J. Am. Ceram. Soc.
, 93 [7] 2004–2011 (2010)
Journal
Influence of Crystallization on the Luminescence Characteristics of
Pr31 Ions in PbO–Sb2O3–B2O3 Glass System
Tallam Satyanarayana,z Michail G. Brik,y Nutalapati Venkatramaiah,z Iwan V. Kityk,w,J
Kazimierz J. Plucinski,ww Vandana Ravikumar,z and Nalluri Veeraiahz
z
Department of Physics, Acharya Nagarjuna University-Nuzvid Campus, Nuzvid-521 201, AP, India
z
Department of Chemistry, Pondicherrry University, Pondicherry-605 014, India
J
Electrical Engineering Department, Technical University of Czestochowa, PL-42-201 Czestochowa, Poland
ww
Electronic Department, Military University of Technology, 00-908 Warsaw, Poland
PbO–Sb2O3–B2O3 glasses mixed with different concentrations
of Pr2O3 (ranging from 0 to 0.6 mol%) were crystallized. The
samples were characterized by X-ray diffraction (XRD) and
transmission electron microscopy techniques. The XRD studies
have revealed the presence of Pb5Sb2O8, Pb3(SbO4)2, PbB4O7,
b-PrSbO4, Pr3SbO7, and Pr3Sb5O12 crystalline phases. Optical
absorption (in the visible and NIR regions) and fluorescence
spectra of these samples have been recorded at room tempera-
ture. The Judd–Ofelt theory could successfully be applied to
characterize the absorption and luminescence spectra of Pr31
ions in these samples. From the luminescence spectra, various
radiative properties like transition probability A, branching ra-
tio br, and the radiative lifetime sr for various emission levels
originating from the 3P0 level of Pr31 ion in the glasses glass
ceramic samples have been evaluated. The radiative lifetime of
the 3P0-3H6 transition is measured and the quantum efficiency
has been estimated. The crystallization causes to improve the
luminescence efficiency to a large extent. The changes observed
in the radiative properties due to crystallization have been dis-
cussed in the light of varying co-ordinations of antimony ions in
the glass network.
I. Introduction
P RASEODYMIUM-doped glasses are being widely investigated, in
view of the fact that these glasses exhibit a very rich emission
extending from the UV to the infrared region. Pr-mixed glass
fibers are currently being used as the most promising candidates
for a 1.3 mm (1G4-3H4) communication window1–3; up-con-
version (yellow to blue) mechanism has also been demonstrated
in some Pr31-doped glasses under an infrared laser pump.4,5
There are several recent reports suggesting that the Judd–Ofelt
(JO) theory is applicable for evaluating the luminescence effi-
ciencies of Pr31 ions in various glasses and glass ceramics.6,7 The
luminescence efficiency of this ion can either be enhanced or
optimized from the systematic characterization of optical fea-
tures of Pr31 ions in variable environments in the host material.
The latter may be both in the crystalline as well as in the dis-
ordered glass state. Further, luminescence study of Pr31 ion is
more interesting when compared with that of the other lan-
thanide ions, such as Er31, Nd31, and Yb31 ions, because Pr31
S. Bhandarkar—contributing editor
Manuscript No. 26838. Received September 25, 2009; approved January 26, 2010.
w
Author to whom correspondence should be addressed. e-mail: ikityk@el.pcz.czest.pl
2004
DOI: 10.1111/j.1551-2916.2010.03696.x
r 2010 The American Ceramic Society
y
Institute of Physics, University of Tartu, Tartu 51014, Estonia
ion gives emission lines originating from three different levels
(3P0, 1D2, and 1G4).8 Earlier, it has been established that the
crystallization of the glasses containing Pr31 ions (or any rare
earth ions) improves the luminescence efficiency to a large
extent.9
Among various glasses and glass ceramics, heavy-metal-ox-
ide-based glass ceramics like lead antimony oxide, find potential
applications in nonlinear optical devices (such as ultrafast opti-
cal switches, optically poled materials, power limiters, and broad
band optical amplifiers operating around 1.5 mm).10 Recently,
we have reported the second-order nonlinear optical effects of
these glasses crystallized with TiO2 and CoO as nucleating
agents. From these studies, we have identified the optimal con-
centrations of the dopant ions/crystallizing agents for obtaining
the maximum nonlinear optical effects.11,12 In general, glass ce-
ramic materials are expected to have several advantages like
good mechanical, electrical, and thermal properties, high chem-
ical durability, and a low coefficient of thermal expansion with
no crack growth inside. If care is taken such that the average
diameter of various nanocrystalline grains produced in the glass
ceramics is sufficiently far away from the wavelengths of the
visible and NIR spectral regions, these samples retain transpar-
ency even after the crystallization. Further, more the antimony-
oxide-based glass ceramic materials are more stable against
pumping light when compared with the amorphous materials.
Sb2O3-based glass ceramics possess a high refractive index and
are transparent to the far infrared wavelengths.13 These factors
favor antimony-oxide-based glass ceramics to offer a suitable
environment for hosting the rare earth ion to provide high lu-
minescence efficiency in the visible and NIR regions. Antimony
ions may also exist in Sb51 state (in addition to Sb31 state) and
participate in the formation of glass network with Sb51O4 struc-
tural units and likely to form the linkages with BO4 structural
units in PbO–Sb2O3–B2O3 glass ceramic network; such linkages
are expected to influence the fluorescence efficiency of Pr31 ions
to a large extent. There are also reports suggesting that the Sb51
ions participate in the glass network with SbO6 (octahedral po-
sitions) structural units especially in the glasses mixed with rare
earth ions.14 In the present investigation, we have attempted to
investigate the influence of crystallization on the fluorescence
characteristics of Pr31 ions incorporated into lead antimony
borate glass systems. The study is further intended to compare
the probabilities of various luminescence transitions of Pr31 ions
in amorphous and crystallized samples and to explore the ad-
vantage of crystallization on the luminescence efficiency. The
Section II describes the experimental methods used. Principal
results of the absorption and luminescence measurements and
an appropriate discussion are given in the Section III.
July 2010 Influence of Crystallization on PbO–Sb2O3–B2O3 Glass System 2005

