Spectroscopic investigations ofAbsorption intensities and Emission Cross- Formatted: Font: 14 pt

Formatted: Centered
section of Nd3+ doped Yin3Al5O12 tTransparent PLZT c Ceramics: Judd-Ofelt
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Theory Formatted: Font: 14 pt

Formatted: Font: 10 pt
Sanjib Karmarkar, Neethu, Rachna Selvamani, Sushil Pathak, Gurvinderjit Singh, Surya Mohan Gupta, V. S. Tiwari
and P. K. Gupta
Laser Materials Development and Devices Division, Raja Ramanan Centre for Advanced TecjhnologyTechnology, Formatted: Font: 10 pt
Indore-452 013 (INDIA) Formatted: Font: 10 pt

Abstract:
A spectroscopic investigation of Nd3+ (1mol%) doped PLZT(9/65/35) transparent
ceramic was performed. We applied Judd–Ofelt theory on measured absorption spectra to
determine Judd–Ofelt intensity parameters. Based on this theory the calculated intensity
parameters are; xcm2, xcm2,xcm2. These intensity
parameters are used to determine the emission probabilities, radiative lifetimes, and branching
ratios of the 4F3/24IJ (J=9/2, 11/2, 13/2, 15/2) transitions. The calculated radiative lifetimes
(179sec.) are in good agreement with the measured life time (166sec.) for 4F3/2 level. Finally,
the emission cross-section of the potential laser transitions at was also evaluated.

1. INTRODUCTION
Transparent lanthanum-modified lead zirconate titanate (PLZT) ceramics are well known
electro-optic (EO) materials and have attracted attention for their applications in electro-optic
devices such as modulator, amplifier, and optical switches [ ]. Recently, neodymium (Nd3+)
doped Pb0.91La0.9(Zr0.65Ti0.35)0.9975O3, PLZT (9/65/35), has been investigated for its potential use
as a laser-host active medium [ ]. Studies have shown that its low phonon energy, negligible
excited state absorption losses and very low down-conversion and up-conversion losses mark it
out as a suitable laser host material [ ]. With the aim of evaluating the potentiality of Nd3+ doped
PLZT ceramics as laser host, in this work we analysed the radiative properties in terms of the
Judd-Ofelt (JO) theory. This is a well-established theory based on the determination of three
intensity parameters (2, 4, 6) of a given system, by assuming that the experimental and
theoretical oscillator strengths. The calculated JO parameters can be used to determine the
emission probabilities, radiative lifetimes, and branching ratios of the f-f transitions.
Although extensive study has been carried out on PLZT ceramics, only two reports are
available on JO calculations for Nd3+ doped PLZT ceramics. The Judd-Ofelt intensity parameters
show large variation in their values for both the publications. Based on Judd-Ofelt intensity
parameters Camargo et al [ ] have calculated radiative properties of Nd3+ doped PLZT ceramics.
According to their calculation the branching ratio of 4F3/24I9/2 emission line is higher for
3/2 I11/2
4F 4 line, which is not experimentally correct. They also did not show how these values
were derived. More importantly they have not taken main absorption bands of 4I9/24G5/2, 2G7/2
(near 586nm) and 4I 4G , 2G , 2K (near 526nm) while calculating Jude-Ofelet
9/2 7/2 9/2 13/2

parameter. The absorption band 4I 4G , 2G , 2K has highest absorption coefficient for
9/2 7/2 9/2 13/2

Nd3+ based laser host materials, therefore, it strongly influence the JO parameters. Similarly the
life time for 4F3/24IJ transition calculated by Zheng et al, comes out to be 325Sec, which is
also much higher than the reported values (140-180sec). Both the authors have not taken
dispersion of refractive index () and actual concentration (N) of Nd3+ ions into account. It is
well known that both these parameters ( and N) strongly affect the radiative properties of laser
host materials. Therefore, a complete and refined spectroscopic analysis of Nd:PLZT, useful to
the laser designer is lacking.
Here we present the spectroscopic properties of Nd3+ doped PLZT ceramics by means of
absorption, luminescence, the associated lifetime and refractive index measurements. The JO
parameters are calculated and used to evaluate transition probability, radiative lifetime,
branching ratios and emission cross section for the fluorescent level 4F3/2 to 4I9/2, 4I11/2, 4I13/2 and
4I
15/2. The dispersion relation of refractive index was derived using Sellmeier’s dispersion
equation. And actual concentration (N) of neodymium in PLZT was evaluated using results of X-
ray diffraction and EDX.

