present glasses are shown in Fig. 7; it
is to be noted in the figure that different borate groups are connected by oxygen and that the Aþ
ion located near the fluorine to serve as charge compensator.
Titanium ions seem to exist mainly in Ti4þ state in the present AF–PbO–B2 O3 glass network.
However, the reduction of Ti4þ to Ti3þ appears to be viable during melting and annealing process
of the present glasses. The Ti4þ ions are largely in six-fold coordination as corner-sharing ½TiO6 2
units in the glass network. The formula ½TiO6 2 suggests that additional oxygen atoms are
required for the co-ordination of titanium (since TiO2 can generate ½TiO4=2  in the network) and it
has to be provided by host network [25]. The band observed in the IR spectra between 640 and
650 cm1 is due to Ti–O–Ti symmetric stretching vibrations of such TiO6 units [20].
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A A

O O F F
A+
O B O B O− O− B O B O
A+
O O O F
B A

Fig. 7. A schematic illustration of alkali fluoro borate glass.

Nevertheless, these ions also present in the glass network with TiO4 structural units; the band
observed in the IR spectra between 710 and 740 cm1 in fact represents vibrations due to such
tetragonal units [26]. Tetragonally positioned Ti4þ ions do not induce the formation of any non-
bridging oxygen ions but octahedrally positioned ions may act as modifiers [26]. The TiO4
tetrahedrons enter the glass network and also alternate with borate structural units and form
linkages of the type B–O–Ti. The position of the common meta-centre B–O–Ti shifts to higher
frequency with a decrease in intensity, where as the position of the band due to TiO6 units shifts
towards lower wavenumber with increasing intensity when the concentration of TiO2 is increased
from 0.2 to 0.6 mol%. These observations suggest that the network of AT2 glass posses higher
concentration of linkages of type B–O–Ti and is more rigid while the disorder in the glass network
goes on increasing, when the concentration of TiO2 increased from 0.2 to 0.6 mol% for all the
three series of glasses. The comparison of the spectra of the three series of glasses shows the
highest concentration of such linkages in LT series of glasses. The modifier ions are expected to
break such linkages; as a result there is a possibility for increase in the degree of deformation in
the glass network with increase in the size of the modifier ion and we expect more disorder in KT
series of glasses. However, the closer values of ionic radii of Kþ (0.133 nm) and Pb2þ (0.132 nm)
may cause the linkages between these two ions and make the network of KT series glasses more
rigid when compared with that of NT series of glasses since the ionic radius of Naþ (0.098 nm) is
far from that of Pb2þ ion.
The two clearly resolved absorption bands observed in the optical absorption spectra of AT2 to
AT6 at 520 and 680 nm are identified due to 2 B2g !2 B1g and 2 B2g !2 A1g transitions of 3d1 electron
of the Ti3þ ions in tetragonal distorted octahedral sites [27–29]. The highest intensity of these
bands observed in the spectrum of glasses AT6 indicates the highest concentration of such Ti3þ
ions. The weak intensity of these bands exhibited by the spectra of the glass AT2 apparently
indicates the presence of low concentration of these ions in this glass. The ESR measurements also
support the presence of Ti3þ ions in these glasses, since the weak asymmetric signal in ESR spectra
at about g ¼ 1:93 (for the glasses AT2 to AT6 ) arises only due to 3d1 -unpaired electron of Ti3þ
ions in a tetragonally distorted octahedral field [30]. Further, these measurements also suggest the
presence of maximum concentration such Ti3þ ions in the glass AT6 and minimum in glasses AT2 :
Further, the comparison of the optical absorption and ESR spectra of the three series of glasses
shows the highest concentration of such Ti3þ ions in NT series of glasses.
The most probable local structure likely to occur for Ti3þ in these glasses is as a TiO6
octahedron entwined with a BO4 tetrahedron TiBO9 where all the oxygens are bridging and
charge compensated by a pair of Pb2þ ions as shown in the Fig. 8.
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- Bridging oxygens, - Pb2+,

- TiO6 Octahedron (of Ti3+), - B

Fig. 8. The local structure of Ti3þ octahedron entwined with BO4 units.