Table I. Physical Parameters of PbO–Sb2O3–B2O3: Pr2O3 Glass and Glass Ceramic Samples
Glasses Glass ceramics

Property/Sample P2 P4 P6 CP2 CP4 CP6

Density (d) (g/cm3) 5.411 5.403 5.393 5.841 5.832 5.821

Average molecular weight (M) 204.6 204.9 205.1 204.6 204.9 205.1
Refractive index (nd) 1.596 1.594 1.591 1.598 1.595 1.593
Pr31 ion concentration (Ni) (1019 ions/cm3) 3.18 6.35 9.50 3.43 6.85 10.25
Interionic distance (ri) (nm) 3.15 2.51 2.19 3.08 2.44 2.14
Polaron radius (rp) (nm) 1.27 1.01 0.88 1.24 0.98 0.86
Molar volume (Vm) (cm3/mole) 37.81 37.92 38.03 35.03 35.13 35.23
Molar refraction (Rm) 12.86 12.87 12.85 11.95 11.94 11.94

II. Experimental Procedures III. Results

From the glass-forming region of PbO–Sb2O3–B2O3 glass sys- From the measured values of the density and the average mo-
tems, the following composition is chosen for the present study: lecular weight M of the samples, various other physical param-
(30x)PbO–40Sb2O3–30B2O3: xPr2O3 with x 5 0.2 (P2), 0.4 eters such as Pr31 ion concentration Ni, mean Pr31 ion
(P4), and 0.6 (P6), and the corresponding postheated samples separation ri, and polaron radius rp in PbO–Sb2O3–B2O3:
are labeled as CP2, CP4, and CP6, respectively. Pr2O3 glass and glass ceramic samples are computed and pre-
Analytical-grade reagents of Sb2O3, H3BO3, PbO, and Pr6O11 sented in Table I.
powders in appropriate amounts (all in mol%) were thoroughly The TEM pictures of one of the samples (doped with 0.6
mixed in an agate mortar and melted in a platinum crucible in mol% of Pr2O3) before and after heat treatment at 5731C are
the temperature range of 10001–10501C in a temperature-con- shown in Fig. 1. The samples heated at 5731C exhibited well-
trolled furnace for about 1 h. The resultant bubble-free melt was defined, randomly distributed crystals (of the size B40 nm) in-
then poured in a brass mold and subsequently annealed grained in a glassy matrix. The residual glass phase is acting as
at 3001C. The glass specimens with various concentrations of interconnecting zones among the crystallized areas making the
Pr2O3 were heat treated in a furnace at a temperature of 5731C samples free of voids and cracks. Thus, these pictures clearly
for 24 h. An automatic controlling furnace was used to keep the indicated that after the heat treatment, the samples were con-
temperature at the desired level. After the heat treatment in the verted into glass ceramics. X-ray diffraction (XRD) studies
furnace at the specified temperature, the samples were chilled in (Fig. 2) have unambiguously indicated the formation of
air to room temperature. The samples prepared were ground and Pb5Sb2O8, Pb3(SbO4)2, PbB4O7, b-PrSbO4, Pr3SbO7, and
optical polished to the dimensions of 1 cm  1 cm  0.2 cm. The Pr3Sb5O12 crystalline phases that are kinetically and thermody-
crystalline phases in the glass ceramic samples were identified namically feasible in these samples (JCPDS card numbers
using Rigaku D/Max ULTIMA III X-ray diffractometer (The 22-0381, 01-0590, 15-0278, 38-1058, 33-1071, and 38-1070, re-
Woodlands, TX) with CuKa radiation. Transmission electron spectively).15 Standard XRD profiles for some of the above
