Optical properties and spectroscopic parameters of Nd

3
-
doped phosphate and borate glasses
V. Mehta
a,1
, G. Aka
a,
*
, A.L. Dawar
b
, A. Mansingh
c
a
Laboratoire de Chimie Appliquee de l'Etat Solide, CNRS-URA, 1466 ENSCP, 11 rue P. et M. Curie, 75231 Paris Cedex 05, France
b
Defence Science Centre, Metcalfe House, New Delhi 110054, India
c
Electronic Materials and Devices Laboratory, Department of Physics and Astrophysics, University of Delhi, New Delhi 110007, India
Received 15 July 1998; accepted 30 October 1998
Abstract
Neodymium doped borate and phosphate glass specimens have been prepared by the melt quenching technique.
Their absorption spectra have been recorded in the region 3001000 nm. The JuddOfelt theory has been applied to the
measured values of absorption line strengths to evaluate the spontaneous emission probabilities from the
4
F
3a2
level,
quantum eciencies and stimulated emission cross sections of the
4
F
3a2

4
I
11a2
transition for Nd
3
. The values of
emission cross sections are comparable with those shown by glasses used in solid state laser applications. 1999
Published by Elsevier Science B.V. All rights reserved.
Keywords: Optical properties; Absorption spectra; JuddOfelt analysis
1. Introduction
The numerous known inorganic glass forming
systems [1] provide many possible hosts for laser
ions. In the three decades since the initial report of
laser action in glass, the spectroscopic properties
of rare earth ions in many dierent glasses have
been investigated [2] including recent extensive
surveys of trivalent neodymium ion (Nd
3
) in sil-
icate [3], phosphate [36], borate [3,7,8], sulphate
[9], tellurite [10,11], acetate [12], aluminate [13,14],
gallate [15,16] and several heavy metal uoride
glasses [1722]. In many cases, signicant changes
in spectroscopic parameters are observed when the
chemical composition of the glass is altered. These
arise from changes in both the glass network
forming and network modifying ions.
A number of optical and spectroscopic prop-
erties of a laser gain material are of prime impor-
tance in designing a laser device. These include
spectral absorbances, branching ratios, emission
cross sections, peak wavelengths, uorescence
lifetimes, quantum eciencies and uorescence-
quenching processes. The relationship between
these parameters and the nature of the glass host is
of particular interest for developing new laser
materials.
In the present work, we report the results on
systematic studies of spectroscopic properties of
Nd
3
ion inborate and phosphate basedglasses, viz.
Na
2
OAl
2
O
3
B
2
O
3
(NaAB), K
2
OBaOAl
2
O
3

