Laser Analysis of Nd3+ Ions in Fluoroaluminate Glasses

Ahmad Marzuki
Department of Physics, University of Sebelas Maret, Surakarta
e-mail: amz@mipa.uns.ac.id
Received 2 May 2005, accepted for publication 14 March 2007
Abstrak
Sifat-sifat dasar laser yang dimiliki oleh gelas Nd3+-fluoroaluminat telah diprediksi dengan menggunakan parameterparameter laser untuk transisi 4F3/2 4I9/2, 4F3/2 4I11/2 and 4F3/2 4I13/2 yang terletak pada daerah inframerah dekat.
Penghitungan parameter-parameter laser ini dilakukan dengan menggunakan parameter Judd-Ofelt. Beberapa
parameter penting yang diperoleh dari hasil analisis ini adalah besar peluang transisi radiatif, life time radiatif dan
fluorescence branching ratio. Branching ratio untuk transisi 4F3/2 4I13/2 serta perbandingan antara intensitas emisi
dengan Exited State Absorption (ESA) untuk gelas-gelas dengan kandungan Pb2+ yang tinggi menunjukkan nilai yang
tinggi sementara parameter life time radiatifnya menunjukkan kecenderungan yang berlawanan. Secara keseluruhan,
hasil penelitian ini menunjukkan bahwa gelas Nd3+-fluoroaluminate yang mengandung ion Pb2+ merupakan material
laser aktif berindeks refraksi tinggi yang cukup menjanjikan.
Kata kunci: Analisis Judd-Ofelt, Gelas fluoride, Penguat optic, Material laser
Abstract
Lasing performance of Nd3+-fluoroaluminate glasses has been predicted with the help of laser parameters for the
transitions 4F3/2 4I9/2, 4F3/2 4I11/2 and 4F3/2 4I13/2 in the near infrared region. Judd-Ofelt parameters have been
used for the calculations of different laser parameters. Analysis yielded some of the important spectroscopic parameters,
namely radiative transition probabilities, radiative lifetimes and fluorescence branching ratios. The branching ratios for
4
F3/2 4I13/2 and their emission to Exited State Absorption (ESA) intensity ratios are higher at the glasses containing
Pb2+ ion while their radiative lifetime shows the opposite trend. The overall results reported here showed that Nd3+
doped fluoroaluminate glasses containing Pb2+ is a promising active laser material with high refraction index.
Keywords: Judd-Ofelt analysis, Fluoride glass, Optical amplification, Laser materials
concentration of Pb2+ ions with the help of the standard
Judd-Ofelt analysis.

1. Introduction
Most of the installed optical fibre
telecommunication systems operate at 1.3 m in the
telecommunication window. Unfortunately, nowadays,
no optical amplifier device either in the form of fibre or
planar amplifier working at 1.3 m is comparable to the
performance of the very successful EDFA (Erbium
Doped Fibre amplifier) working at 1.5 m. It was
shown that Nd-doped fluoroaluminate glasses had
promising spectroscopical properties that can be used
for an optical amplification at 1.3 m (Naftaly et al.,
1999). Due to its high Nd doping solubility, optical
amplification on a planar waveguide of about 1 cm
length can be produced. To fabricate such a waveguide,
a high ionic polarizability ion, such as K+, Ag+, Tl+,
Pb2+ and Cl-, can be incorporated into the glass. As can
be expected, apart from the refractive index changes,
the absorption spectra and thus the emission spectra
will also change. This report aims at investigating the
change in the lasing performance of Nd3+ ions in
aluminium fluoride glasses doped with different

2. Methods
The aluminium fluoride glasses with batch
99 x
composition (mol%)
(39AlF3-6MgF2-22CaF2 99
6SrF2-6BaF2-10LiF-8NaF-2NaPO3)-x PbF2-1NdF3 (x =
0, 5, 10, 12, 15) were prepared in a dry glove box under
N2 atmosphere. Mixtures of these chemicals (supplied
by Merck) were melted in a platinum crucible at 1025
o
C in N2 gas atmosphere for 30 minutes. The melts
were then poured into a brass mold at 260 oC and
cooled naturally to room temperature. The unbroken
glasses thus obtained were then annealed at a
temperature of 365 oC for 1 hour and then cooled to
room temperature at a cooling rate of 2 oC/min. The
obtained samples were cut into the shape of
parallelepipeds and optically polished. The refractive
indices were measured at = 589 nm using an Abbe
refractometer and the density were using AccuPyc 1330
pycnometer. The absorption spectra were recorded
32