The alkali ions viz., Liþ ; Naþ ; Kþ have closed structure, do not have energy levels within 10 eV
of the ground state hence these ions do not participate directly in luminescence but may act as
activator ions. The lead ions occur as Pb2þ ; in the activation process the substitution of Aþ
ðLiþ ; Naþ ; Kþ Þ by doubly charged lead ions, the charge balance would be upset. To maintain the
charge balance an equal number of F ions in the lattice have to be introduced. Since the lead ion
is doubly charged, the energy levels of the surrounding oxygen ions will be slightly lifted up in
comparison with the normal ions and give rise to occupied energy levels close to the top of the
valance band. These levels form the ground state of the luminescence. The lifting of these energy
levels is in a lesser extent in glasses containing Kþ ions when compared with the NT glasses since
the ionic radius of Kþ is very close to that of Pb2þ as mentioned before. The lesser degree of
deformation in Kþ ion present glasses indicate deeper trap depths for the colour centres in these
glasses giving rise to the highest TL light output with the highest activation energies (Table 4) as
observed. Similarly the co-activator F ions give rise to unoccupied energy levels close to the
bottom of the conduction band and these levels act as traps.
The action of X-ray irradiation on glasses is to produce secondary electrons from the sites
where they are in a stable state and have excess energy. Such electrons may traverse in the glass
lattice depending upon their energy and the composition of the glass and are finally be trapped,
thus forming colour centres (or alternatively they may form excitons with energy states in the
forbidden gap). The trapping sites may be the metal cations, which constitute the glass structure,
ions of admixtures to the main composition and the structural defects due to impurities in the
glass. Thus this process leads to the formation of (1) boron E centres (BEC), (2) non-bridging
oxygen hole centres, and (3) boron oxygen hole centres (BOHC). Thermoluminescence is a
radiative recombination between the electrons (released by heating from a BEC) and an anti-
bonding molecular orbital of the nearest of the BOHCs. However, the TL emission due to such
recombination is possible only at low temperature at about 140 K as reported earlier [31].
Alternatively, the TL emission in these glasses may be explained as follows: During the
heating process for recording the TL light output the electrons that were captured by Pb ions are
liberated and later trapped by holes in the recombination centre giving out TL light output as
shown in Fig. 9a.
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EC

Electron traps Pb EC

Electron center Pb

Recombination
center TL light Ef

Ti Killer center
TL light Ef
Hole center

Hole traps

EV EV

(a) (b)

BOHC
A
hν
A′

(c)

Fig. 9. (a) A proposed TL mechanism pure AF–PbO–B2 O3 glasses; (b) a proposed TL mechanism with killing action of
Ti4þ ions in AF–PbO–B2 O3 glasses; (c) mechanism of recombination of BOHC and the electron from the neighbouring
Ti ion impurity.

In the absence of Ti4þ ion in the glass network, each electron released by heating from electron
centres would be caught by an anti-bonding molecular orbital of the nearest of the oxygen hole
centre giving out maximum TL light output. Let us assume that these Ti4þ ions are uniformly
distributed throughout the glass; a fraction of the electrons released by heating would be trapped
at Ti4þ ions thereby reducing these ions to the Ti3þ state and the remaining electrons may be
trapped by the holes leading to a decrease in the TL light output (Fig. 9b). This process inhibits
the radiative recombination of electron and hole centres causing a reduction in the TL light
output.
Or alternatively the killing action of Ti4þ ions may be explained as follows; the delocalized anti-
bonding state of substitutional neighboring Ti4þ ions in tetrahedral sites as described earlier may
play an intermediate role in the recombination reaction either through by passing or by resonance
energy conditions, so that the radiative transition is no longer possible in the site A1 as shown in
the Fig. 9c.
The larger the number of octahedral Ti4þ ions in the glass network, the higher is the TL
quenching. The high reduction in TL light output of LT series glasses indicate that the
concentration of Ti4þ ions is much higher in this series of glasses when compared with the other
two series. Thus the analysis of the TL data of AF–PbO–B2 O3 : TiO2 glasses suggests, though the
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overall efficiency of TL emission is reduced due to the presence of Ti4þ ions for all the glasses, the
NT glass seems to be a better candidate for TL emission (in view of relatively high TL light output
with deeper trap depths (Table 4)).

5. Conclusions

The summary of conclusions drawn from the study of various optical properties of
AF–PbO–B2 O3 glasses doped with different concentrations TiO2 is as follows: The results of
infrared spectral studies suggest that, the Ti4þ ions mostly exist in four-fold co-ordination (which
do not induce any non-bridging oxygen ions) in all the three series of the glasses when the
concentration of TiO2 is 0.2 mol%. The exploration of the results of ESR and optical absorption
studies reveal that there is a little probability for the titanium ions to exist in Ti3þ state that
weaken the network of AT2 glasses. The thermoluminescence studies also indicate the presence of
high proportion of Ti4þ ions (that act as TL killers) in AT2 glasses. The comparison of the
experimental results among the three series (LT, NT, and KT) of the glasses however shows the
maximum concentration of titanium ions in Ti4þ state that participate in the glass network with
TiO4 structural units in LT series of the glasses containing any particular concentration of TiO2 ;
Finally, it may be concluded that the AF–PbO–B2 O3 glasses containing TiO2 around 0.2 mol%
are more suitable for the practical applications like non-linear optical devices.

Acknowledgements

The authors wish to thank Dr. P. Yadagiri Reddy, Department of Physics, Osmania University,
Hyderabad, for kindly allowing to record TL light output of the samples used in the present
investigations in his laboratory.

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