microscopy (TEM) studies were also carried out on these sam- crystalline phases are given as the insets of Fig. 2 for ready ref-
ples to observe the crystallinity using JEM-1011 TEM (Jeol, erence. The Pr-rich areas in the samples might have enhanced
Tokyo, Japan). These observations were performed in a bright the reactivity with the other oxides that precipitate as a high
field regime with an objective aperture of size 9 nm1 in a back
focal plane. The density d of the bulk samples was determined to
an accuracy of (70.0001) by the standard principle of Archi-
medes’ using o-xylene (99.99% pure) as the buoyant liquid. The
mass of the samples was measured to an accuracy of 0.1 mg us-
ing an Ohaus digital balance (Ohaus Corporation, Pine Brook,
NJ), Model AR2140. The refractive index (n) of the samples was
measured (at l 5 589.3 nm) using an Abbe refractometer
(ATAGO Make, Tokyo, Japan) with monobromo naphthalene
as the contact layer between the glass and the refractometer
prism. The optical absorption spectra of the samples were re-
corded at room temperature in the spectral wavelength range
covering 300–2200 nm with a spectral resolution of 0.1 nm using
a JASCO Model V-670 UV-vis-NIR spectrophotometer (Tokyo,
Japan). The photoluminescence spectra of the samples were
recorded at room temperature on a Photon Technology Inter-
national Spectrofluorometer. This instrument contains an
autocalibrated quadrascopic monochromator for wavelength
selection and a quadracentric sample compartment. The light
source is a high-intensity continuous xenon lamp with a
high-sensitivity TE-cooled InGaAs detector with a lock-in
amplifier and chopper for noise suppression and an additional
emission mono with a 600 groove grating blazed at 1.2 mm.
The system provides unmatched NIR luminescence recording
capability from 500 nm–2.2 mm. The spectral resolution was
0.1 nm. The fluorescence decay curves were recorded by using Fig. 1. Transmission electron microscopic pictures of PbO–Sb2O3–B2O3
a Jobinyvon spectrofluorolog-3 (Irvine, CA) with a pulsed glass doped with 0.6 mol% of Pr2O3 (a) preheated, (b) after heat treating
xenon lamp of 450 W. at 5731C.
2006 Journal of the American Ceramic Society—Satyanarayana et al.
Fig. 2. X-ray diffraction (XRD) patterns of PbO–Sb2O3–B2O3:Pr2O3
glass ceramics. (1) b-PrSbO4, (2) Pb3(SbO4)2, (3) Pr3Sb5O12, (4) Pr3SbO7,
(5) PbB4O7, and (6) Pb5Sb2O8. Insets represent the standard XRD
profiles of two of the crystalline phases.
density of fine Pr rich crystals. These tiny crystals act as hetero-
geneous nuclei for the crystallization of the remaining glass. The
diffraction data also indicate that, in these samples, the anti-
mony ions coexist in an Sb51 state with the Sb31 state.
The optical absorption spectra (Fig. 3) of Pr31-doped
PbO–Sb2O3–B2O3 glasses and glass ceramics recorded at room
temperature in the wavelength range from 300–2100 nm, have
exhibited the following absorption bands:
3
H4 !3P2 ; 3P1 ; 3P0 ; 1D2 ; 3F4 ; 1G4 ; 3F3 ; 3F2 ; and 3 H6
Out of these, 3H4-1G4, 3F4, 3F3, and 3F2 transitions
are found to be in the infrared region, 3H4-1D2 in the orange
