Absorption intensities and emission cross sections of Tb

3+
4f
8
in TbAlO
3
Dhiraj K. Sardar,
a
Kelly L. Nash, Raylon M. Yow, and John B. Gruber
Department of Physics and Astronomy, University of Texas at San Antonio, San Antonio, Texas 78249-0697
Uygun V. Valiev
Physics Faculty, Uzbekistan National University, 700174 Tashkent, Uzbekistan
Edvard P. Kokanyan
Institute for Physical Research, National Academy of Sciences, 378410 Ashtarak, Armenia
Received 24 May 2006; accepted 17 July 2006; published online 23 October 2006
Trivalent terbium absorption intensities in single-crystal TbAlO
3
are analyzed using the Judd-Ofelt
model to assess the crystals potential as a solid state laser system. The standard Judd-Ofelt model
was applied to the room temperature absorption intensities of Tb
3+
4f
8
to determine the
phenomenological intensity parameters
2
,
4
, and
6
. Seven multiplet manifolds are identied
and the absorption intensities of these manifolds are least-squares tted to the calculated intensities
to obtain the intensity parameters:
2
=40.5210
20
cm
2
,
4
=8.7410
20
cm
2
, and
6
=2.26
10
20
cm
2
in TbAlO
3
. These intensity parameters are then applied to determine the radiative
decay rates and branching ratios of Tb
3+
transitions from the
5
D
4
to the
7
F
J

multiplet manifolds.
Based on the results, the radiative lifetime of the excited state manifold
5
D
4
is determined from the
radiative decay rates and found to be 3.5 ms. The calculated lifetime is longer than the measured
lifetime, reecting the nonradiative interactions between the Tb
3+
ions and the lattice in the pure
compound. The intensity parameters, radiative lifetime, and emission cross sections are then
compared to those reported in other laser hosts. The quantum efciency of the laser transition
5
D
4

7
F
5
of Tb
3+
is approximately 57.0% in TbAlO
3
. 2006 American Institute of Physics.
DOI: 10.1063/1.2358401
I. INTRODUCTION
There has been considerable interest in trivalent terbium
doped into various hosts for use as solid state lasers. In par-
ticular, there has been interest in terbium for its stimulated
emission at 544 nm. Shaw et al. reported on the mid- and
long wavelength infrared IR laser potential for Tb
3+
in
chalcogenide glass bers.
1
Strong Tb
3+
emission in TbAlO
3
at room temperature and detailed spectroscopic studies on
TbAlO
3
have been investigated by Sekita et al.
2,3
Jenssen
et al.
4
reported room temperature pulsed laser operation at
544 nm for the Tb
3+ 5
D
4

7
F
5
manifold transition in
Tb
3+
: YLF yttrium lithium uoride with a lifetime for this
transition as approximately 5.0 ms. However, Weber et al.
5
reported a predicted lifetime of 2.07 ms and measured life-
time of 1.7 ms for this same Tb
3+
transition in YAlO
3
, while
Boehm and Spector have reported a measured lifetime of
2.2 ms for this transition in germinate glass.
6
In this article, we characterize the optical properties of
Tb
3+
ions in TbAlO
3
using the theory of forced electric
dipole transitions in rare-earth-doped materials developed by
Judd
7
and Ofelt.
8
The Judd-Ofelt JO theory has long been
considered to be one of the most successful theories in esti-
mating the magnitude of the forced electric dipole transitions
of rare earth ions. The standard JO analysis is applied to the
room temperature absorption intensities of Tb
3+
4f
8
to de-
termine the optical intensity parameters, radiative transition
probabilities decay rates, radiative lifetime, and branching
ratios of Tb
3+
manifold to manifold transitions in the sto-
ichiometric host TbAlO
3
. Since the JO intensity parameters
used to determine the radiative transition probabilities de-
pend on the particular rare earth ion and its local environ-
ment, accurate values of these parameters are necessary to
characterize the spectroscopic and laser properties of
TbAlO
3
.
II. EXPERIMENTAL PROCEDURE
The TbAlO
3
crystal used in this study was obtained from
Sekita through one of the authors U.V.V.; the single crystals
of TbAlO
3
were grown by the Czochralski CZ method in
both an inert nitrogen gas and a reducing atmosphere con-
taining a mixture of nitrogen and hydrogen gas.
2
A detailed
description of the crystal growth is given in Sekita et al.
2
The
Tb
3+
concentration in the stoichiometric crystal TbAlO
3
is
determined to be 1.7710
22
/ cm
3
. The sample was polished
to at and parallel faces for optical measurements.
The room temperature absorption spectrum of Tb
3+
4f
8