Marzuki, Laser Analysis of Nd3+ Ions in Fluoroaluminate Glasses 33

using Perkin-Elmer UV-VIS-NIR Lamda-19 in the

wavelength region 170-1000 nm.
3. Results and Discussion
The absorption spectra for all samples recorded
at room temperature over a wavelength range from
170 to 1000 nm are similar and the peak wavelengths
are approximately the same. The only difference is the
relative peak intensities in the spectrum. Typical
absorption spectra recorded are shown in Figure 1. The
peaks correspond to transitions from 4I9/2 (ground state)
to the 2S+1LJ energy states of Nd3+ (Dieke and
Crosswhite, 1963). The assignments of the peaks
wavelength are given in Table 1.
Because of
inhomogeneous broadening, the Stark structures are
poorly resolved and some of adjacent energy levels
appear in the spectrum as one level.
In connection with the use of glasses as a lasing
medium, some useful information can be obtained from
these measurements. Using the Judd-Ofelt analysis
method (Judd, 1962; Ofelt, 1962), we can predict the
radiative lifetime of the initial laser state 4F3/2, the
branching ratios and the radiative transition
probabilities from 4F3/2 to 4IJ manifolds (J = 9/2, 11/2,
13/2 and 15/2) as well as the emission to ESA intensity
ratios. We start here with the calculation of intensities
of absorption bands measured in terms of the line
strength area method.

3ch(2 J + 1)
3 2

8 e N

0.6

(n

9n
2

+2

2.3

OD( )d

(1)

J J

where J and J are the total angular momentum

quantum numbers of the initial and the final states,
respectively, is the mean wavelength of an
absorption band, n is the glass refractive index at , c
is the light velocity, e is the electron charge, h is the
Planck constant, N is the Nd3+ ion concentration, t is the
sample thickness and OD is the optical density defined
by
I ( )

OD( ) = log b
I s ( )

(2)

where Is() and Ib() are the intensities of the wave

transmitted by a glass sample and a blank sample,
respectively. The measured line strengths of all glass
samples are shown in Table 1.
Once the measured line strengths are obtained,
these values can then be used to calculate the JuddOfelt parameters 2, 4 and 6. This is done by
solving a number of equations for transitions from the
initial state (S, L )J to the final state (S , L)J as
expressed by (Judd,1962; Ofelt, 1962)
f calc (J J )
=

797

(S , L )J U (t ) (S , L)J

(3)

t = 2, 4 , 6

0.5

577

Optical density

f meas

where the elements

741

U (t )

are the doubly reduced

unit tensor operators. Values of the doubly reduced

0.4

matrix elements

0.3

522

353
0.2

00

868

0.1

289

328

429

473

625

679

0.0
200

300

400

500

600

700

800

900

Wavelength, nm

Figure 1. Optical absorption spectrum of Nd3+ ions in

aluminium fluoride glass with no Pb2+ content at room
temperature.
3.1 Line strengths and Judd-Ofelt parameters
In the Judd-Ofelt treatment, the line strength of
the dielectric dipole transition between the two J states
can be measured from the absorption spectra data using
the relationship (Reinsfield and Jorgensen, 1977) given
below:

U (t )

of unit tensor operators for

these bands were taken from the reference (Sudo,

1977). The values of t (t = 2, 4, 6) obtained are
presented in Table 2.
The values of line strengths obtained in this
calculation are in agreement with the reported values
obtained in other glass matrices (Jacobs and Weber,
1976; Ratnakaram et al., 2002). From Table 1 it can be
seen that among all the recorded absorption bands, the
effect of the environment is much more significant on
the intensity values of the hypersensitive transition
(4I9/2 - 4G5/2) in all glasses. This particular band as
can be seen from Table 1 has the highest values of
spectral intensities in all observed glasses. The different
values between this transition and 4I9/2 4F5/2, 2H9/2 as
well as 4I9/2 4F7/2, 2S3/2, however, are less than those
are observed in e.g., zinc chloride borophosphate
glasses (Jacobs and Weber, 1976). At those glasses, the
intensity values of the hypersensitive transition are
nearly twice as much as those of the 4I9/2 4F5/2, 2H9/2

34 JURNAL MATEMATIKA DAN SAINS, MARET 2007, VOL. 12 NO. 1

as well as the 4I9/2 4F7/2, 2S3/2 transitions. The

intensity values of the 4I9/2 4F5/2, 2H9/2 for glasses
reported here (Table 1) are much higher than all other
transition (apart from hypersensitive transition). As the

So do 4 and 6. Jorgensen et al. (1964) in Rao et al.,

1998 noted that the 2 parameters are indicative of
covalent bonding. Accordingly, as shown in Figure 2,
the 2 parameters are

Table 1. Measured and calculated line strengths (10-20cm2) of Nd3+-doped fluoroaluminate glasses containing different
concentration of PbF2
Transition
from 4I9/2

Glass with x =

(nm)

