Journal of Non-Crystalline Solids 353 (2007) 1397–1401

www.elsevier.com/locate/jnoncrysol

Characterization of Eu3+-doped fluorophosphate glasses

for red emission
R. Balakrishnaiah a, R. Vijaya a, P. Babu b, C.K. Jayasankar a,*
, M.L.P. Reddy c

a
Department of Physics, Sri Venkateswara University, Tirupati 517 502, India
b
Department of Physics, Government Degree College, Wanaparthy 509 103, India
c
Regional Research Laboratory, C.S.I.R., Thiruvananthapuram 695 019, India

Available online 26 March 2007

Abstract

Fluorescence spectra and decay curves of the 5D0 level for different concentrations of Eu3+ (4f 6) ions in K–Ba–Al fluorophosphate
glasses have been measured at room temperature and are analyzed. The Judd–Ofelt intensity parameters X2 and X4 have been determined
from the intensity ratios of emission peaks corresponding to 5D0 ! 7FJ (J = 2 and 4) to 5D0 ! 7F1 transitions for 1.0 mol% glass. The
intensity parameters thus obtained are in turn used to calculate the radiative properties of the fluorescent levels of Eu3+ ions. Second and
fourth rank crystal-field parameters have been evaluated by assuming a C2V site symmetry for the local environment of Eu3+ ions to
estimate the crystal-field strength experienced by Eu3+ ions in the present host. The decay profiles of the 5D0 ! 7F2 transition of
Eu3+ ions in the present glasses are found to be single exponential for all the studied Eu3+ ion concentrations. A marginal increase
in lifetime of the 5D0 level has been noticed with Eu3+ ion concentration up to 2.0 mol% and then the lifetime marginally decreases
for higher Eu3+ ion concentrations.
 2007 Elsevier B.V. All rights reserved.

PACS: 79.60.Ht; 78.55. m; 71.70.Ch; 42.70.Ce

Keywords: Optical properties; Luminescence

1. Introduction erties by reducing the number of hydroxyl (OH ) groups in

Alkali aluminometaphosphate glasses are the promising
hosts among oxide glasses for lanthanide (Ln) ions due to
their relatively higher refractive indices, lower dispersion,
larger stimulated emission cross-sections, higher gain, bet-
ter chemical durability and lower thermo-optical qualities
when compared with many other hosts such as silicates
[1]. They are very easy to prepare in various compositions
in bulk form and they preserve useful properties upon the
introduction of a significant amount of Ln ions. Addition
of fluoride contents will further improve the radiative prop-
*
Corresponding author. Tel.: +91 877 2248033; fax: +91 877 2225211.
E-mail address: ckjaya@yahoo.com (C.K. Jayasankar).
the glass network [2].
Among Ln ions, trivalent europium (Eu3+) ion is the
best candidate to be used as a probe to investigate the local
structure around Ln ions in condensed matter. This is
because, the low lying energy level scheme of Eu3+ ions is
simple and the transition between 7F0 and 5D0 non-degen-
erate levels is convenient to apply the fluorescence line nar-
rowing technique to analyze changes from site to site
through energy level scheme analysis [3]. Also Eu3+-doped
materials are frequently used in photonic applications as
red phosphors for field emission technology due to the nar-
row and monochromatic emitting nature of the 5D0 ! 7F2
transition of Eu3+ ions at 610 nm. The present work
reports the fluorescence and local field properties of differ-
ent concentrations of Eu3+ ions in K–Ba–Al fluorophos-
phate glass.