in TbAlO
3
was recorded on an upgraded Cary model 14R
spectrophotometer controlled by a computer with data acqui-
sition software from OLIS. The spectrum ranging from
330 to 500 nm is displayed in Fig. 1. The spectral bandwidth
was set at 0.25 nm for this measurement, and the spectrom-
eter was internally calibrated to an accuracy of 0.3 nm.
The room temperature uorescence spectrum of the
TbAlO
3
was taken between 460 and 660 nm by exciting the
sample with 363 nm light from a 150 W xenon-arc lamp
with a UG-1 lter. The uorescence spectrum was analyzed
a
Electronic mail: dsardar@utsa.edu
JOURNAL OF APPLIED PHYSICS 100, 083108 2006
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by a Spex scanning monochromator model 1250M
equipped with a 1200 grooves/ mm grating blazed at
0.5 m. The monochromator slits were set at 2 mm with a
10 ms integration time. The signal was detected with a pho-
tomultiplier tube PMT. A desktop computer was used to
control the monochromator and to acquire and analyze the
data. The room temperature uorescence spectrum is shown
in Fig. 2.
III. DATA ANALYSIS
A. Judd-Ofelt analysis
The room temperature absorption spectrum of Tb
3+
4f
8

observed between 330 and 500 nm is shown in Fig. 1. Seven

absorption bands in this spectrum, representing manifolds of
5
D
4
,
5
G
6
+
5
D
3
,
5
L
10
,
5
G
5
,
5
D
2
,
5
G
4
, and
5
L
9
, were chosen to
determine the phenomenological JO intensity parameters for
Tb
3+
in TbAlO
3
. These multiplet manifolds were identied
earlier by Gruber et al.
9
for Tb
3+
in Y
3
Al
5
O
12
and
Tb
3
Al
5
O
12
. The peak wavelengths of the Tb
3+
bands are
given in Table I. The JO theoretical analysis has been applied
by many researchers in the past to determine the important
spectroscopic and laser parameters of rare-earth-doped
crystals.
1015
A short synopsis is provided below.
The measured line strengths S
meas
JJ of the chosen
bands are determined using the following expression:
S
meas
J J =
3ch2J + 1n
8
3

e
2
N
0

9
n
2
+ 2
2

, 1
where J and J are the total angular momentum quantum
numbers of the initial and nal states, respectively, n is the
refractive index, N
0
is the Tb
3+
ion concentration,

is the
mean wavelength of the specic absorption band,
=d is the integrated absorption coefcient as a func-
tion of , and c and h have their usual meanings. The factor
9/ n
2
+2
2
in Eq. 1 represents the local eld correction
for electric dipole transition for the effective eld for the ion
in the dielectric host medium of isotropic refractive index n.
For these and other calculations in this article, the
wavelength-dependent index of refraction n was determined
from Sellmeiers dispersion equation. The refractive indices
of TbAlO
3
have been measured at several wavelengths using
the Brewster angle method.
16
Experimental data were least-
squares tted to the Sellmeier dispersion equation, Eq. 2, to
determine the coefcients S and
0
.
n
2
= 1 +
S
2

2

0
2
. 2
The Sellmeier coefcients, S=2.007 and
0
=115.3 nm, that
were previously obtained for TbAlO
3
host
16
have been ap-
plied to Eq. 2 to determine the indices of refraction for the
mean wavelengths of the absorption bands investigated in
this study and are given in Table II.
The measured line strengths are used to obtain the phe-
nomenological parameters
2
,
4
, and
6
by solving a set of
eleven equations simultaneously for the corresponding tran-
sitions between J and J manifolds in the following form:
S
calc
J J =