III. EXPERIMENTAL METHODS:

PLZT (9/65/35) powder doped with 1mol%Nd2O3 was synthesized by conventional dry
route. The synthesis procedure of transparent Nd:PLZT ceramic is reported in our earlier
publication [ ]. The theoretical density of Nd:PLZT was calculated from X-ray diffraction of the
sintered powder [ ]. The absorption spectrum of Nd:PLZT was recorded in the spectral region
350-1000 nm, which was measured with UV-VIS-NIR spectrophotometer (VARIAN
CARY5000). Photoluminescence (PL) of the sample was measured by exciting it by a diode laser

operating at 808 nm. The signals were filtered in a 1/4m monochromator and collected by
a germanium (Ge) photodiode. The band pass of the monochromator was kept about 4nm. The
PL measurements were carried out in reflection mode in the range of 850-1600nm wavelength.
Excited states lifetimes was obtained from the luminescence intensity decay curves in time,
which were measured by exciting the samples with a LED operating at 590nm. The output
power of the LED was modulated with the different frequencies. The PL signal modulated in
response to excitation was filtered and detected by Si-photodiode. The lower cut-off wavelength
of the long-wavelength pass filter used was 800 nm. The modulation of the excitation intensity
was provided by a lock-in amplifier, which measures the phase shift of the luminescence signal
as well as intensity of the output signal. Before performing the actual experiment with
Nd:PLZT, the setup was checked with Nd:glass sample for its reliability. The delay due to
electronic elements was also measured and it was found less than 1 μSec. The refractive index of
Nd:PLZT was measured at different wavelengths using Metricon’s make prism-coupling based
system. The measured refractive index was fitted to Sellmeier’s dispersion equation by least-
square sense to find the wavelength dependence of the refractive indices. The neodymium (Nd3+)
ion concentration was measured using EDX. We determined Nd3+ concentration of the sample
used in our study to be 1.44x1020 cm-3. It is important to note that this value correspond to
averaging over at least four different locations for Nd:PLZT sample.

II RESULTS and DISCUSSION

Refractive index studies
The refractive indices measured at room temperature a for four different wavelengths is shown in
figure1. The wavelength dependent refractive index for Nd:YAG was determined using two
term Sellmeier’s dispersion equation:
A 2 C 2
2 (λ)  1   2 ...( 2.1 )
 B  D
2
Where, A, B, C and D are Sellmeier’s coefficients and were determined by fitting the above
equation to the measured data points. Figure 2 shows excellent fit of Sellmeier’s equation to the
experimental data. The observed A, B, C and D coefficients are depicted in figure 1.
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Jude –Ofelet Analysis of absorption spectra

Figure 2 shows the absorption spectra of 1at% Nd doped YAG transparent ceramic in
wavelength ranging from 490-1000nm s. The various absorption lines corresponding to 4I9/2
initial ground state of Nd3+ ion can be observed. These absorption lines are due to 4f–4f intra- Formatted: Not Superscript/ Subscript

band electric dipole (ED) transitions which are generally not allowed because of the same parity Formatted: Font: (Default) Times New Roman, 12 pt
Formatted: Font: (Default) Times New Roman, 12 pt
of initial and final states but become allowed due to resultant mixed parity in 42m (D2d) non-
Formatted: Font: (Default) Times New Roman, 12 pt
centrosymmetric site symmetry around Nd3+ ion in YAG crystal structure. The measured mean
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wavelength and integrated absorption coefficient with assigned excited state for every absorption Formatted: Font: (Default) Times New Roman, 12 pt
line of 4f to 4f transition is summarized in table 1 and utilized for Judd-ofelt (JO) analysis. The Formatted: Font: (Default) Times New Roman, 12 pt

experimentally measured line strength (Sexp) of forced electric dipole transition from ground state Formatted: Font: (Default) Times New Roman, 12 pt
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J to excited state J is calculated from the absorption spectrum using expression
Formatted: Font: (Default) Times New Roman, 12 pt
Formatted: Font: (Default) Times New Roman, 12 pt,
27ch(2 J  1).
8 3 N  e2 (  2  2) 2 
Smeas ( J  J )   ( ) d  ...1 Superscript
Formatted: Font: (Default) Times New Roman, 12 pt
Formatted: Font: (Default) Times New Roman, 12 pt
Formatted: Font: (Default) Times New Roman, 12 pt
Where c is speed of light in vacuum, h is Planck’s coefficient, e is charge on one electron,
Formatted: Font: (Default) Times New Roman, 12 pt
J (J′) is the angular momentum quantum number of initial (final) state, N is the Nd3+ number Formatted: Font: (Default) Times New Roman, 12 pt