region whereas 3H4-3P2, 3P1, 3P0 are in the violet and blue
regions.
The increasing concentration of praseodymium ions in the
glass matrix does not alter the spectral positions of the absorp-
tion bands but the absorption strength under the given peak is
found to be slightly increased. When the samples are crystal-
lized, the peak positions are slightly affected with a significant
enhancement in the area under the absorption bands when com-
pared with that of corresponding precrystallized samples
(Fig. 3). In view of these observations, further calculations in
the present work have been confined to the samples doped with
only 0.6 mol% of Pr2O3.
Conventional JO theory16,17 has been used to perform anal-
ysis of theexperimental
 absorption spectra. The reduced matrix
elements U l  of the unit tensor operators needed for calcula-
tions have been recalculated, using newer literature data on
the Pr31 Hamiltonian parameters taken from Carnall et al.18
The procedure of fitting of the calculated oscillator strengths to
those deduced from the experimental spectra is described in
Görller-Walrand and Binnemans19 However, it should be noted
Vol. 93, No. 7
Fig. 3. A comparison plot of the absorption spectra of PbO–Sb2O3–
B2O3 glasses and glass ceramics doped with different concentrations of
Pr2O3 (all the transitions are from the ground state 3H4).
here that very often, application of the standard JO theory to the
Pr31-doped glasses and crystals results in negative values of the
second-order intensity parameter O2.20–23 Such an unphysical
result can lead eventually even to nonrealistic negative values of
the radiative transition probabilities. The reason for this is a
strong mixture between the 4f2 and 4f5d states of Pr31, which is
not accounted for in the conventional JO theory. To overcome
this drawback, the modified JO theory24,25 has been used
" #
8p2 mcvw X EJ 0  2Ef0
fcal ¼ 1þ Ol
3hð2J þ 1Þ l¼2;4;6 E5d  Ef0
   2
 f N ½g; S; LJ U l f N ½g0 ; S0 ; L0 J 0 (1)
where EJ 0 , E5d, Ef0 are the energies of the final state, lowest
4f15d1 state, and the average energy of all 4f2 states of Pr31, re-
spectively. E5d was taken as 48 385 cm1,26 and Ef0 was set at
10 000 cm1.27
The summary of the JO theory intensity parameters Ol
(l 5 2,4,6) for the glass and glass ceramics doped with 0.6
mol% of Pr2O3 is presented in Table II.
The values of Ol are found to be in the following order for the
glass ceramic: O64O44O2. The collection of the data on Ol
parameters of Pr31 ion in various other glass matrices (Table
III) indicated a similar trend with few exceptions.
The bonding parameter (d) is computed using the standard
equations38,39 for the glass and ceramic samples and presented in
Table II. The value of d is found to be more negative for the
glass ceramic (partially crystallized) sample when compared
with that of an amorphous material.
The excitation spectrum for the glass ceramic sample CP6 re-
corded at room temperature by monitoring the emission at 607
nm is shown in Fig. 4. The excitation spectrum exhibited three
distinct spectral bands corresponding to 3H4-3P2, 3P1, 3P0 tran-
July 2010 Influence of Crystallization on PbO–Sb2O3–B2O3 Glass System 2007