t=2,4,6

t
S, LJU
t
S, LJ
2
, 3
where
2
,
4
, and
6
are the Judd-Ofelt intensity param-
eters and U
t
are the doubly reduced matrix elements of
rank t t =2, 4, 6 between states characterized by the quan-
tum numbers S, L, J and S, L, J. The matrix elements
FIG. 1. Room temperature absorption spectrum of Tb
3+
in TbAlO
3
from
330 to 500 nm.
FIG. 2. Room temperature uorescence spectrum of Tb
3+
in TbAlO
3
from
460 to 660 nm.
TABLE I. Values of reduced matrix elements for the absorption transitions
of TbAlO
3
at 300 K.
Transition from
7
F
6

nm U
2

2
U
4

2
U
6

2
5
D
4
485 0.0010 0.0008 0.0013
5
G
6
+
5
D
3
379 0.0017 0.0047 0.0132
5
L
10
367 0.0000 0.0004 0.0592
5
G
5
360 0.0012 0.0018 0.0135
5
D
2
359 0.0000 0.0000 0.0080
5
G
4
353 0.0001 0.0003 0.0091
5
L
9
349 0.0000 0.0021 0.0466
083108-2 Sardar et al. J. Appl. Phys. 100, 083108 2006
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depend only on the angular momentum of the Tb
3+
states and
are independent of the host and can be found in
Kaminiskii.
17
Values of the squared reduced matrix elements
are given in Table I. The JO parameters, however, exhibit the
inuence of the host on the transition probabilities since they
contain the crystal-eld parameters, intercongurational ra-
dial integrals, and the interaction between the central ion and
the intermediate environment. The values of the measured
absorption line strengths S
meas
are tabulated in Table II. A
least-squares tting of S
meas
to S
calc
provides the following
values for the three JO parameters for TbAlO
3
:

2
= 40.52 10
20
cm
2
,

4
= 8.74 10
20
cm
2
,

6
= 2.26 10
20
cm
2
.
The values of the intensity parameters are then used to
recalculate the transition line strengths of the absorption
bands using Eq. 3. The calculated line strengths S
calc
are
tabulated in Table II. A measure of the accuracy of the t is
given by the rms deviation,
S
rms
=

q p
1

S
2

1/2
, 4
where S=S
calc
S
meas
is the deviation, q is the number of
spectral bands analyzed, and p is the number of the param-
eters sought, which in this case is 3. The values in Table II
provide an rms deviation of 0.0910
20
cm
2
.
The JO parameters can now be applied to Eq. 3 to
calculate the line strengths corresponding to the transitions
from the upper manifold state
5
D
4
J=4 to the lower-lying
manifold states
7
F
J

J=06. These values are given in

Table III. Using these line strengths, the radiative decay
rates, A JJ, for electric dipole transitions between an
excited manifold J and the lower-lying terminal manifolds
J can be calculated using the following expression:
AJ J =
64
4
e
2
3h2J + 1
3
nn
2
+ 2
2
9
S
calc
J J. 5
The radiative lifetime
r
for an excited state J is calculated
by

r
=
1

AJ J
, 6
where the sum is taken over all nal lower-lying states J.
The radiative decay rates for the transitions determined by
using Eq. 5 are given in Table III. The values of the radia-
tive decay rates are added to obtain the total radiative rates of
2.46, 11.55, 10.11, 95.64, 6.43, 147.77, and 15.13 s
1
for the
7
F
J

J=06 states, respectively. These values are given in

Table IV. According to Eq. 6, the radiative lifetime of the
5
D
4
level is determined to be 3.5 ms. The transition from the
individual excited states to the lower-lying manifolds should
have the same measured lifetimes, because they all originate
from the same excited state. Therefore, while predicting the
radiative lifetime of an individual upper level, according to
the Judd-Ofelt analysis, one should add all the decay rates
for the corresponding transitions from that level to all lower
levels and then invert the sum.
The uorescence branching ratios JJ can be de-
termined from the radiative decay rates by the following ex-
pression:
J J =
AJ J

AJ J
= AJ J
r
, 7
where the sum runs over all nal states J. The energy level
diagram for trivalent terbium free ion and for the measured
absorption energy of TbAlO
3
is given in Fig. 3. From the
measured absorption spectrum the values of the branching
ratios for the
5
D
4