0022-3093/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2006.10.063
1398 R. Balakrishnaiah et al. / Journal of Non-Crystalline Solids 353 (2007) 1397–1401
2. Experimental
Eu3+-doped fluorophosphate glasses with composition
(in mol%) (56 x/2)P2O5 + 17.0K2O + (15 x/2)BaO +
8.0Al2O3 + 4.0AlF3 + xEu2O3 (referred as PKBAFEu) for
x = 0.01, 0.1, 1.0, 2.0, 4.0 and 6.0 mol%, were prepared
by the conventional melt quenching technique using high
purity chemicals of KH2PO4, Ba(PO3)2, Al(PO3)3, AlF3
and Eu2O3 as starting materials. The batch composition
was melted around 1075 C for 1 h. The samples were then
kept for annealing at 350 C for 10 h and then slowly
allowed to cool to room temperature (RT). Refractive
index, density, optical absorption, emission and fluores-
cence decay measurements were carried out following the
similar methods mentioned in Refs. [4,5].
3. Results
3.1. Emission spectra – determination of Judd–Ofelt
parameters
The optical absorption and emission spectra for the
1.0 mol% Eu3+-doped PKBAFEu fluorophosphate glass
(referred as PKBAFEu10) were recorded at RT and are
shown in Figs. 1 and 2, respectively. The bands in the
absorption spectra correspond to the transitions originat-
ing from the 7F0 and 7F1 levels and the peaks in the emis-
sion spectra correspond to the well-known 5D0 ! 7FJ
(J = 0–6) transitions. The Judd–Ofelt (JO) intensity param-
eters, Xk (k = 2, 4 and 6) have been calculated using the
ratio of intensities of 5D0 ! 7FJ (J = 2, 4 and 6) transitions
to that of the 5D0 ! 7F1 transition [5–9].
3.2. Radiative properties
The calculated JO parameters have been used to deter-
mine the radiative properties by following the procedure
Fig. 1. Optical absorption spectrum of PKBAFEu10 glass at room
temperature (all the transitions are originated from the ground 7F0 level,
unless otherwise specified).
Fig. 2. Emission spectrum of the PKBAFEu10 glass at room temperature
(weak intense 5D0 ! 7F5,6 peaks are also shown with tenfold
magnification).
outlined in the earlier reported works [7–10]. The Xk,
(·10 20 cm2), experimental (sexp) and calculated (scal) life-
times (ms), quantum efficiencies (g), non-radiative transi-
tion probabilities (Wnr, s 1) and intensity ratios (R(J/1) =
(5D0 ! 7FJ)/(5D0 ! 7F1), J = 2 and 4) have been deter-
mined for the PKBAFEu10 glass and are presented in
Table 1. Similar results obtained for other Eu3+:glasses
such as 58.5P2O5 + 17K2O + 14.5BaO + 9Al2O3 +1Eu2O3
(PKBAEu10) [5], 55.5P2O5 + 17K2O + 11.5BaO + 6BaF2 +
9Al2O3 + 1Eu2O3 (PKBFAEu10) [5], Eu3+:Ba(PO3)2 (PBEu)
[11], Al(NO3)3 + SiO2 + Eu2O3 (ASEu) [12] and 57ZrF4 +
36BaF2 + 3LaF3 + 3AlF3 + 1EuF3 (Eu3+:ZBLA) [13]; and
SiO2 + Al2O3 + Eu2O3 xerogels (SAEu) [14] are also pre-
sented in Table 1 for comparison. The emission peak wave-
lengths (kp, nm), radiative transition probabilities (A, s 1),
experimental and calculated branching ratios (bR), effective
bandwidths (Dkeff, nm) and peak stimulated emission cross-
sections (r(kp), ·10 21 cm2) have been determined for dif-
ferent transitions originating from the luminescent 5D0
level of Eu3+ ions in PKBAFEu10 glass and are shown
in Table 2.
3.3. Crystal-field analysis
A careful observation of 5D0 ! 7FJ (J = 1 and 2) peaks
in the emission spectrum shown in Fig. 2 yields Stark split-
tings of these peaks into 3 and 5 components, respectively.
The second and fourth rank crystal-field (CF) parameters
Bkq and the CF strength parameter (S) have been calcu-
lated by assuming the C2V site symmetry around Eu3+ ions
in PKBAFEu10 glass [15–18]. The CF parameters Bkq
and their ratios B22/B20 and B44/B40 for the present
PKBAFEu10 glass are presented in Table 3 along with sim-
ilar parameters for the PKBAEu10 and PKBFAEu10
glasses [5] for comparison.
 R. Balakrishnaiah et al. / Journal of Non-Crystalline Solids 353 (2007) 1397–1401 1399