Table II. The Absorption Band Energies and the Oscillator Strengths for the Transitions of Pr31 Ion in PbO–Sb2O3–B2O3 Glasses
and Glass Ceramics
Energy (cm1) Glass (P6) Ceramics (CP6)

Absorption band Glass (P6) Ceramics (CP6) fexp (106) fcal (106) fexp (106) fcal (106)
3
H4-3F2,3H6 5177 5162 5.804 5.827 4.706 4.735
3
F3,3F4 6634 6614 20.765 20.639 19.858 19.789
1
D2 16 886 16 843 3.106 3.318 3.754 3.192
3
P0 20 584 20 555 2.863 2.979 2.950 2.895
3
P1 21 212 21 214 3.198 3.088 2.950 3.008
3
P2 22 422 22 431 12.374 12.374 11.929 12.176
RMS 5 70.189  106 RMS 5 70.360  106
d value: 0.0808 d value: 0.199
O2 5 5.917  1020 cm2; O2 5 2.476  1020 cm2;
O4 5 4.770  1020 cm2; O4 5 4.638  1020 cm2;
O6 5 21.350  1020 cm2. O6 5 20.727  1020 cm2.

sitions. From these spectra, lexc is identified as 442 nm
(3H4-3P2) and the same was used for recording the emission
spectra for the glasses and glass ceramics; the emission spectra
(Fig. 5) exhibited bands due to the following transitions:
3
P0 !3F2 ; 3F3 ; 3F4 ; 3H6 ; 3H4 ; 3H5 ; 1D2 !3H5
Out of these, 3P0-3H6, 3H5 are observed to be strong and the
rest of them are weak. The spectra further indicated that there is
a substantial increase in the luminescence efficiency associated
with all the transitions due to the heat treatment. In this case,
substantial role begin to play electron–phonon interaction, in-
cluding the anharmonic ones.
Figure 6 shows the fluorescence decay curve for the glass (P6)
and glass ceramic (CP6) recorded at room temperature corre-
sponding to the emission line 3P0-3H6 at 607 nm excited by 442
nm; the inset of Fig. 6 represents the plot of log (I/I0) vs t. From
these curves, the lifetime texp for the glass and glass ceramic
samples are estimated to be 5.89 and 7.9 ms, respectively. The
order of the radiative decay time (for 3P0 level) measured for the
present samples, is well within the range reported in a number of
other glass systems.5,40
The energy-level diagram containing the absorption and
emission transitions of Pr31 ion observed for the glass ceram-
ics (sample CP6) is shown in Fig. 7.
A further application of the JO theory is related to the esti-
mations of the radiative lifetimes of excited states and branching
ratios of emission transitions, following standard proce-
dure19,22,23,28,34,37 (this list of references is representative and
not exhaustive). The summary of the emission parameters for
one of the samples (CP6) is presented in Table IV.
It may be noted here that even though, the 3P0-3H5 transi-
tion exhibits a significant intensity, the transition probability is
zero as the reduced matrix elements U2, U4, and U6 are zeros for
this transition.
It is necessary to emphasize that phonons play an important
role, both in upconversion as well as in nonradiative decay be-
tween levels in these two sets. This will be a subject of a separate
work in future.
The comparison table of lifetimes for the 3P0 level for the
glass and glass ceramic doped with 0.6 mol% of Pr2O3 is pre-
sented in Table V.
Following this table, one can conclude that the existed times
are determined by a superposition of the long-range ordered
crystalline fields and the local disordered chemically ordered
states.
IV. Discussion
In PbO–Sb2O3–B2O3 glass system, Sb2O3 is an incipient glass
network former and as such does not readily form the glass but
does so in the presence of the modifier oxides like PbO and the