P
2
O
5
(KBAP) and ZnOLi
2
OP
2
O
5
(ZLP). The
Optical Materials 12 (1999) 5363
*
Corresponding author. Tel.: 33 1 44276707; fax: 33 1
46347489; e-mail: akagp@ext.jussieu.fr
1
On leave from Kalindi College (University of Delhi), East
Patel Nagar, New Delhi 110008, India.
0925-3467/99/$ see front matter 1999 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 5 - 3 4 6 7 ( 9 8 ) 0 0 0 7 4 - 3
refractive indices of the glasses are calculated as a
function of wavelength. The absorption spectra are
analysed on the basis of the JuddOfelt theory
[23,24], which has become a standard tool for cal-
culating the parity forbidden electric dipole radia-
tive rates between various levels of rare earth ions in
both crystalline and glassy hosts. The three phe-
nomenological J-O intensity parameters X
t
(t =2, 4
and 6) are determined, by performing a least squares
t of calculated and observed absorption line in-
tensities. These intensity parameters are then used
todetermine the spontaneous emissionprobabilities
and branching ratios from the Nd
3 4
F
3a2
metasta-
ble state to the ground manifolds. A comparison of
the radiative probability found in this way with
values (deduced experimentally from the uores-
cence decay curves) of the average lifetime of the
metastable level yielded the absolute quantum e-
ciency of uorescence from this level. This is com-
bined with measured uorescence spectral data to
calculate stimulated emission cross sections.
2. Experimental
2.1. Sample preparation
The samples were prepared in batches weighing
about 100 g, by fusing together appropriate
quantities of analytical reagent grade chemicals.
Glass formers were introduced as phosphoric an-
hydride NH
4
H
2
PO
4
, boric acid H
3
BO
3
and alu-
minium oxide Al
2
O
3
while glass modiers were
introduced as their respective carbonates. Neo-
dymium was added as trivalent neodymium oxide
Nd
2
O
3
. Nd
2
O
3
was of 99.9% purity. The dry in-
gredients were thoroughly mixed and then melted
in alumina or platinum crucibles at working tem-
peratures between 1200C and 1250C for borate
glass and 1000C and 1150C for phosphate
glasses. The melt was allowed to heat for a period
of 45 h and occasionally stirred to get homoge-
neous and bubble free glass. The homogeneous
glass was cast in the form of a block in suitable
mould and then annealed to make it strain free.
The samples of desired sizes were cut from the best
portion of the block and were nally ground and
polished for characterization work.
The Nd concentration in the samples used for
present studies, as given in Table 1, was deter-
mined by atomic absorption spectrometry.
The glasses were examined for crystallinity by
X-ray diraction. A Phillips PW 1130/00 X-ray
diractometer with BraggBreutano arrangement
was used for recording X-ray diractograms.
Monochromatic CuK
a
(k =1.5405
#
A) radiation
was used as an X-ray source.
2.2. Optical measurements
Optical reectance and transmittance measure-
ments were performed on a Hitachi 330 double
beam spectrophotometer. Absorption spectra were
recorded using a Cary 5 spectrophotometer. The
areas under the absorption bands were determined
using a graphing program (Kaleidagraph).
Fluorescence spectra were acquired by exciting
neodymium uorescence with a 1 W, CW tuneable
titanium sapphire laser (Coherent 890) pumped by
a 6 W argon-ion laser (Coherent-Innova 90).
Fluorescence was chopped and dispersed by a Jo-
bin-Yvon HR-25 grating monochromater. A PbS
cell detector, associated with a lock-in amplier
(EG and G), ensured the acquisition of spectra
with a good signal-to-noise ratio in the near IR
range.
For uorescence lifetime measurements, exci-
tation wavelength was selected by using an Optical
Parameteric Oscillator (OPO) which allows the
selection of excitation wavelengths in the range
4202500 nm, after pulsed excitation at 355 nm,
third harmonic of a Q-switched Nd:YAG laser.
Various excitation wavelengths in the Nd absorp-
tion band were selected to check the emission with
dierent Nd centers in the samples. The emitted
light was detected by means of an InGaAs cell and
seen on an oscilloscope TDS 420 (Tektronix). The
data was later stored in a microcomputer and the
Table 1
Concentration of Nd
3
ions in selected samples
Glass Nd
3
concentration
Wt% Ions/cm
3
Na
2
OAl
2
O
3
B
2
O
3
(NaAB) 1.3 1.18 10
20
K
2
OBaOAl
2
O
3
P
2
O
5
(KBAP) 3.4 3.86 10
20
ZnOLi
2
OP
2
O
5
(ZLP) 2.2 2.28 10
20
54 V. Mehta et al. / Optical Materials 12 (1999) 5363
decay curves were subjected to appropriate math-
ematical tting procedures in order to determine
the rst e-folding lifetimes.
The uorescence decay proles at 77 K were
recorded by placing the sample in a liquid nitrogen
Dewar. For still lower temperatures (down to
12 K), a liquid helium cryogenerator was used.
FTIR transmittance spectra were recorded
using Bruker IFS48 spectrometer.
3. Results and discussion
3.1. X-ray diraction pattern
Prepared glasses contained no crystalline phases
as revealed by the X-ray diractograms.
3.2. Refractive index
The refractive indices of the glasses were eval-
uated using transmittance (T) and reectance (R)
data recorded on very thin samples. An iterative
computer program employing the technique of
simplex minimization [25,26] was used. The equa-
tions used in the program are equivalent to the
equations given by Heavens [27]. Several trial
values of refractive index, n and extinction coe-
cient, k were put in these equations and the values
of R and T were calculated. These calculated val-
ues of R and T were compared with the observed
values and the dierence between the actual and
the calculated values was minimized using the
simplex method. The iterations were continued,
each time the range of trial values of n and k was
reduced until the dierence between the observed
and calculated values was within the desired ac-
curacy.
The values of n are plotted as a function of
wavelength in Fig. 1. The variation of n is in ac-
cordance with the typical shape of dispersion curve
of an optical glass [28].
3.3. Absorption spectra and JuddOfelt analysis
The room temperature absorption spectra were
recorded for all the samples in the wavelength
range 2001000 nm and are shown in Fig. 2. The
peaks in Fig. 2 correspond to transitions from the
4
I
9a2
ground state to the [SL] J energy states of
Nd
3
[29,30]. Because of inhomogeneous broad-
ening, the Stark structure is poorly resolved. Ad-
jacent energy levels often overlap and appear in
the spectrum as one. It may be mentioned that the
absorption spectra of Nd
3
in dierent hosts are
very similar. The observed peak positions are ap-
proximately at the same wavelengths. The only
eect of the host is to cause small changes in the
relative peak intensities [31].
The data from these absorption spectra can be
used to predict the radiative lifetime of the initial
laser state
4
F
3a2
, the branching ratios and the ra-
diative transition probabilities of uorescence
transitions from
4
F
3a2
to
4
I
t
/ manifolds (J
/
=9/2
15/2) of Nd
3
ions, using the JuddOfelt (J-O)
analysis method. Only a brief outline of the per-
tinent equations used in the analysis is given here.
A more detailed theory and applications can be
found in the literature [23,24,32,33].
Fig. 1. Variation of the refractive index, n, as a function of
wavelength, k, of Nd
3
-doped NaAB, KBAP and ZLP glasses.
V. Mehta et al. / Optical Materials 12 (1999) 5363 55
The line strength of the electricdipole transi-
tion between two J states can be measured from
the acquired absorption spectra, using the relation
[34,35]