Table 1
20
Various parameters: Xk (·10 cm2), sexp (ms), scal (ms), g (=sexp/scal), Wnr (s 1) and R(J/1) (J = 2 and 4) in different Eu3+:glass systems
Glass system X2 X4 X6 sexp scal g Wnr R(2/1) R(4/1)
PKBAFEu10 8.12 5.79 0 2.46 2.35 1.05 19 5.29 1.77
PKBAEu10 [5] 6.91 5.01 5.76 2.51 2.64 0.95 20 4.55 1.56
6.91 5.01 0 2.68 0.94 26
PKBFAEu10 [5] 7.13 5.18 5.78 2.52 2.60 0.97 12 4.69 1.50
7.13 5.18 0 2.65 0.95 19
PBEu [11] 5.9 1.4 1.8 2.30 2.80 0.82 78 3.16 –
ASEu [12] 5.61 3.47 2.91 – 3.70 – – 3.38 –
Eu3+:ZBLA [13] 0.49 4.15 2.76 – 7.35 – – – –
0.49 4.15 0 7.52 – –
PNBYFEu [14] 4.9 5.2 4.0 – 3.41 – – – –
4.9 5.2 0 3.46 – –

Table 2
Emission characteristics: kp (nm), A (s 1), bR, Dkeff (nm) and r(kp)
(·10 21 cm2) for 5D0 ! 7FJ (J = 0–6) transitions in PKBAFEu10 glass
5
D0 ! kp A bR Dkeff r(kp)
exp cal
7
F6 809.7 0 0 0 8.5 0
7
F5 745.3 0 0 0 3.5 0
7
F4 701.6 98 0.21 0.23 6.8 1.95
7
F3 653.1 0 0.02 0 6.8 0
7
F2 611.3 275 0.64 0.65 10.4 2.04
7
F1 591.8 53 0.12 0.12 10.1 0.35
7
F0 579.0 0 0 0 0.7 0

Table 3
Crystal-field parameters Bkq (cm 1) and CF strength parameter S (cm 1)
for Eu3+-doped glass systemsa Fig. 3. Fluorescence decay curves for the 5D0 level of Eu3+ ions in
Parameter PKBAFEu10 PKBAEu10 [5] PKBFAEu10 [5] PKBAFEu10 glass for (a) 0.01, (b) 0.1, (c) 1.0, (d) 2.0, (e) 4.0 and (f)
6.0 mol% Eu3+ ion concentrations.
B20 306 (±40) 314 348
B22 215 (±43) 168 209
B40 990 (±73) 865 881
B42 292 (±55) 358 280 Table 4
B44 1100 (±56) 1073 1098 Experimental lifetimes (sexp, ms) for the 5D0 level for different Eu3+ ion
B22/B20 0.70 0.54 0.60 concentrations in Eu3+:glass systems
B44/B40 1.11 1.24 1.25
S 380 364 371 Concentration (mol%) sexp
r(N)b ±22 (10) ±20 (10) ±22 (10) PKBAFEu10 PKBAEu [5] PKBFAEu [5]
a
The values (cm 1) shown in parenthesis of CF parameters are 0.01 2.39 2.44 –
uncertainties. 0.1 2.41 2.47 2.52
b
N Value shown in the parenthesis of r.m.s. deviation, r, indicates the 1.0 2.46 2.51 2.52
number of levels used in the fit. 2.0 2.49 2.52 2.52
4.0 2.49 2.50 –
6.0 2.43 2.44 –
3.4. Fluorescence decay