7
F
J

are given in Table III. The lumines-

cence branching ratio is a critical parameter to the laser de-
signer, because it characterizes the possibility of attaining
stimulated emission from any specic transition.
TABLE II. Measured and calculated average absorption line strengths of
TbAlO
3
at 300 K.
Transition from
7
F
6

nm
S
meas
10
20
cm
2

S
calc
10
20
cm
2

S
2
10
40
cm
4

5
D
4
485 0.011 0.050 0.0016
5
D
6
+
5
D
3
379 0.195 0.140 0.0031
5
L
10
367 0.186 0.138 0.0024
5
G
5
360 0.039 0.095 0.0032
5
D
2
359 0.034 0.018 0.0003
5
G
4
353 0.158 0.027 0.0170
5
L
9
349 0.035 0.124 0.0078
TABLE III. Values of branching ratios and radiative decay rates of TbAlO
3
at 300 K.
Transition from
5
D
4

nm
S
cal
10
20
cm
2
n
A
JJ

s
1
B
JJ

rad
ms
7
F
0
680 0.019 1.751 2.46 0.009 3.5
7
F
1
671 0.087 1.752 11.55 0.040
7
F
2
649 0.069 1.753 10.11 0.035
7
F
3
621 0.565 1.755 95.64 0.331
7
F
4
588 0.032 1.757 6.43 0.022
7
F
5
543 0.578 1.761 147.77 0.511
7
F
6
488 0.042 1.768 15.13 0.052
TABLE IV. Optical properties predicted by JO theory and intermanifold
emission cross section of Tb
3+
in AlO
3
.
Radiative lifetime
r

5
D
4
=3.5 ms
Branching ratios
5
D
4

7
F
5
=0.511

5
D
4

7
F
6
=0.052
Emission cross section
5
D
4

7
F
5
=0.42110
22
cm
2

5
D
4

7
F
6
=7.4110
22
cm
2
083108-3 Sardar et al. J. Appl. Phys. 100, 083108 2006
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B. Emission cross section
The intermanifold emission cross section of the
5
D
4

7
F
6
transition of Tb
3+
4f
8
in stoichiometric laser host
TbAlO
3
can be obtained using the following equation:
J, J; =

2
8cn
2
J, J

J
g . 8
where is the wavelength at the peak emission, =
1
is the
wave number, J, J is the uorescence branching ratio for
the transition from the upper manifold J to the lower mani-
fold J,
J
is the radiative lifetime of the excited manifold J
J=4, and g is the line shape function. The line shape
function is obtained from the uorescence spectrum using
the following expression:
g =
I

I d
, 9
where I is the intensity at . The line shape function for
the
5
D
4

7
F
6
transition can be therefore determined by di-
viding the peak intensity I by the integrated areas of the
respective uorescence spectrum. The value of g , along
with the values of radiative lifetime and intermanifold
branching ratio from Table III, and the values of and n are
applied to Eq. 8 to determine the emission cross section for
the
5
D
4

7
F
6
and
5
D
4

7
F
5
intermanifold transitions,
which are given in Table IV.
IV. DISCUSSION
The spectroscopic analysis of Tb
3+
in TbAlO
3
has been
performed following the standard Judd-Ofelt theory. The
three phenomenological parameters were found to be
2
=40.5210
20
cm
2
,
4
=8.7410
20
cm
2
, and
6
=2.26
10
20
cm
2
. These values are provided in Table V and are
compared to those obtained for other hosts.
1,5,6,18,19
The
value obtained for
2
, when compared to Tb
3+
in other hosts,
varies signicantly, while values for
4
and
6
seem to fall
within a reasonable range. It should be noted that
4
and
6
,
which are higher ordered terms in the calculation, are less
sensitive to the local crystal-eld environment. Although the
reduced matrix elements are themselves independent of the
host and crystal-eld site, the Judd-Ofelt coefcients
t
s, in
particular
2
, seems to be extremely sensitive to the local
environment for this crystal. This sensitivity is due to the
conguration admixing. The spectroscopic quality factor X
=
4
/
6
, for Tb
3+
in TbAlO
3
was found to be 3.86, which is
comparable to 3.57 obtained by Weber et al.
5
It has been
shown that the probability of spontaneous transition prima-
rily depends on the fourth and sixth order terms
4
and
6
.
17
As a result, the major laser transitions for Tb
3+
in TbAlO
3
host are likely to be signicantly stronger due to the large
spectroscopic quality factor.
The radiative transition probabilities radiative decay
rates and the branching ratios are determined for all possible
transitions from the upper
5
D
4
manifold to the lower mani-
folds
7
F
0
,
7
F
1
,
7
F
2
,
7
F
3
,
7
F
4
,
7
F
5
, and
7
F
6
. The radiative
lifetime is determined to be 3.5 ms for the
5
D
4
upper mani-
fold. The measured lifetime for the Tb
3+ 5
D
4

