High Pressure Research

ISSN: 0895-7959 (Print) 1477-2299 (Online) Journal homepage: https://www.tandfonline.com/loi/ghpr20

3+
High pressure fluorescence studies of Sm -doped
K–Ba–Al phosphate glass

C. K. Jayasankar, R. Balakrishnaiah, P. Babu, Th. Tröster, W. Sievers & G.

Wortmann

To cite this article: C. K. Jayasankar, R. Balakrishnaiah, P. Babu, Th. Tröster, W. Sievers & G.
3+
Wortmann (2006) High pressure fluorescence studies of Sm -doped K–Ba–Al phosphate glass,
High Pressure Research, 26:4, 349-353, DOI: 10.1080/08957950601106299

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High Pressure Research
Vol. 26, No. 4, December 2006, 349–353

High pressure fluorescence studies of Sm3+ -doped

K–Ba–Al phosphate glass
C. K. JAYASANKAR*†, R. BALAKRISHNAIAH†, P. BABU‡, Th. TRÖSTER§,
W. SIEVERS¶ and G. WORTMANN¶
†Department of Physics, Sri Venkateswara University, Tirupati 517 502, India
‡Department of Physics, Government Degree College, Wanaparthy 509 103, India
§University of Applied Science, Faculty of Automotive Systems and Production,
D-50679 Cologne, Germany
¶Universitat Paderborn, Department Physik, D-33095 Paderborn, Germany

(Received 21 September 2006; revised 11 October 2006; in final form 20 October 2006)

Pressure-induced fluorescence spectra and decay curves for the 4 G5/2 level of Sm3+ ions in
P2 O5 + K2 O + BaO + Al2 O3 glass have been studied up to 24.4 GPa at room temperature. The study
reveals that 4 G5/2 → 6 HJ (J = 9/2, 7/2 and 5/2) emission band positions are shifted to lower energy
(red shift) in the order of 2.4, 2.6 and 2.7 cm−1 per GPa, respectively. The increase in Stark level
splittings has also been noticed with increasing pressure for the emission bands mentioned above.
The decay profiles show increased non-exponential behaviour at higher pressures accompanied by a
shortening of lifetimes. The non-exponential decay curves were fitted to the Inokuti–Hirayama model.
The decrease in the lifetime with an increase in pressure is caused by an increase in the electronic
transition probabilities. This is a result of the increased crystal-field strength around Sm3+ ions. The
original results obtained after the release of pressure confirm that no structural hysteresis takes place
around the Sm3+ ions.

Keywords: Glass; Optical materials; Energy transfer; Structural properties; Crystal-field

1. Introduction

The ability to predict and to control the luminescence properties of lanthanide (R) systems
has been an aim of the optical materials community for a long time. Solid state lasers, solar
energy conversion, optical sensoring, optical data storage, phosphors and fibre amplifiers, are
examples of areas where precise control over the wavelength, line shape and efficiency of
luminescence is essential to optimise performance and to extend the range of applications.
Luminescence properties of R ions are ultimately controlled by the chemical and physical
interactions in the nearest neighbour coordination shell where factors such as bond lengths,

*Corresponding author. Tel.: +91-877-2248033; Fax: +91-877-2225211; Email: ckjaya@yahoo.com

High Pressure Research

ISSN 0895-7959 print/ISSN 1477-2299 online © 2006 Taylor & Francis
http://www.tandf.co.uk/journals
DOI: 10.1080/08957950601106299
350 C. K. Jayasankar et al.

bond angles, coordination number and covalency determine the energy, mixing and splittings
of the electronic states involved in luminescence [1].
Phosphate glasses, in particular alkali aluminometaphosphate glasses, are the promising
hosts for laser application due to their relatively lower refractive indices, lower dispersion,
larger stimulated emission cross-sections and lower thermo-optical qualities than those in
many other hosts such as silicates [2]. Sm3+ ion having different emission channels is one
of the most interesting lanthanide ions due to its wide applications in high density optical
storage, under sea water communications and colour displays.
The tremendous advances in high pressure techniques over the past decade have prompted
growing interest in research at high pressure conditions. The effect of high pressure on fluores-
cence and lifetime properties of the 4 G5/2 level of Sm3+ ions in P2 O5 + K 2 O + BaO + Al2 O3
glass is presented in this contribution.