The normalized decay curves for the 5D0 ! 7F2 transi-

tion of Eu3+ ions in the present PKBAFEu glasses for dif-
ferent concentrations of Eu3+ ions are shown in Fig. 3. The
graphs are shifted along the positive y-axis for clarity as
reported by Alombert-Goget et al. [19]. These decay curves
are found to be single exponential for all the concentrations
of Eu3+ ions. The single exponential nature of decay curves
is found to be similar to those of borate and fluoroborate
glasses reported in our earlier work [20]. The experimental
lifetimes (sexp) of the 5D0 level of Eu3+ ions for different
concentrations of Eu3+ ions in the present PKBAFEu
glasses along with PKBAEu and PKBFAEu glasses [5]
for comparison are presented in Table 4.
4. Discussion
4.1. Emission spectra – determination of Judd–Ofelt
parameters
Fig. 1 shows the optical absorption spectrum originated
due to transitions from the ground (7F0) and the next
1400 R. Balakrishnaiah et al. / Journal of Non-Crystalline Solids 353 (2007) 1397–1401
higher and thermally populated (7F1) levels to different
excited states of Eu3+ ions in PKBAFEu10 glass measured
at RT. The absorption spectrum is similar to those of
PKBAEu10 and PKBFAEu10 glasses [5]. As can be seen
from Fig. 1, the intensities of the absorption peaks corre-
sponding to the hypersensitive transitions, 7F1 ! 5D1 and
7
F0 ! 5D2, are found to be lower than that of the maxi-
mum intensity 7F0 ! 5L6 transition. The detailed analyses
along with similar results will be reported in our future
work.
Fig. 2 shows the emission spectrum of Eu3+ ions in
PKBAFEu10 glass measured at RT. The band positions
are identified and assigned to the 5D0 ! 7FJ (J = 0–6) tran-
sitions of Eu3+ ions. The emission spectra for all the con-
centrations of Eu3+ ions show the peaks at same energy
positions but with different intensities due to change in con-
centration. The observed emission spectra are similar to
those of other reported Eu3+-doped systems such as
Eu3+:KNbW2O9 crystal [4], PKBAEu10 [5], PKBFAEu10
[5], PBEu [11], ASEu [12] and 64SiO2 + 16K2O + 16-
BaO + 4Eu2O3 (SKBEu) [21] glasses and SAEu xerogels
[14]. The emission peak corresponding to the hypersensitive
5
D0 ! 7F2 transition, in red region around 611 nm, is the
most intense one. The spectrum has been normalized with
respect to the maximum intensity of this transition. The JO
parameters have been calculated based on the analysis of
emission spectra and are shown in Table 1.
The hypersensitive ratio R(2/1), known as the asymmet-
ric ratio, allows one to estimate the covalent nature and
polarization of the surrounding of the Eu3+ ions by short
range effects and centrosymmetry distortion of the Eu3+
ion site. The higher asymmetric ratio (5.29) for
PKBAFEu10 glass indicates higher asymmetry around
Eu3+ ions in the present host compared to other Eu3+:glass
systems [5,11,12] shown in Table 1. As can be seen from
Table 1, PKBAFEu10 glass is having higher Xk values
and the order is found to be X2 > X4 > X6. The highest
value of X2 for PKBAFEu10 glass indicates the highest
asymmetry and/or the highest covalence nature of the
Eu3+ ions–ligand bonds in the present host compared to
other reported systems [5,11–14]. The intensity of the
5
D0 ! 7F6 transition is very small in PKBAFEu10 glass
similar to those of other reported systems [5,11,12], which
made the intensity ratio R(6/1) almost negligible (zero)
compared to that of R(2/1) and R(4/1). Hence X6 value
has been assumed to be zero [10] for this system and radi-
ative properties have been calculated by considering only
X2 and X4 parameters. As can be seen from Table 1, there
is no larger deviation in the calculated lifetimes of the 5D0
level of Eu3+ ions with and without considering the X6
value. For instance, the radiative lifetimes of the 5D0 level
for PKBAEu10, PKBFAEu10 [5], Eu3+:ZBLA [13]
and 58Na(PO3)2 + 11BaF2 + 30YF3 + 1EuF3 (PNBYFEu)
[14] glasses have been calculated for both the cases and are
presented in Table 1 for comparison. Therefore, X6 param-
eter may be ignored while predicting radiative properties
for the 5D0 level of Eu3+ ions.
4.2. Radiative properties
As the intensity of the 5D0 ! 7F6 transition is very weak
(Fig. 2), R(6/1) value for PKBAFEu10 glass is very small
and hence the X6 value has been taken as zero and calcu-