10

12

15

F3/2

868

fmeas
0.95

fcalc
1.03

fmeas
1.14

fcalc
0.70

fmeas
1.30

fcalc
0.82

fmeas
1.39

fcalc
1.03

fmeas
1.63

fcalc
0.97

F5/2, 2H9/2

797

3.12

3.08

2.35

2.33

2.63

2.61

3.65

3.53

3.61

3.46

F7/2, 2S3/2

742

2.94

3.02

2.3

2.38

2.55

2.63

3.49

3.66

3.44

3.64

F9/2

678

0.20

0.21

0.17

0.17

0.18

0.18

0.23

0.25

0.23

0.25

H11/2

624

0.04

0.05

0.03

0.04

0.03

0.05

0.05

0.06

0.04

0.06

G7/2, G5/2

576

3.19

3.21

2.57

2.59

2.79

2.81

4.05

4.09

3.98

4.01

K13/2, 4G7/2

521

1.66

1.36

1.39

1.00

1.47

1.13

1.99

1.50

1.95

1.45

474

0.41

0.31

0.41

0.22

0.41

0.26

0.46

0.34

0.42

0.32

427

0.09

0.14

0.07

0.09

0.08

0.11

0.09

0.13

0.09

0.12

354

2.05

2.16

1.29

1.44

1.58

1.71

1.89

2.10

1.72

1.20

K15/2, D3

P1/2, D5/2
2

D3/2, I11/2

RMS = 0.12

RMS = 0.20

RMS = 0.20

RMS = 0.22

RMS=0.29

Table 2. Judd-Ofelt intensities parameters (10-20cm2) for Nd3+ in aluminium fluoride glasses
Glass
(in mol% Pb2+)
0
5
10
12
15

4/6

Aem/AESA

0.89
0.87
0.89
1.86
1.96

3.45
2.56
2.86
3.23
2.94

4.52
3.39
3.77
6.32
6.31

0.80
0.76
0.76
0.61
0.55

3.0
2.8
2.8
3.3
3.3

trend of this value increases as the Pb2+ content

increases, the pumping efficiency at wavelength of
800 nm will be better at a higher Pb2+ containing glass
than at a lower Pb2+ containing glass.
The three Judd-Ofelt parameters shown in Table 2
clearly shows that 2 < 4 < 6. The values of 2 and
6 increase as the Pb2+ content increases. It is observed
from Figure 2 that 2 behaves in the same way as the
line strength for the transition 4I9/2 - 4G5/2 which is
consistent with the work of Ratnakaram (Jorgensen and
Judd, 1964) who observed that the intensities of the
hypersensitive transition decrease with a decrease in the
2 parameters.

larger in glasses with larger lead concentration and

smaller in the glasses with smaller Pb concentration. By
comparing the 2 parameters observed from this
experiment and those obtained for example for
fluorophosphates glasses (Tanabe et al., 1992) and
borate glasses (Kruple, 1974), very low values of the
2 parameter as given in Table 2 indicates the strong
ionic nature of the metal ligand bond in aluminium
fluoride glasses.
3.2 Radiative properties
With the above calculated Judd-Ofelt
parameters, the radiative transition rates and the
branching ratios for the electric dipole transition from

Marzuki, Laser Analysis of Nd3+ Ions in Fluoroaluminate Glasses 35

an initial manifold 4 f n , ( S , L) J

[(S , L )J ; (S , L)J ]

to a final manifold

A[( S , L) J ; ( S , L) J ]
A[( S , L) J ; ( S , L) J

4 f n , ( S , L) J can now be calculated.

(5)

S , L , J
7

fmeasured
fcalculated
2
4
6

5
2

-20

-20

f x 10 /cm

f x 10 /cm

where the sum is over all possible terminal manifolds.

In the case of Nd3+, the terminal manifolds are 4I9/2,
4
I11/2, 4I13/2 and 4I15/2.
The radiative lifetime R of an excited state is
related to the total transition probability as (Kaminskii,
1975)

-2

10

12

14

R = A[( S , L) J ; ( S , L) J ]

S , L , J

2+

Figure 2. 2 and line strength for the transition 4I9/2 -

4
G5/2 versus Pb concentration.
The transition rate A for this transition is given
by Kruple (1974).
n2 + 2

3h ( 2 J + 1) 3 9
64 4 e 2 n

t ( S , L ) J U ( S , L) J

(6)

The calculated values of the transition

probability (A), total radiative probability (AT),
radiative lifetime (R) and branching ratio () are
presented in Table 3. The radiative lifetime calculated
in such a way represents an effective average from site
to site variations in the local Nd3+ environment. From
equations (4), (5) and (6) it is obvious that the radiative
lifetime is inversely proportional to the linear
combination of the 2, 4 and 6 parameters. As these
parameters increase, therefore, the radiative lifetime
decreases. The correction for the local field at the Nd3+
site has introduced a dependence on the refractive
index. Thus, although the branching ratios for all
transitions are relatively invariant with the glass
composition (Table 3), the total transition rate and
therefore the radiative lifetime indicates significant
variations even for nearly similar glasses.