means
(t t
/
)
=
3h(2t 1)
8p
3
e
2
1
x
9n
(n
2
2)
2
2X3
"
kt
_
tt
/
OD(k) dkY
(1)
where J and t
/
are the total angular momentum
quantum numbers of the initial and nal states,
respectively,
"
k is the mean wavelength of the spe-
cic absorption band, n = n(
"
k) the refractive index
at the mean wavelength
"
k, c the velocity of light, e
the electron charge, h the Planck's constant, N the
Nd
3
ion concentration, t the sample thickness and
OD the optical density.
The measured line strengths can then be used to
calculate the J-O intensity parameters X
2
, X
4
and
X
6
by solving a set of equations for the corre-
sponding transitions between initial [(Y v)t) and
terminal [(
/
Y v
/
)t
/
) manifolds expressed by Judd
[23] and Ofelt [24] in the form

calc
(t t
/
)
=

t=2Y4Y6
X
t
(Y v)t|
(t)
|(
/
Y v
/
)t
/
_

2
Y (2)
where the elements |
(t)
|
_
are the doubly re-
duced unit tensor operators calculated in the in-
termediate coupling approximation. Since the 4f
3
electrons are well shielded by other layers in tri-
valent rare earth ion (RE
3
), the reduced matrix
elements |
(t)
|
_
are virtually independent of the
ligand species surrounding the RE
3
ions and thus
approximately unchanged from host to host [36].
Numerous sets of reduced matrix elements data
calculated through various approaches in the lit-
erature conrm this fact [37,38] and thus can be
readily applied in intensity analysis. The three
phenomenological parameters X
2
, X
4
and X
6
, on
the other hand, exhibit the inuence of the host on
the radiative transition probabilities, since they
contain implicitly the eects of the odd-symmetry
crystal-eld terms, intercongurational radial in-
tegrals and energy denominators.
Ten absorption bands lying between 350 and
1000 nm region were chosen and numerically in-
tegrated. Values of the doubly reduced matrix el-
ements |
(t)
|
_
of unit tensor operators for these
bands were taken from the set of values for Nd
3
listed by Kaminskii et al. [38]. When two or more
absorption manifolds overlapped, the matrix ele-
ment was taken to be the sum of the corresponding
squared matrix elements. The best set of X
t
(t =2,
4 and 6) parameters was determined by a least
squares tting of the calculated S values given by
Eq. (2) to the experimental ones given by Eq. (1).
The quality of the t obtained from the absorption
Fig. 2. Absorption spectra of Nd
3
in NaAB, KBAP and ZLP
glasses.
56 V. Mehta et al. / Optical Materials 12 (1999) 5363
spectra is shown in Table 2 where measured (S
m
)
and calculated (S
c
) line strengths are compared for
the borate and phosphate glasses under study. The
largest dierences occur for transitions to the
4
F
3a2
and (
2
K
13a2
,
4
G
7a2
,
4
G
9a2
) states [39,40]. The J-O
parameters obtained from this tting are given in
Table 3. These values are in good agreement with
those reported for the Nd
3
ion in dierent glass
matrices [34,40,41].
The radiative transition rates and the branching
ratios for the electricdipole transitions from
4
F
3a2
manifolds to the
4
I
t
/ manifolds (J
/
=15/2,
13/2, 11/2, 9/2) of the Nd
3
ion can now be cal-
culated from the X
t
parameters. The transition rate
from initial J manifold (Y v)t [ ) to terminal man-
ifold (
/
Y v
/
)t
/
[ ) is given [42] by
e[(Y v)tY (
/
Y v
/
)t
/
[
=
64p
4
e
2
n
3h(2t 1)
"
k
3
(n
2
2)
2
9
_ _

