Inte rnational Journal of Nanotechnology and

Application (IJNA)
ISSN(P): 2277-4777; ISSN(E): 2278-9391
Vol. 4, Issue 4, Aug 2014, 23-28
TJPRC Pvt. Ltd.

A PHOTOLUMINESCENCE STUDY OF ND 3+ DOPED DIFFERENT

CHLORO-PHOSPHATE GLASSES FOR SOLID STATE LASER APPLICATIONS
K. VENKATA RAO1 & Y. C. RATNAKARAM2
1

Department of Physics, S. B. V. R. Degree College, Badvel, Kadapa, Andhra Pradesh, India

2

Department of Physics, Sri Venkateswara University, Tirupati, Aandhra Pradesh, India

ABSTRACT
Investigations of glasses as host materials for rare earth fluorescence with potential for laser is confined to borate,
phosphate, silicate, tellurite and fluoride glasses. Glass materials are attractive hosts because planer waveguides and optical
fibers can be fabricated easily compared to crystalline materials. Absorption and emission spectra of 1mol% of Nd 3+ doped
different chlorophosphate glasses have been studied. By applying, Judd-Ofelt theory, three intensity parameters 2 , 4 and
6 . These parameters are useful to evaluate the radiative properties such as radiative transition probabilities (A rad ),
branching ratios (), integrated absorption cross-sections (), radiative lifetimes (R). From emission spectrum, emission
cross-sections (p) is calculated for all chlorophosphate glasses and reported.

KEYWORDS: Absorption Spectra, Phosphate Glasses, Emission Spectra, Rare Earth Ions
INTRODUCTION
Applications in solid-state lasers, integrated optical amplifiers, infrared display devices and up-conversion fibers
have stimulated the development of rare earth doped glasses. Among rare-earth ions, neodymium (Nd 3+) is one of the most
efficient ions for solid-state lasers due to its intense emission at 1060 nm. The Nd 3+ ion has been used in a number of laser
systems, due to the relatively wide availability of samples of this ion doped in a range of host materials [1]. So, a primary
disadvantage of pure vitreous P2 O5 and phosphate glasses is their low chemical stability. Glasses con taining more than
50 mol% P2 O5 are more vulnerable to hydrolytic action of water than those containing less P 2 O5 . The low chemical
durability of phosphate glasses can be improved also by the addition of both network formers and glass modifiers [2].
In this work, a detailed study of the spectroscopic and laser properties of Nd 3+ doped different phosphate (Na, K, Mg, Ca,
Na-K, Na-Mg and Na-Ca) glass matrices. Using Judd-Ofelt theory [3, 4], Judd-Ofelt parameters are calculated in these
glass matrices. The radiative properties of 4f-4f transitions in rare-earth ions doped glasses are very important for the
characterization of laser properties. The radiative properties such as, total radiative transition probabilities (A T) and raditive
lifetimes (R), branching ratios ( R) and integrated absorption cross -sections () of certain excited sates are estimated.
From the emission spectra, peak stimulated emission cross -sections (p ) are calculated. Our main interest in the present
work is to identify the good transitions for laser excitation.

EXPERIMENTAL
Rare-earth doped different phosphate glasses were prepared using melt quenching technique method.
The chemical compositions: 69 P2 O5 -20 Na2 HPO4 -10 R-Cl-1Nd 2 O3 (R= Na, K, Mg and Ca) and 69 P2 O5 -20 Na2 HPO4 -5
NaCl-5 R-Cl-1Nd 2 O3 (R= K, Mg and Ca) were used for glass preparation. All these chemicals used in the present work are
99.99% purity. The samples were polished to obtain smooth, transparent and uniform surface for optical measurement.
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K. Venkata Rao & Y. C. Ratnakaram

Also, physical measurements such as thickness, density and refractive index were carried out. The prepared glasses were
polished on both sides to obtain planar surfaces before measuring their optical properties. All these measurements were
carried out at room temperature.
The amorphous nature of the prepared Nd 3+ doped different phosphate glasses were confirmed through the X-ray
diffraction (XRD) studies using on a C 120 diffractometer employing Co K radiation. Optical absorption spectra were
obtained using JASCO; V-570 UV-VIS-NIR spectrophotometer. Emission spectra of Nd 3+ doped glasses were measured
using SPEX Fluorolog-2 fluorometer under the excitation wavelength, 514.5 nm using Xe arc lamp (150 W) as the
excitation source in the wavelength region 800-1400 nm.