Table III. A Comparison Table of Ol 1020 (cm2) Parameters for a Number of Other Glass Systems Containing Pr31 Ions
Glasses References O2 O4 O6 Relation

PbO–Sb2O3–B2O3 glass ceramics Present work 2.476 4.638 20.727 O64O44O2

Lithium borate Babu and Jayasankar28 2.14 7.19 7.83 O64O44O2
Lithium fluoroborate Babu and Jayasankar28 1.17 3.83 4.58 O64O44O2
Li2O–B2O3 Takebe et al.29 0.10 4.71 5.28 O64O44O2
Na2O–B2O3 Takebe et al.29 0.98 4.76 4.86 O64O44O2
K2O–B2O3 Takebe et al.29 2.33 4.65 3.84 O44O64O2
Zinc cadmium fluoride Bunuel et al.30 0.72 4.80 7.93 O64O44O2
Calcium boroaluminate Nachimuthu and Jagannathan31 4.84 8.42 11.08 O64O44O2
ZnO–TeO2 Hormadaly and Reisfeld32 3.84 7.64 5.90 O44O64O2
Na2O–TeO2 Zhang et al.33 3.68 6.97 5.16 O44O64O2
LKBBT Zhang et al.33 4.14 6.88 4.71 O44O64O2
LKBBG Zhang et al.33 3.85 7.20 3.10 O44O24O4
Oxyfluoride Genova et al.34 0.13 4.09 6.33 O64O44O2
NaTFP Moorthy et al.35 0.229 7.312 6.149 O44O64O2
KTFP Moorthy et al.35 0.498 8.814 6.426 O44O64O2
Fluorozirconate Newhouse et al.36 2.8 4.9 5.3 O64O44O2
Mixed alkali–halide Newhouse et al.36 2.7 4.4 5.4 O64O44O2
ZBLAN Quimby et al.37 2.44 4.41 5.52 O64O44O2
2008 Journal of the American Ceramic Society—Satyanarayana et al.
Fig. 4. An excitation spectrum for CP6 sample (lemis 5 607 nm).
glass former B2O3. Antimony oxide participates in the glass
network with SbO3 structural units with the oxygen at three
corners and the lone pair of electrons of antimony at the fourth
corner. The coordination polyhedra are joined by sharing the
corners to form double infinite chains with the lone pairs point-
ing out from the chains. These chains are held together by weak
secondary Sb–O bonds with lengths greater than 2.6 Å.41–43
XRD studies of the present investigation have indicated that
antimony ions also exist in the Sb51 state in these glass ceramics.
These Sb51 ions participate in the glass network with SbVO4
units and play a similar structural role to BO4 units and
may form cross linkages of the type Sb–O–B with the BO4
units.44 B2O3 is a network former with BO3 and BO4 structural
units. PbO when incorporated into B2O3 glass network, nor-
mally converts sp2 planar BO3 structural clusters into more sta-
ble sp3 tetrahedral BO4 units and may also create nonbridging
oxygens (depending upon whether PbO goes into modifying po-
sitions or network-forming positions). In general, PbO partici-
pates in the glass network both with covalent and ionic bondings
and participates in the glass network with [PbO4/2] pyramidal
units connected in puckered layers.
The energies and spectral profiles of certain transitions in the
absorption spectra of Ln31 ions throw some light on their co-
ordination.31,45,46 The energy of B21 000 cm1 for the 3H4-3P0
transition for Pr31 suggest predominately eight coordinations
for these ions in the present glass host.31,45,46 These distorted
PrO8 structural units form a one-dimensional chain through
edge-sharing in the glass network. The XRD studies have indi-
cated that there is a formation of Pr3SbO7 crystallites. In such
type of crystal phases, it was reported earlier that the Sb51 ions
occupy octahedral positions and participate in the glass network
with SbO6 structural units. The earlier investigations have
Fig. 5. Emission spectra of PbO–Sb2O3–B2O3 glasses and glass ceramics doped with different concentrations of Pr2O3 (lexc 5 442 nm). All the