t=2Y4Y6
X
t
(Y v)t|
(t)
|(
/
Y v
/
)t
/
_

2
Y (3)
where n(n
2
+2)
2
/9 is the local-eld correction for
the Nd
3
ion [43] in the initial J manifold.
The uorescence branching ratios for transi-
tions originating on a specic initial manifold
(Y v)t [ ) are dened [42] by
Table 2
Measured (S
m
) and calculated (S
c
) absorption line strengths (10
20
cm
2
) for Nd
3
in borate and phosphate glasses
Glass Transition k (nm) S
m
S
c
Di.
NaAB
4
I
9a2

4
F
3a2
871.7 1.50 1.08 0.30
4
F
5a2
,
2
H
9a2
801.2 4.02 4.29 0.27
4
F
7a2
,
4
S
3a2
745.1 3.79 3.69 0.10
4
F
9a2
677.0 0.24 0.28 0.04
2
H
11a2
622.9 0.08 0.07 0.01
2
G
7a2
,
4
G
5a2
581.1 7.64 7.68 0.04
2
K
13a2
,
4
G
7a2
,
4
G
9a2
523.7 2.94 2.32 0.62
2
K
15a2
,
2
D
3a2
,
2
G
9a2
,
4
G
11a2
472.4 0.79 0.68 0.11
2
P
1a2
,
2
D
5a2
429.4 0.23 0.25 0.02
4
D
3a2
,
2
I
11a2
,
4
D
5a2
,
4
D
1a2
,
2
L
15a2
356.6 3.90 3.90 0
KBAP
4
I
9a2

4
F
3a2
873.0 0.94 1.20 0.26
4
F
5a2
,
2
H
9a2
800.0 3.23 3.31 0.08
4
F
7a2
,
4
S
3a2
744.5 3.08 3.09 0.01
4
F
9a2
679.0 0.21 0.22 0.01
2
H
11a2
624.1 0.04 0.06 0.02
2
G
7a2
,
4
G
5a2
580.9 6.03 6.06 0.03
2
K
13a2
,
4
G
7a2
,
4
G
9a2
523.5 2.11 1.67 0.44
2
K
15a2
,
2
D
3a2
,
2
G
9a2
,
4
G
11a2
472.5 0.56 0.34 0.22
2
P
1a2
,
2
D
5a2
428.4 0.21 0.16 0.05
4
D
3a2
,
2
I
11a2
,
4
D
5a2
,
4
D
1a2
,
2
L
15a2
356.1 2.44 2.46 0.02
ZLP
4
I
9a2

4
F
3a2
872.7 1.09 1.56 0.46
4
F
5a2
,
2
H
9a2
803.1 3.80 3.98 0.18
4
F
7a2
,
4
S
3a2
746.4 3.67 3.59 0.08
4
F
9a2
679.6 0.26 0.26 0
2
H
11a2
624.9 0.07 0.07 0
2
G
7a2
,
4
G
5a2
582.2 7.03 7.06 0.03
2
K
13a2
,
4
G
7a2
,
4
G
9a2
525.2 2.41 2.05 0.36
2
K
15a2
,
2
D
3a2
,
2
G
9a2
,
4
G
11a2
472.7 0.71 0.42 0.29
2
P
1a2
,
2
D
5a2
428.5 0.17 0.21 0.04
4
D
3a2
,
2
I
11a2
,
4
D
5a2
,
4
D
1a2
,
2
L
15a2
356.8 3.33 3.22 0.11
RMS DS=10
21
.
V. Mehta et al. / Optical Materials 12 (1999) 5363 57
b[(Y v)tY (
/
Y v
/
)t
/
[
=
e[(Y v)tY (
/
Y v
/
)t
/
[