density in per cm3,  is the mean wavelength of absorption band, () is linear absorption Formatted: Font: (Default) Times New Roman, 12 pt
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coefficient,   ( )d  is the area under the absorption band (i.e. integrated absorption Formatted: Font: (Default) Times New Roman, 12 pt

coefficient) and is the refractive index of Nd:YAG ceramic obtained from fitted Sellemier Formatted: Font: (Default) Times New Roman, 12 pt
Formatted: Font: (Default) Times New Roman, 12 pt
equation (table1). The resulted values of Smeas are tabulated in table 1.
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According to Judd-Ofelt theory the line strength of forced electric dipole transition (Scal)
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between initial manifold J 4f9[L, S] J and final J 4f9[L,S] J is Formatted: Font: (Default) Times New Roman, 12 pt
Field Code Changed


2
Field Code Changed
Scalc ( J  J )  t  J U  J 
t
...2
t  2,4,6
 2 Field Code Changed
Where  J U t  J  are the doubly reduced matrix elements of the unit tensor operator

Ut of rank t, corresponding to transitions between states  J and   J  . These matrix elements Field Code Changed
Field Code Changed
are invariant with respect to the environment around the rare ion, and were calculated by Carnell
et al. [] for various ions. The reduced matrix elements used for the Nd3+ ion are listed in table1.
The coefficients 2 , 4, 6 are phenomenological Judd-Ofelt (JO) intensity parameters. These
JO intensity parameters can be calculated by assuming that experimental and calculated line
strengths are equal [ ] i.e. Smeas =Scalc. Using this equality, the parameters 2, 4 and 6 were
calculated by solving the set of equations by means of MATLAB. The determined JO parameter
(2, 4 and 6) and theoretical value of absorption line strength (Scalc), calculated from
equation-2, are presented in Table-1. To determine the Judd–Ofelt (JO) parameters for Nd3+
transitions in YAG transparent ceramic, room temperature absorption spectra of seven absorption
bands with corresponding twelve transitions shown in table 1 were used. In Fig.-1 the linear
absorption cross section for 1.0mol% Nd3+ doped YAG ceramics ranging from 490-1000nm is
presented. All the absorption bands originate from the ground 4I9/2 state. The band positions
along with assignment in the absorption spectrum are shown in Table-1.
Application of the JO theory to the experiment has been described in detail in ref.[] and
only a brief outline of the procedure is given here. The procedure starts with measuring the
absorption line strengths, Smeas (J→J′) of the transitions between the ground 4I9/2 (J=9/2)
manifold and the excited J′ manifolds using the following expression:

27ch(2 J  1).
8 3 N  e2 (  2  2) 2 
Smeas ( J  J )   ( ) d  ...1

Where c is speed of light in vacuum, h is Planck’s coefficient, e is charge on one electron,

J (J′) is the angular momentum quantum number of initial (final) state, N is the Nd3+ number
density in per cm3,  is the mean wavelength of absorption band, () is linear absorption
coefficient,   ( )d  is the area under the absorption band (i.e. integrated absorption
coefficient) and is the refractive index of Nd:PLZT. The mean wavelength, refractive indices,
integrated absorption coefficients, and measured line strengths for several Nd3+ transitions in
PLZT ceramic are given in Table-I.
 According to the Judd-Ofelt theory, the line strength (Scalc) of an electric-dipole transition
between initial J manifold and excited J′ manifold can be linearly expressed in terms of the three
phenomenological parameters (2, 4 and 6) by relation


2
Scalc ( J  J )  t  J U t  J  ...2
t  2,4,6
2
Where  J U t  J  are the reduced matrix elements of the tensor operator Ut of rank t,

corresponding to transitions between states  J and   J  . These matrix elements do not depend

on the environment around the rare ion, and are taken from the literature [ ]. The JO intensity
parameters can be calculated by assuming that experimental and calculated line strengths are
equal [ ] i.e. Smeas =Scalc. Using this equality and measured line strength (S meas) one can calculate
2, 4 and 6 by solving the over-determined set of equations by means of least square method.
We have solved these equations for three variables (2, 4 and 6) using MATLAB. The
determined JO parameter and theoretical value of absorption line strength (Scalc), calculated from
equation-2, are presented in Table-1. A measure of Tthe quality of fit between the measured
(Smeas) and calculated line intensity (Scalc) was estimated by the rms deviationaccuracy of the fit
is given by rms deviation,