transitions are from 3P0.
Vol. 93, No. 7
revealed that in the crystals of the type Ln3SbO7, the SbO6,
and PrO8 chains lie in alternate parallel planes.14,47 The local
structure of Sb51 ions that participate in the glass network with
SbO6 structural units is expected to be more asymmetric and the
strain energy in the glass network increases as a whole, thus re-
sulting in a decrease in the additional activation energy that is
necessary for glass network rearrangement. As a consequence,
we expect more degree of disorder in glass ceramics containing
more SbvO6 structural units rather than SbIIIO3 and SbvO4
structural units. If we consider the varying coordination of an-
timony ions to be incorporated between the long-chain mole-
cules in the vicinity of Pr31 ion in the antimony borate network,
then the symmetry and/or covalency at the Pr31 ions should be
different for the glass ceramic and the glass. Additionally, the
variations in the concentration of different structural units of
antimony ions are also expected to modify the crystal field
around Pr31 ions in the network.48,49 Such variations might
be responsible for the enhancement of the luminescence intensity
of various transitions observed in the glass ceramic sample with
respect to that of amorphous materials.
The rare earth ions that occupy different coordination sites
with a noncentro symmetric potential contribute significantly to
O2. Even with a similar coordination, the differences in the dis-
tortion at these ion sites may lead to a distribution in the crystal
field. The variations in the sites with a noncentro symmetric po-
tential (that may arise due to the influences of the dielectric of
media, the environment of the rare earth ion, and nephelauxetic
effect) lead to changes in the O2 value. Among the three JO pa-
rameters, the parameter O2 is related to the covalency and struc-
tural changes in the vicinity of the Pr31 ion (short-range effect)
and O4 and O6 are related the long-range effects and are strongly
influenced by the vibrational levels associated with the central
rare earth ions bound to the ligand atoms. The comparison of
the O2 parameter for the glass and glass ceramic shows a slightly
lower value for the glass ceramic. According to the JO theory,
the intensity parameters contain two terms: (i) crystal field pa-
rameter that determines the symmetry and distortion related to
the structural change in the vicinity of Pr31 ions. In the present
context, this may be understood as follows: in the glass ceramic
samples, the presence of larger concentrations of SbvO6 struc-
tural units causes more structural distortion (such high distor-
tions were reported in various other glass systems consisting of
octahedral AlO6, TiO6, WO6, and MoO6).12,50–53 This leads to
the increase of the average Pr–O distance, and therefore pro-
duces a weaker field around the Pr31 ion leading to a decreasing
value of O2 when compared with that of amorphous samples. (ii)
The second term is the covalency between the rare earth ion and
the oxygen ion; for oxide glasses, this is related to the radial in-
tegral of the wave functions between the 4f states of Pr31 and 2p
July 2010 Influence of Crystallization on PbO–Sb2O3–B2O3 Glass System 2009

Fig. 6. A fluorescence decay curve for the glass (P6) and glass ceramic (CP6) recorded at room temperature. Inset represents the semilog graph of the
luminescence decay.