/
Yv
/
Yt
/
e[(Y v)tY (
/
Y v
/
)t[
Y (4)
where the sum is over all possible terminal mani-
folds (

Y v

)t

[ ). The sum represents the total tran-

sition probability for radiative decay from the
initial manifold.
The radiative lifetime of a level is related to the
total transition probability [42] as
s
c
rad
=

/
Yv
/
Yt
/
e[(Y v)tY (
/
Y v
/
)t
/
[
_
_
_
_
_
_
1
= e
1
total
X (5)
4
F
3a2
spontaneous emission transition rates A
and branching ratios b for the Nd
3
ion in the
three borate and phosphate glasses under study,
are listed in Table 5, together with the total
spontaneous emission probability (A
total
). From
Eq. (3), it is clear that the radiative transition rate
A for the transitions
4
F
3a2

4
I
t
/ (J
/
=15/2, 13/2,
11/2 and 9/2) depends on the intensity parameters
X
4
and X
6
only because the matrix elements of
rank 2 for transitions between these states are
equal to zero [38]. Therefore, the branching ratios
given by Eq. (4) can be expressed in terms of only
the ratio X
4
/X
6
, called the spectroscopic quality
factor v [44]. By substituting Eq. (3) into Eq. (4),
the analytical expression for the branching ratio
becomes
b
tt
/
=
1
"
k
3
t
/
v (Y v)t|
(4)
|(
/
Y v
/
)t
/
_

2
(Y v)t|
(6)
|(
/
Y v
/
)t
/
_

2
_ _

/
Yv
/
Yt
/
1
"
k
3
t
/
v (Y v)t|
(4)
|(
/
Y v
/
)t
/
) [ [
2
(Y v)t|
(6)
|(
/
Y v
/
)t
/
) [ [
2
_ _
(6)
Fig. 3 shows a plot of b
tt
/ versus v, for the four
Nd
3
laser transitions of interest [45]. To maximize
the intensity of the (
4
F
3a2

4
I
11a2
) transition, it is
clearly necessary that X
6
X
4
whereas to maxi-
mize (
4
F
3a2

4
I
9a2
) the opposite is required. From
the values obtained for the glasses under study, the
highest spectroscopic quality factor corresponds to
the NaAB glass (see Table 3). Fig. 3, however,
also shows that large changes in b are possible only
if the ratio X
4
/X
6
varies signicantly. In our case,
X
4
/X
6
is varying only in the relatively narrow
range of 0.941.28. Thus, variation in the values of
b among dierent glasses is small, as can be seen
from Table 4.
The radiative lifetime s
c
rad
, computed as the re-
ciprocal of total transition probability A
total
, is
given in Table 5. This radiative lifetime calculated
from J-O intensity parameters represents an eec-
tive average over the site-to-site variations in the
local Nd
3
environment. It is inversely propor-
tional to a linear combination of X
4
and X
6
pa-
rameters. The correction for the local eld at the
Nd
3
site, however, introduces a dependence on
the refractive index also. The refractive index
which enters as n(n
2
+ 2)
2
in Eq. (3), has a non-
negligible eect. Thus, although the branching
ratios for all transitions are relatively invariant
Table 3
JuddOfelt intensity parameters (10
20
cm
2
) for Nd
3
in borate
and phosphate glasses
Intensity parameter NaAB KBAP ZLP
X
2
3.53 3.42 3.60
X
4
6.57 4.09 5.41
X
6
5.12 4.35 4.99
v =X
4
/X
6
1.28 0.94 1.08
Fig. 3. Fluorescence branching ratios for Nd
3
from the
4
F
3a2
state to the
4
I
t
/ (t
/
=15/2, 13/2, 11/2, 9/2) level versus the
spectroscopic quality factor, v =X
4
/X
6
.
58 V. Mehta et al. / Optical Materials 12 (1999) 5363
with composition, the total transition rate or life-
time varies signicantly among dierent glass
matrices.
3.4. Fluorescence measurements
3.4.1. Emission cross sections
The room temperature uorescence spectra
were recorded for all the samples in the spectral
range 8001400 nm. The peak wavelengths k
p
of
the main peak corresponding to the transition
4
F
3a2