7
F
5
transition
in other hosts has been reported to be approximately
2.0 ms.
5,6
The shorter lifetime for this particular transition
can be attributed to lattice interactions with the Tb
3+
ions.
The quantum efciency =
meas
/
rad
of this particular tran-
sition is therefore determined to be approximately 57.0%.
FIG. 3. Energy level diagram Tb
3+
free ion and Tb
3+
in AlO
3
.
TABLE V. JO parameters for Tb
3+
in different hosts.
Sample

2
10
20
cm
2

4
10
20
cm
2

6
10
20
cm
2
X=
4
/
6
TbAlO
3
a
40.52 8.74 2.26 3.86
TbYAlO
3
b
3.25 7.13 2.00 3.57
TbLiYF
4
c
28.30 1.65 2.15 0.77
TbYVO
4
d
1.40 4.80 0.29
TbGAGSe
e
7.50 4.40 2.40 1.83
Tb in Phosphate Glass
f
33.80 0.89 1.84 0.48
a
Reported in this paper.
b
Data from Ref. 5.
c
Data from Ref. 17.
d
Data from Ref. 18.
e
Data from Ref. 1.
f
Data from Ref. 6.
083108-4 Sardar et al. J. Appl. Phys. 100, 083108 2006
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The emission cross sections of the
5
D
4

7
F
6
494.1 nm
and
5
D
4

7
F
5
543.6 nm intermanifold transitions have
been determined using the room temperature emission spec-
trum. The emission cross sections of the transitions are found
to be 7.4110
22
and 0.42110
22
cm
2
for the
5
D
4

7
F
6
and
5
D
4

7
F
5
intermanifold transitions, respectively. These
values are comparable to those calculated by Amaranath
et al.
20
V. CONCLUSION
The Judd-Ofelt model has been applied to the room tem-
perature absorption spectrum of Tb
3+
in TbAlO
3
to deter-
mine the radiative decay rates and branching ratios of the
transitions from the
5
D
4
upper manifold state to the lower-
lying manifolds
7
F
0
,
7
F
1
,
7
F
2
,
7
F
3
,
7
F
4
,
7
F
5
, and
7
F
6
. The
radiative lifetime of the
5
D
4
upper manifold state is 3.5 ms.
The spectroscopic quality factor,
4
/
6
, of Tb
3+
in TbAlO
3
is found to be 3.86; this value is compared to values obtained
for Tb
3+
in other hosts, thus suggesting that the TbAlO
3
ma-
terial is a serious contender for a laser system. The radiative
transition probabilities, branching ratios, radiative lifetime,
and emission cross sections are important spectroscopic pa-
rameters for laser materials. From the radiative lifetime
3.5 ms and uorescence lifetime 2.0 ms, the quantum ef-
ciency of the most important laser transition
5
D
4

7
F
5
0.543 m of Tb
3+
in TbAlO
3
is found to be approximately
57%. The uorescence lifetime of 2.0 ms for the Tb
3+ 5
D
4
state is long enough for storing energy, thus enabling it to
become an ideal candidate for a Q-switch operation.
In conclusion, this study shows that Tb
3+
in TbAlO
3
pos-
sesses several competitive spectroscopic properties, suggest-
ing that this material has potential for laser operation in the
visible region. In particular, owing to the long lifetime
2.0 ms, higher branching ratio 51%, and the suitable
emission cross section 0.42110
22
cm
2
of the Tb
3+ 5
D
4

7
F
5
intermanifold transition, TbAlO
3
could be an excel-
lent candidate for 0.54 m laser operation.
ACKNOWLEDGMENTS
This work was in part supported by the National Science
Foundation Grant No. DMR-0602649 and the U.S. Civilian
Research and Development Foundation CRDF Grant No.
AP2-2556-AK-03. One of the authors K.N. would like to
acknowledge the nancial support from the Department of
Physics and Astronomy at the University of Texas at San
Antonio.
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