16

Pb concentration/mol%

A ( S , L ) J ; ( S , L ) J =

(4)

and the fluorescence branching ratio for such

transition is given by Kaminskii and Li (1975).

Table 3. Radiative rate (in s-1), branching ratio and radiative lifetime (s) for 4F3/2 transition down to 4IJ
Glass
(in Pb
mol%)
0
5
10
12
15

Transition from the initial 4F3/2 manifold to

4
4
4
I9/2
I11/2
I13/2
A
A
A

634
0.379
857
0.513
173
498
0.372
693
0.518
141
567
0.373
787
0.517
160
697
0.343
1093
0.538
232
699
0.332
1150
0.456
248

The results in Table 3 also clearly show that the

transition probability and hence the branching ratio is
maximum for the 4F3/2 4I11/2 transition and minimum
for the 4F3/2 4I15/2 transition in all glass compositions
studied. The same result can also be observed in all
Nd3+ doped glass hosts. Because of the high value of
the transition probability for the 4F3/2 4I11/2
transition, it can be expected that the stimulated
emission cross-section is also a maximum for this
transition.

0.103
0.106
0.105
0.114
0.118

I15/2
A
7.1
6.9
6.7
9.7
10

0.004
0.004
0.004
0.005
0.005

AT

1672
1338
1521
2032
2107

598
747
658
492
475

Further from Table 3 it can be seen that the

fluorescence decay times of the 4F3/2 level generally
decrease as the Pb2+ content increases. Apart from the
phonon energy the glasses may have, this trend partly
may be due to the line strength behaviour of either
4
I9/2 4F5/2 or 4I9/2 4F3/2 transition. This
relationship is clearly shown in Figure 3. As the line
strength defined in equation (1) is partly due to the
width of the energy band (E) or wavelength band ()
of an absorption peak, higher line strength may mean

36 JURNAL MATEMATIKA DAN SAINS, MARET 2007, VOL. 12 NO. 1

lower E. The line strength of the 4I9/2 4F3/2

transitions are much less than those reported in
reference (Surana et al., 2001). Therefore, according to
the Heisenbergs uncertainty principle we can thus
expect that a glass with a higher Pb2+ content may have
a lower fluorescence decay time.
8

Acknowledgements

7
6

f( F5/2)
lifetime

7
6

lifetime (x100/s)

-20

line strength x (10 /cm )

f( F3/2)

0
0

10

12

14

ratio are improved by the increase of Pb2+ ion content

in the glass. Unfortunately, this trend is not followed by
their radiative lifetime. The values of the radiative
lifetime, although still high, decrease as the Pb2+ ion
content increases. In this case, Nd3+ doped fluoroaluminate glasses containing different concentration of
Pb2+ ion is still favourable for an active laser material
where high refractive index is required.

16

2+

Pb concentration/mol%

Figure 3. Fluorescence decay time of the 4F3/2 level

and the line strength of the 4I9/2 4F5/2 or 4I9/2 4F3/2
transition against Pb2+ concentration.
Finally, as can be seen from Table 2, the JuddOfelt parameters can also be used to estimate the
emission/ESA intensity ratio (Ratnakaram et al., 2002)
as given by
Aem
0.21 6
(7)
=
AESA 0.11 2 + 0.063 4
where Aem and AESA are the emission intensity and ESA
intensity, respectively. The results are in a good
agreement with those given by Naftaly et al. (1999).
The ratios that are higher than 1 means Aem > AESA or
amplification can occur in these glasses. The ratios of
the emission/ESA intensity of about 3, as shown in
Table 2, are comparable to those of high ratios reported
in fluoroberyllate glasses or even much higher than
those reported in fluorophosphates glasses (Aggarwal,
1991). By referring to the above equation, it can be
seen that a glass with a higher value of 6 and a lower
value of 2 is desirable since such a glass will provide
a higher value of Aem /AESA ratio. This suggests that a
more ionic glass may need to be tailored.

4. Conclusions
The Judd-Ofelt analysis of neodymium doped
fluoroaluminate glasses containing different concentration of Pb2+ ions are presented in this work. The
branching ratio of 4F3/2 4I13/2 transitions and the
emission/ESA (Excited State Absorption) intensity

The author acknowledges the support of Due

Project Sebelas Maret University and thanks Prof. A.
Jha, Department of Materials, University of Leeds, for
his help.
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