  (Smeas  Scalc ) 2 
1/2

Srms =   ...3
 pq 

where ‘p’ is the number of the transition bands analyzedconsidered, and ‘q’ is the number
of the fitting parameters, those are 7 and 3 in our case are 7 and 3, respectively. The observed Formatted: Font color: Red

rms deviation of 0.058x10−20 cm2 indicate that calculated line intensities Smeas are in agreement Formatted: Font color: Auto

with experimentally measured values (of Smeas and Scalc). Formatted: Font color: Auto
Formatted: Font color: Auto
The ratio 4/6 is an important characteristic in predicting the stimulated emission for
the laser active media. For small values the emission around 4F3/24I11/2 is stronger while for
larger values the emission around 4F3/24I9/2 is stronger. The obtained value of 4/6 ratio for
Nd:YAG transparent ceramic in our case is 0.563 which is within the expected range as the value
of 4/6 for single crystal is 0.54.
in Table-I provide rms deviation of 0.058x10−20 cm2. Formatted: Font color: Red

Radiative Properties:
 A spectroscopic quality factor X=4/6 is an important characteristic in predicting the
stimulated emission for the laser active media. For small values of X the 4F3/24I11/2 branching
ratio is large while for large value of X the 4F3/24I9/2 branching ratio is large. The value of X has
been found to vary from 0.22 to 1.5 for neodymium in different host materials [ ]. It is 0.54 for
Nd:YAG single crystal [ ]. For Nd:PLZT transparent ceramic, this factor is 0.563 (Table-1),
within the expected range.
Using the determined JO parameters ( 2, 4 and 6 )parameters the emission
characteristics of line strength (Sems) corresponding to transition from 4F3/2 to 4I9/2, 4I11/2, 4I13/2 and
4I manifolds can be specucalculated.
15/2

The line strengths (Sems) corresponding to these emission lines can be calculated using
equation-1. The reduced matrix elements for the chosen Nd3+ emission bands are given in Table
2 with their calculated emission line strength values. by using equation-2. The reduced matrix
elements for these transitions are taken from ref…. From the obtained emission line strength
values the, radiative transition rate (A) can be calculated by using equation

64 4 e 2  (  2  2) 2
A( J  J )  Sems ( J  J ) ...4
27 h(2 J  1) 3

The radiative lifetime r for an excited state J is calculated by

1
r  ...5
 A( J  J )
and the fluorescence branching ratio () are given by

A( J  J )
 ( J  J )  ...6
 A( J  J )

where the sum is taken over all possible terminal manifolds. The calculated values of emission
line strengths, radiative transition rate, branching ratio and radiative life time for 4F3/24I9/2,
4I 4 and 4I15/2 are listed in Table-3II. The 1064 nm fluorescence decay curve was measured
11/2, I13/2 Formatted: Font color: Dark Red

(Fig.2), and the measured fluorescence lifetime of 4F level determined by exponential fitting is
3/2

166(±10%) sec (Fig.2). The measured and calculated radiative lifetimes are in good agreement Formatted: Font: Times New Roman, Font color: Dark
Red
and within the expected range of experimental error.
Formatted: Font color: Dark Red
Emission Cross section:
The fluorescence spectra for Nd:PLZT , at room temperature, is shown in Fig.3. The
emission spectrum consists of three large and non-symmetric bands centered near 881, 1064 and
1348nm. The emission cross section (ems) of the transition was calculated by Fuchtbauer-
Ladenburg relation [ ]

4
 ems ( )= A(J  J) ...7
8 ceff
2

where  is the mean wavelength of emission band, is the refractive index, and eff is the

effective line-width of the transition. Since the emission band is asymmetric, an effective line-
width of the fluorescence intensity (I) defined by [ ]

eff   I (Imax) d 
Here Imax is the intensity at the peak fluorescence emission wavelength. The calculated emission
cross-sections for 4F3/24I9/2, 4I11/2, and 4I13/2 fluorescence transitions are given in Table 23. It
should be noted that Tthe emission cross-section for the transition 4F3/24I11/2 is maximum
compared to other transitions. The emission cross-section for this transition is comparable with
that of Nd3+ doped silica-glasses.