4
I
11a2
are given in Table 5.
From the uorescence spectra, the stimulated
emission cross section at wavelength k for a me-
dium of refractive index n can be calculated from
the relation [46,47]
r =
k
5
8pn
2
b(t t
/
)
s
c
rad
g(k)Y (7)
where g(k) is the line shape function expressed as
g(k) =
s(k)
_
ks(k) dk
X (8)
Here I(k) represents the uorescence intensity as a
function of wavelength. For computing g(k), the
uorescence spectra were fully corrected for the
spectral intensity response of the detection system.
Fig. 4 shows the plots of emission cross section
of borate and phosphate glasses under study for
the
4
F
3a2

4
I
11a2
uorescence emission. The val-
ues of the peak stimulated emission cross-sections
r
p
calculated at k
p
for these glasses are listed in
Table 5. These values are comparable with those
shown by other glasses used in solid state laser
applications [29].
3.4.2. Fluorescence lifetime and quantum eciency
The uorescence decays of the Nd
3 4
F
3a2
manifold were found to be purely exponential for
all the samples studied. The lifetimes s
f
(the rst e-
folding times), measured in the representative
glasses are given in Table 5. To check the presence
of water in the phosphate glasses which could
shorten their lifetimes [4], their IR transmission
spectra were recorded in the range 20004000
cm
1
. However, no OH content was found in the
samples. The radiative quantum eciencies g
c
de-
ned by the ratio s
f
(measured uorescence life-
time)/s
c
rad
(calculated radiative lifetime) are also
listed in Table 5. As can be observed from this
table, the uorescence lifetimes s
f
are much shorter
than the JO predicted radiative lifetimes s
c
rad
which
leads to quite low values of quantum eciencies
in these glasses. Multiphonon non-radiative
Table 5
Radiative properties of Nd
3
doped phosphate and borate glasses
Property NaAB KBAP ZLP
Calculated radiative lifetime, s
c
rad
(ls) 295 376 284
Measured uorescence lifetime, s
f
(ls) 59 43 54
Calculated radiative quantum eciencies, g
c
0.20 0.11 0.19
4
F
3a2

4
I
11a2
transition
k
p
(nm) 1057 1057 1057
Peak stimulated emission cross section, r
p
(10
20
cm
2
) 3.1 2.3 3.2
Table 4
4
F
3a2
radiative transition rates A and branching ratios b for Nd
3
doped borate and phosphate glasses
Glass Transition
4
F
3a2

4
I
9a2
4
I
11a2
4
I
13a2
4
I
15a2
A
total
(s
1
)
A (s
1
) b A (s
1
) b A (s
1
) b A (s
1
) b
NaAB 1600 0.47 1500 0.44 280 0.08 6.8 0.003 3386.8
KBAP 1200 0.45 1200 0.45 250 0.09 6.3 0.002 2656.3
ZLP 1600 0.45 1600 0.45 310 0.09 7.7 0.002 3517.7
V. Mehta et al. / Optical Materials 12 (1999) 5363 59
theoretical approach can be used to explain this
low quantum eciency in these materials.
Excited electronic states of RE
3
ions in solids
can decay non-radiatively by exciting lattice vi-
brations. When the energy gap between the excited
state and the next-lower state is larger than the
maximum phonon energy in the material, emission
of several phonons is required to conserve energy.
Relaxation by multiphonon processes is well es-
tablished from studies of rare earths in both
crystals and glasses [48,49]. These results demon-
strate that for high-order processes ( P3 pho-
nons), the decay state is determined predominantly
by the number of phonons required to bridge the
energy gap. Since the highest-energy phonons can
conserve energy in the lowest-order process, they
are most important in the relaxation.
Several theoretical approaches of the multi-
phonon relaxation process are available in the lit-
erature [5053]. According to these, the rate of
non-radiative multiphonon emission W
p
in a pth-
order process across an energy gap DE, in which p
phonons, each of energy
"hx = Diap
are involved, is given by

p
= g[n() 1[
p
exp(a Di)X (9)
Here a = ln()a"hx; =
p
a
p1
and C is a host-
dependent constant. n(T) is the occupation num-
ber of a phonon mode, described by the Bose
Einstein relationship
n() = (e
"hxak
1)
1
X (10)
Eq. (9) shows the exponential dependence of W
p
on DE as well as its temperature dependence.
Combining Eqs. (9) and (10), we can write

p
() =
0
exp("hxak )
exp("hxak) 1
_ _
p
Y (11)
where W
0
=W
p
(T=0 K) =C exp( a DE).
The IR transmittance spectra of borate and
phosphate glasses under study are shown in Fig. 5.
The energies of the highest frequency vibrations in
these glasses are listed in Table 6. These phonon
energies are in good agreement with the literature
values [54].
The energy gap DE between the
4
F
3a2
and
4
I
15a2
states is about 5400 cm
1
. This leads to predict the
number of phonons p = Dia"hx ~ 4.
Assuming that no cross relaxation phenomenon
occurs, W
p
(T) is related to the calculated s
c
rad
and
measured s
f
(T) lifetimes of the
4
F
3a2
excited state,
by the following expression:
1
s
f
()
=
p
()
1
s
c
rad
X (12)
4
F
3a2
Nd
3
lifetimes were measured versus
temperature (from 15 to 700 K) for Nd: borate and
Fig. 4.
4
F
3a2