lated the radiative properties. As can be seen from Table
1, the calculated radiative lifetime of the 5D0 level
(2.35 ms) is found to be lower than the experimental fluo-
rescence lifetime (2.46 ms), yielding a quantum efficiency
of more than one (g = 1.05) and negative value for non-
radiative decay rate (Wnr = 19 s 1) for PKBAFEu10
glass. This inconsistent result may be due to uncertainty
of the radiative decay rate calculated on the basis of the
JO theory. Because of the large energy gap between the
emitting (5D0) and next lower (7F6) level of Eu3+ ions,
the non-radiative transition probability for the 5D0 level
is very small and hence the calculated (scal) and the exper-
imental (sexp) lifetimes almost coincide with one another.
Within this marginal difference between scal and sexp values
observed in the present study, the inconsistency may also
arise due to the inherent uncertainty (±30%) of the JO the-
ory. Similar types of negative quantities for Wnr were also
noticed by Toratani et al. [22] in case of Nd3+-doped water-
free phosphate glasses. As can be seen from Table 2, the
experimental and calculated bR for PKBAFEu10 glass
are found to be in good agreement.
4.3. Crystal-field analysis
As can be seen from Fig. 2, the degeneracies of 7F1 and
7
F2 levels prove that the site symmetry of the Eu3+ ions
could be described by low symmetry point groups such as
C1, C2, Cs or C2V [4,15–18]. Using these Stark energy level
positions and free-ion parameters of PKBFAEu10 glass [5]
and assuming C2V orthorhombic site symmetry around
Eu3+ ion sites, CF analysis has been performed to derive
second and fourth rank CF parameters. The CF parame-
ters and CF strength obtained for PKBAFEu10 glass along
with similar parameter values for PKBAEu10 and
PKBFAEu10 glasses [5] are shown in Table 3. The CF
parameters are comparable with those of reported
Eu3+:glass systems [11,18]. The CF strength experienced
by Eu3+ ions in PKBAFEu10 glass is found to be more
or less similar to those of PKBAEu10 and PKBFAEu10
glasses [5]. The energy difference between the extreme Stark
levels for the 7F1 (174 cm 1) and 7F2 (282 cm 1) levels
observed in the PKBAFEu10 glass are comparable with
those of PKBAEu10 and PKBFAEu10 glasses [5].
4.4. Fluorescence decay and lifetime measurements
As can be seen from Table 4, lifetime of the 5D0 level in
PKBAFEu10 glass is found to be almost constant with
increase in Eu3+ concentration except a slight increase
from 2.39 ms (for 0.01 mol%) to 2.49 ms (for 2.0 mol%)
and then a slight decrease to 2.43 ms (for 6.0 mol%). This
indicates that the probability for non-radiative energy
 R. Balakrishnaiah et al. / Journal of Non-Crystalline Solids 353 (2007) 1397–1401
transfer between the Eu3+ ions in the present systems is
negligible and is almost independent of Eu3+ ions
concentration.
5. Conclusions
The JO parameters have been derived for the 1.0 mol%
Eu3+-doped fluorophosphate glass by analyzing its emis-
sion spectrum measured at RT. A relatively higher value
of X2 indicates higher covalence and/or higher asymmetry
around Eu3+ ions in the present host. Radiative properties
for the 5D0 level of Eu3+ ions can be predicted by assuming
X6 = 0 when the intensity of the 5D0 ! 7F6 transition is
very weak. The inconsistent quantitative values obtained
for quantum efficiency and the non-radiative relaxation
rate may be due to uncertainty in calculating the radiative
lifetime from the JO analysis. The experimental and calcu-
lated branching ratios are found to be in good agreement.
Addition of a fluoride contents (AlF3/BaF2) to a meta-
phosphate glass does not alter the CF strength experienced
by the Eu3+ ions. The decay profiles of the 5D0 level of
Eu3+ ions in the present fluorophosphate glass systems
are found to be single exponential for all the studied
Eu3+ ion concentrations. A marginal variation in the life-
time of the 5D0 level with Eu3+ ions concentration indicates
the almost absence of energy transfer between Eu3+ ions in
the present glass host.
Acknowledgments
This work has been carried out under a major research
project supported by DAE-BRNS, Govt. of India (Sanc-
tion No. 2003/34/4-BRNS/600). C.K.J. is also grateful to
Department Physik, Universität Paderborn, Germany, for
his stay as a Guest Scientist.
1401
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