RESULTS AND DISCUSSIONS

XRD and Absorption Spectra
The XRD patterns of Nd 3+ doped different chlorophosphate glass matrices are shown in Fig ure 1, which is the
characteristic feature of structural disorder that confirms the amorphous nature of the prepared glass es under investigation
(expect sodium magnesium and sodium calcium). The optical absorption spectra of Nd 3+ doped sodium chlorophosphate
glass matrix observed in the wavelength region 325-900 nm is shown in Figure 2 From the absorption spectra twelve
absorption peaks pertaining to 4 F3/2 , 4 F5/2 +2 H9/2 , 4 F7/2 +4 S3/2 , 4 F9/2 , 2 H11/2 , 4 G5/2 +2 G7/2 , 2 K13/2 +4 G7/2 , 4 G9/2 , 2 K15/2 +2 G9/2 +2 D3/2 ,
4

G11/2 , 2 P1/2 and 4 D3/2 +4 D5/2 with 4 I9/2 as the ground state are observed for all the Nd 3+ doped different chlorophosphate glass

matrices expect for sodium calcium chloro phosphate glass matrix (4 D3/2 +4 D5/2 transition is not observed in this glass
matrix). Though the observed spectra appear similar for all the glass matrices, the spectral intensities and spectral profiles
of certain transitions vary from one glass matrix to another glass matrix. In the present work, the spectral profile of the
transition 4 D3/2 +4 D5/2 clearly indicates such variation for different glass matrices.
Spectral Intensities and Judd-Ofelt Parameters
The measured spectral intensities and calculated spectral in tensities for all the spectral intensities of different
absorption bands of Nd 3+ ions calculated. It is observed that among four chlorophos phate glass matrices potassium glass
matrix showing higher spectral intensities. Among the three mixed chlorophosphat e glass matrix sodium potassium glass
showing higher spectral intensity values. The best set Judd-Ofelt intensity parameters [3, 4], 2 , 4 , 6 , and parameters
are presented in Table 1. The 2 parameter indicates the covalence of the metal-ligand bond, whereas 4 and 6 indicate
the rigidity of the host materials. In the calculation of the above intensity parameters, the spectral of transitions 2 P1/2 and
4

D3/2 +4 D5/2 are not included in the least square fitting procedure because there is some uncertainty in the measurement of

the spectral intensities. Due to overlapping of certain absorption peaks, i.e. 4 F5/2 on 2 H9/2 , 4 F7/2 on 4 S3/2 , 4 G5/2 on 2 G7/2 and
2

K13/2 on

G7/2 . It is observed that 2 and 6 parameters are more sodium, potassium and sodium potassium

chlorophosphate glass matrices when compared with other glass matrices. It indicates more covlance of Nd-O bond in
these glass matrices. It is also indicates that crystal field asymmetry at the site of Nd 3+ ion is high for sodium, potassium
and sodium potassium chlorophosphate glass matrices. it is also observed that, 4 parameter lower for sodium-potassium
glass matrix indicating lower rigidity of the glass matrix. Jacob and Weber introduced new parameter which is called
spectroscopic quality factor (4/ 6 ) is presented in table. In the present work, the value range 0.76-0.24 for different
phosphate matrices.