states of oxygen and the energy denominator between these two
levels.
Further support for the argument that there is more struc-
tural disorder in a ceramic network than in the glass network
can also be cited from the value of the bonding parameter d; the
value of d for these glasses is found to be lower (more negative);
this observation indicates a lower covalent environment for the
Pr31 ion in glass ceramic samples than in glasses.
Branching ratio ‘‘b’’ (that defines the luminescence efficiency
of the transition) of the orange emission due to 3P0-3H6 tran-
sition, among various transitions originated from 3P0, is found
to be the highest 440% for the glass crystallized with 0.6 mol%
of Pr2O3 and it is B35% for the preheated sample.
The fluorescence decay curve (for both glass and glass ce-
ramic samples) corresponding to the emission line 3P0-3H6 is
observed to be a single exponential; the measured fluorescence
lifetime t are apparently shorter than the calculated lifetimes
from the JO theory. Such a difference obviously suggests some
nonradiative losses in both glass and glass ceramic samples.
The quantum yield (Z) is defined as the radiative portion of
the total relaxation rate of a given energy level40
Arad texp
Z¼ ¼ (2)
Arad þ Wnr trad
where Arad is the total radiative relaxation rate, Wnr is the rate of
total nonradiative transition, texp is the experimental lifetime,
and trad is the radiative lifetime. The value of Z (for the 3P0 level)
determined for glass and glass ceramic is presented in the Table
V. For the heat-treated samples, the value of Z is increased to

Fig. 7. An energy-level diagram containing absorption and emission transitions of the Pr31 ion in the glass ceramic CP6.
2010 Journal of the American Ceramic Society—Satyanarayana et al.
Table IV. Various Radiative Properties of Transitions of Pr31
Ions in PbO–Sb2O3–B2O3 Glass Ceramic (CP6)
Transition Energy (cm1) A (s1)
3
P0-3H4 20 000 16 921
3
H5 18 382 0 0.0
3 mpd., 475, 569–76 (2009).
H6 16 474 17 796
3 G. Lakshminarayana, H. Yang, Y. Teng, and J. Qiu, ‘‘Spectral Analysis of
F2 15 291 P 6909
1
j Aij ¼ 41 626 s
t 5 24 ms
Table V. A comparison Table of Radiative Life Times (in ls)
for the 3P0 Level
Glass Glass ceramic
Measured (tm) 5.89
Calculated (tr) 23.6
Quantum yield (Z%) 25.0
32.9 (from 25.0 for the amorphous sample); such a rise is con-
nected not only with the rise of the radiative relaxation proba-
bility but also with a reduction of the nonradiative transition
probability. This is possibly due to the decrease of the electron–
phonon coupling of the Pr31 ion with the high-energy phonons
in the glass phase and a relative increase of this coupling with
low-energy phonons of the crystalline phase.54
It may be noted here that neither absorption spectroscopy
nor emission spectroscopy has indicated extraordinary changes
of positions of various spectral transitions due to crystallization.
However, the increase of the experimental lifetime of 3P0 state
observed after heat-treatment caused that the quantum yield for
this sample reached a value of 32.9 with a simultaneous decrease
of total nonradiative transition. This decrease of nonradiative
transitions is concerned with the transition from 3P0 to 1D2. This
may be understood as due to the participation of the 1D2 state in
the nonradiative depopulation of the 3P0 level.40
V. Conclusions
A series of the (30x)PbO–40Sb2O3–30B2O3: xPr2O3 with
x 5 0.2 (P2), 0.4 (P4), and 0.6 (P6) glass and ceramics was syn-
thesized and studied spectroscopically. Absorption spectra of
the samples were analyzed using the modified JO theory. The
values of the JO theory intensity parameters were compared
with the available data for other glasses; the relation between the
values of these parameters with the physical properties of the
synthesized samples is discussed. Estimations of the 3P0 level
radiative lifetime and comparison with the corresponding ex-
perimental values yield a quantum efficiency of about 32% for
the ceramic samples and about 25% for the amorphous sample.
An increase of the quantum efficiency in the heat-treated sample
is explained by the decrease of the Pr31 interaction with the host
phonons.
Acknowledgments
T. Satyanarayana and N. Veeraiah, wish to thank DRDO, Government of
India for the financial support to carry out this work. M. G. Brik appreciates the
financial support from the Estonian Science Foundation (grants nos. 7456, JD69,
6999, and 6660).
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