2. Experimental details

The composition (in mol%) of the K–Ba–Al phosphate glass used in the present work
was 58.5P2 O5 + 17.0K2 O + 14.5BaO + 9.0Al2 O3 + 1.0Sm2 O3 (referred as PKBAS10). The
glass was prepared by a conventional melt quenching technique [3, 4] using high purity
chemicals of Al(PO3 )3 , Ba(PO3 )2 , KH2 PO4 and Sm2 O3 as starting materials.
A special miniature diamond anvil cell was used to generate pressures up to 24.4 GPa at room
temperature. A mixture of methanol:ethanol:water (16:3:1) was used as the pressure transmit-
ting medium with ruby as the pressure sensor. The fluorescence spectra were recorded by a
double monochromator equipped with a photomultiplier tube and using Ar+ laser (476.5 nm)
as an exciting source and under conditions similar to those in [5].

3. Results and discussion

When Sm3+ (4f5 ) ions are excited to any energy level above the 4 G5/2 multiplet, a fast non-
radiative multi-phonon relaxation will occur down to the 4 G5/2 multiplet due to small energy
differences between these higher energy states. The radiative emission will start only from the
4
G5/2 level to lower lying 6 FJ (J = 11/2, 9/2, 7/2, 5/2, 3/2 and 1/2) and 6 HJ (J = 15/2,
13/2, 11/2, 9/2, 7/2 and 5/2) levels. In the present work, attention is concentrated only on
the 4 G5/2 → 6 HJ (J = 9/2, 7/2 and 5/2) transitions.
The room temperature fluorescence spectra of PKBAS10 glass at ambient pressure as well
as at different high pressures are shown in figure 1. The spectral peaks are assigned to the
4
G5/2 → 6 HJ (J = 9/2, 7/2 and 5/2) transitions of Sm3+ ions, whose wavelengths are given
by 645, 598 and 562 nm, respectively, at ambient pressure. These emission spectra of Sm3+
ions are very much similar to the emission spectra in fluorozincate [6], borate and fluoroborate
[5, 7–9] and lead fluoroborate [10] glasses and vitreous (Sm2 O3 )0.248 (P2 O5 )0.752 [11] systems.
As can be seen from figure 1, the peak positions corresponding to the 4 G5/2 → 6 HJ (J =
9/2, 7/2 and 5/2) transitions are shifted towards lower energy with increasing pressure. The
shift of the peak positions can be described by linear equation,

Ei (p) = Ei (0) + αi p, (1)

where Ei (p) are the energies (in cm−1 ) of the studied transition (4 G5/2 → 6 HJ , J = 9/2, 7/2
and 5/2) at pressure p (in GPa) and αi are the energy shift coefficients (in cm−1 per GPa). The
values of coefficients, αi , derived from the linear fit are −2.4, −2.6 and −2.7 cm−1 per GPa
 High-pressure fluorescence studies 351

Figure 1. Emission spectra corresponding to the 4 G5/2 → 6 HJ (J = 9/2, 7/2 and 5/2) transitions of Sm3+ ions
in PKBAS10 glass at (a) 0, (b) 7.0, (c) 15.0 and (d) 24.4 GPa pressures.

for 4 G5/2 → 6 H9/2 , 6 H7/2 and 6 H5/2 transitions, respectively. The negative sign of αi indicates
the red shift with increasing pressure. It is attributed to a reduction of Slater parameters (F k )
and spin–orbit coupling parameter (ξ4f ) due to changes in the overlap of the ligand orbitals
with the 4f-wave function of Sm3+ ions with increasing pressure.
Figure 1 also shows that the degeneracy of all the 4 G5/2 → 6 HJ , (J = 9/2, 7/2 and 5/2)
states is partially enhanced since the emission peaks are split into two Stark components
well resolved even at higher pressures. The magnitude of these Stark splittings is found to
increase with increasing pressure, from 86, 92 and 128 cm−1 at ambient pressure to 228, 234
and 225 cm−1 at pressure 24.4 GPa, for 4 G5/2 → 6 HJ (J = 9/2, 7/2 and 5/2) transitions,
respectively. This points to an increase in the crystal-field strength around the Sm3+ ions
with increasing pressure. An attempt to estimate quantitatively the crystal-field strength for
Sm3+ -doped systems has not been made due to the complex electronic structure of Sm3+ ions.
The decay profiles of the 4 G5/2 level of Sm3+ ions in PKBAS10 glass were measured
at different pressures by an excitation of the sample with 476.5 nm line of Ar+ laser and by
monitoring of the 4 G5/2 → 6 H7/2 transition. The decay profiles are shown in figure 2. The non-
exponential decay has been observed at ambient pressure as well as with increasing pressure
where this non-exponential nature is more pronounced. The non-exponential decay curves
were fitted by a bi-exponential function and the average lifetime τavg was evaluated by using
the following equation:

t · I (t) dt
τavg =  , (2)
I (t) dt
where I (t) is the fluorescence intensity at time t starting from excitation [12, 13].
The fluorescence lifetimes (τavg ) of the 4 G5/2 level at different pressures are presented in
table 1. As can be seen from table 1, a rapid shortening of the lifetimes is observed with
increasing pressure, from τavg = 2397 μs at ambient pressure to τavg = 1192 μs at a maxi-
mum pressure of 24.4 GPa. It is interesting to note that the lifetime observed for the PKBAS10
glass (1.0 mol% Sm3+ ) at 11.7 GPa is equal to the lifetime observed for the PKBAS20 glass
352 C. K. Jayasankar et al.