IV. CONCLUSIONS

We have studied the spectroscopic properties of the Nd3+ doped PLZT ceramic. Using the
JO theory, three intensity parameters 2, 4 and 6 were determined. The JO parameters were
used to estimate the radiative probabilities, radiative lifetimes and branching ratios between
initial 4F3/2 level to terminal 4I9/2, 4I11/2, and 4I13/2 levels. The measured radiative life time of 4F3/2
level is in good agreement with the JO predicted life time. A spectroscopic quality factor
X=4/6 for Nd:PLZT was determined to be 0.56, which is within the range for other hosts.
Finally the emission cross sections were determined by Fuchtbauer-Ladenburg equation for
different transitions.

ACKNOWLEDGEMENT:
 We wish to thank Dr. I Bhaumik and Rajeev Bhatt of RRCAT for many useful
discussions during the course of this study. We also thank Mr. Sendhil Raja, Dr. Tapas Ganguly,
Dr. C. Mukhopadhaya and Mrs. Pragya Tiwari of RRCAT for providing experimental facilities.
Table-2.2 Absorption bands with their experimental and calculated line strength of 0.9at.% Nd3+ doped YAG ceramic

Transition (from 4I9/2)

    ( )d 
2 2 2 Smeas Scal
U2 U4 U6
(x10-19 cm2) (x10-19 cm2)
(nm) (10-7)
4D +4D +2I 4
3/2 5/2 11/2 + D1/2 355 1.85419 9.17 0.005 0.5256 0.0478 0.2867 0.3362
4G 2 2 2
11/2 + K15/2+ G(1)9/2 + D(1)3/2 481 1.84124 3.75 0.0010 0.0472 0.0364 0.1122 0.0495
4G 4 2
9/2 + G7/2+ K13/2 532 1.83581 9.966 0.0665 0.2182 0.1271 0.2166 0.2160
4G 2 2
5/2 + G(1)7/2 + H(2)11/2 588 1.830540 19.94 0.9737 0.5968 0.0777 0.4922 0.4936
4F 683 1.825282 1.538 0.0009 0.0092 0.0417 0.0225 0.2775
9/2
4F 4
7/2 + S3/2 748 1.822736 35.23 0.001 0.045 0.6598 0.4921 0.4565
2H(2) 4
9/2 + F5/2 808 1.820368 45.52 0.0102 0.2451 0.5127 0.6470 0.4774
4F 885 1.818417 7.75 0 0.2293 0.0548 0.0952 0.1686
3/2
2=0.99x10-20cm2, 4= 5.79x10-20cm2, 6 = 6.52x10-20cm2. X=/ = 0.88

Table 2.3 Reduced matrix elements for the Nd3+ emission bands

Transition λp (nm) [U(2)]2 [U(4)]2 [U(6)]2

from 4F3/2
4I 946 0 0.2293 0.0548
9/2

4I 1064 0 0.1136 0.4104

11/2

4I 1320 0 0 0.2085
13/2
Table-2.4 Spectroscopic parameters of 0.9 atm% Nd3+ doped YAG ceramic
Transition  (nm) Sems A(J→J') (J→J') ems r
(from 4F3/2) (x10-20 cm2) (sec-1) (x10-20 cm2) (sec.)
4I 946 1.686 2046 0.37 19.1
9/2
4I 1064 3.335 2830 0.51 34.8 182
11/2
4I 1320 1.360 603 0.11 10.1
13/2
 4 2 4
H(2) + F
9/2 5/2
)

G5 / 2  G(1)7 / 2  H( 2 )11/ 2
4 2 2
-1
(Absorption Coefficient cm

3
4
G11/ 2  2K15/ 2  2G(1)9/ 2  2D(1)3/ 2 4
F7 / 2  4S3/ 2

G7/ 2 4G9/ 2 2K13/ 2

2

4
D3/ 2  4D5/ 2  2I11/ 2  4D1/ 2
1 4
F3/ 2
4
F9 / 2
0
300 400 500 600 700 800 900
Wavelength (nm)

F I
3/2 11/2
Intensity (arb. units)

F I
3/2 9/2
F I
3/2 13/2

900 1000 1100 1200 1300 1400

Wavelength (nm)