4
I
11a2
emission cross section (r) for Nd
3
-doped
NaAB, KBAP and ZLP glasses.
60 V. Mehta et al. / Optical Materials 12 (1999) 5363
phosphate glasses. The dependence of the multi-
phonon emission rate was found, using Eq. (12) by
subtracting the calculated radiative rate from the
measured lifetimes at each temperature. Fig. 6
shows the resulting temperature dependence of
Table 6
Phonon energies of borate and phosphate glasses
Glass Phonon energy (cm
1
)
NaAB 1379.5
KBAP 1419.3
ZLP 1419.7
Fig. 6. Measured temperature dependence of multiphonon
emission rate for Nd
3
in NaAB, KBAP and ZLP glasses,
compared with theoretical curves, calculated from Eq. (11) as-
suming relaxation by 4() and 5(- - -) 1724 cm
1
phonons for
NaAB glass, 1595 cm
1
phonons for KBAP glass and 1753
cm
1
phonons for ZLP glass.
Fig. 5. IR transmittance spectra of NaAB, KBAP and ZLP
powdered glasses.
V. Mehta et al. / Optical Materials 12 (1999) 5363 61
W
p
. These experimental points were tted with
Eq. (11) for which W
0
(T=0 K) was evaluated
using the measured lifetimes at 15 K. The curves in
Fig. 6 are temperature dependencies predicted
from Eq. (11) using the following numbers and
energies of phonons:
Nd:NaAB glass 45 phonons, 1724.4 cm
1
,
Nd:KBAP glass 45 phonons, 1594.7 cm
1
,
Nd:ZLP glass 45 phonons, 1752.7 cm
1
,
i.e. if the above values of energies are used in
Eq. (11) instead of those given in Table 6, the model
ts the observed temperature dependence with the
multiphonon emission rate occurring between 4 and
5 phonons. Thus the observed quantumeciencies,
listed in Table 5, seem to be in agreement with the
multiphonon non-radiative relaxation.
It may be mentioned that although the above
values of phonon energies, used in the ts, are
higher than those reported in similar glasses [29],
these are in agreement with the FTIR spectra re-
corded in the range 5002000 cm
1
. More spec-
troscopic investigations are required for a complete
understanding. For example, NMR study is cur-
rently in progress in the laboratory to determine
the type of borate or phosphate group present in
the NaAB, KBAP and ZLP glass systems.
4. Conclusions
(a) Good optical quality glass specimen could
be prepared in sizes as large as 1.5 1 1 cm by
the melt quenching technique.
(b) The X-ray diractograms of the samples
conrm the amorphous nature of the glasses.
(c) In the wavelength range 2002500 nm, re-
fractive index of the 1.3 wt% Nd:NaAB glass
varies from 1.834 to 1.522, of the 3.4 wt%
Nd:KBAP glass from 1.976 to 1.523 and 2.2 wt%
Nd:ZLP glass from 1.925 to 1.552.
(d) Intensity parameter X
2
is found to have
substantial value for all the glasses studied. This
indicates that the local coordination at the Nd
3
site in these glasses is of suciently low symmetry.
(e) The magnitude of the spectroscopic quality
factor X
4
/X
6
varies in a narrow range from 0.94 to
1.28 and thus, the branching ratios b also do not
vary signicantly among dierent glasses.
(f) The measured uorescence lifetimes s
f
are
found to be much shorter than the radiative life-
times s
c
rad
predicted by J-O theory. The low values
of quantum eciencies in these materials have
been shown to be due to multiphonon non-radia-
tive relaxation processes.
(g) The values of the stimulated emission cross
sections for neodymium doped borate and phos-
phate glasses studied, compare well with the values
displayed by laser glasses of technological impor-
tance and therefore could be regarded as possible
candidates for laser applications.
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