Figure 2. Fluorescence decay profiles of the 4 G5/2 level of Sm3+ ions in PKBAS10 glass at (a) 0, (b) 7.0, (c) 15.0
and (d) 24.4 GPa pressures. Solid symbols represent the experimental decay data and the solid lines represent the IH
model fit for S = 6.

(2.0 mol% Sm3+ ) [14] at ambient conditions. The quenching of lifetime with increasing pres-
sure is attributed to an increase in the electronic transition probabilities of the emitting 4 G5/2
level and to an energy transfer between Sm3+ –Sm3+ ions. In order to determine the nature
of energy transfer, the decay curves of the 4 G5/2 level of Sm3+ ions in PKBAS10 glass have
been fitted in the frame of the Inokuti–Hirayama (IH) model [15], where τ0 is assumed to
the τavg value at 0 GPa. As can be seen from figure 2, best fit of experimental curves were
obtained for S = 6, at all the studied pressures indicating the dominant dipole–dipole interac-
tion for energy transfer. The lifetimes (τavg ) of the 4 G5/2 level of Sm3+ ions in PKBAS10 glass
at different pressures along with energy transfer parameter (Q), dipole–dipole interaction
parameter (CDA ) and the critical distance (R0 ) between the donors and acceptors are listed

Table 1. Fluorescence lifetime (τavg , μs) of 4 G5/2 level,

energy transfer parameter (Q) of Sm3+ ions and critical
distance between donor and acceptor (R0 , nm) and
dipole–dipole interaction parameter (CDA ,
×10−42 cm6 /s) in PKBAS10 glass at different pressures.

Pressure τavg Q R0 CDA

Pressure increasing
0 2397 0 0 0
1.7 2280 0.25 0.52 8.0
4.1 2040 0.39 0.60 19.3
7.0 1698 0.93 0.80 110.2
11.7 1660 0.99 0.82 125.0
15.0 1467 1.30 0.90 215.9
17.4 1444 1.33 0.90 224.7
20.4 1218 1.71 0.98 371.8
24.4 1192 1.77 0.99 400.0
Pressure decreasing
14.8 1373 1.25 0.88 199.1
8.3 1615 0.83 0.77 87.6
2.8 2069 0.42 0.61 22.4
 High-pressure fluorescence studies 353

in table 1. It can be observed that R0 , Q and CDA values increase with increasing pressure,
where as the lifetime follows the opposite trend. The results obtained during the release of
pressure show that the application of pressure on the present system is a reversible process
without any permanent deformation of structure around Sm3+ ions. The general trends in the
fluorescence and decay times of R-ion-doped glasses under pressure will be a main focus in
our future publication.

4. Conclusions

The effect of pressure on fluorescence properties of Sm3+ ions in PKBAS10 glass has been
investigated. A red shift and enhancement of crystal-field splittings of 4 G5/2 → 6 HJ (J =
9/2, 7/2 and 5/2) emission bands with increase in pressure are observed and are attributed
to an expansion of the 4f electron wave function with increasing covalency and increase
in crystal-field strength around Sm3+ ions, respectively. The decay profiles show increased
non-exponential behaviour at higher pressures accompanied by shortening of lifetimes. The
non-exponential behaviour of decay profiles is attributed to the energy transfer between the
donor (Sm3+ ) and acceptor (Sm3+ ) ions due to dipole–dipole interactions. The amount of
energy transfer is found to increase with increase in pressure, which is due to additional
possible channels of non-radiative decay. The decrease in the lifetime with increase in pressure
is due to an increase in the electronic transition probabilities, which is a result of the increased
crystal-field strength around Sm3+ ions. The results obtained after release of pressure remain
unchanged, indicating that no structural hysteresis takes place around Sm3+ ions.

Acknowledgements

This work has been carried out under the financial assistance of a major research project
sponsored by DAE-BRNS, Government of India (no. 2003/34/4-BRNS/600, dt. 11-07-2003).
C. K. Jayasankar is grateful to Department Physik, Universität Paderborn, Germany also for
his stay as a Guest Scientist.

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