Impact Factor (JCC): 1.8003

Index Copernicus Value (ICV): 3.0

A Photoluminescence Study of Nd3+ Doped Different Chloro-Phosphate Glasses for Solid State Laser Applications

25

Hypersensitive Transitions
The spectral intensity of hypersensitive transition is largely dependent on the surrounding environment of Nd 3+
ion and in turn it shows the effect on intensity parameters. For Nd 3+ ion, the hypersensitive transition is 4 I9/2 4 G5/2. The
shift in the peak wavelength of the hypersensitive transition towards longer wavelength indicates increase in the degree of
covalency of Nd-O bond. Normally the intensity parameter 2, indicates covalence decreases/increases with the
decrease/increase of intensity of the hypersensitive transition. There is no peak splitting and also there is no change in the
spectral profile of the hypersensitive transition. The shift of the peak wavelength of the hypersensitive transition towards
longer wavelength indicates increase in the covalent nature of Nd -O bond. In the present work, the 4 I9/2 4 D3/2 +4 D5/2 splits
in two peaks clearly and also there is a change in the spectral profile of the transition from one glass matrix to another glass
matrix. It indicates structural changes for different environments.
Radiative Properties
In the present work, certain radiative properties of Nd 3+ doped different chlorophos phate glasses are estimated
using Judd-Ofelt intensity parameters. These radiative properties are radiative transition probabililities (A rad ), radiative
lifetimes (R), branching ratios ( R) and integrated absorption cross -sections () of different transitions are calculated.
The radiative lifetimes (R) for the excited states 4 G9/2 , 4 G7/2 , 4 G5/2,, 2 H11/2 , 4 F9/2 , 4 F5/2 and 4 F9/2 are presented in Table 2 from
the table, it is observed that radiative lifetimes of all the excited states are minimum for magnesium glass matrix and
maximum for sodium calcium glass matrix. The branching ratios (R) are more for 4 G5/2 4 I9/2 transition. Among various
glass matrices, magnesium glass matrix showing higher branching ratio values. It is also observed that, the integrated
absorption cross-sections () are higher for 4 G7/2 4 I11/2 transition.

EXCITATION AND EMISSION SPECTRA

The emission spectra of Nd 3+ doped different chlorophosphate glass matrix recorded at room temperature in the
wavelength region 600-1600 nm under excitation wavelength 514.5 nm are shown in Figure 3. In the emission spectra,
three peaks, 4 F3/2 4 I9/2 and 4 F3/2 4 I11/2 and 4 F3/2 4 I13/2 are observed nearly at 909, 1071 and 1339 nm respectively.
From the emission spectra, radiative transitions probabilities (A rad ), branching ratios ( exp ), effective linewidths
( eff ) and emission cross-sections (p ) of the above three transitions are presented in Table 3. The emission
band 5 F3/2 4 I11/2 at 1071nm has been considered as potential lasing transition due to the large stimulated emission
cross-section. From the table it is observed that, among the four chlorophosphate glass matrices, potassium glass has
maximum peak emission cross-section. Among three chlorophosphate glass matrices, sodium potassium glass has higher
peak emission cross-section (p ) values for this transition. Hence this glass matrix may be useful for lasing material.

CONCLUSIONS
Spectroscopic properties of Nd 3+ doped different chlorophsophate glass have been investigated using optical and
emission spectra. The amorphous nature of studied glass matrices is confirmed through XRD profiles. Among four chloro
phosphate glass matrices potassium glass matrix showing higher spectral intensities, but three mixed chlorophosphate glass
matrix sodium potassium glass showing higher spectral intensity values. The Judd -Ofelt intensity parameters 2 and
are more sodium, potassium and sodium potassium chlorophosphate glass matrices when compared with other glass
matrices. From the radiative properties, it is concluded that radiative lifetimes of all the excited states are minimum for
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26

K. Venkata Rao & Y. C. Ratnakaram

magnesium glass matrix and maximum for sodium calcium glass matrix. From the emission spectra, the four
chlorophosphate glass matrices, potassium glass has maximum peak emission cross -section. Among three chlorophosphate
glass matrices, sodium potas sium glass has higher peak emission cross -section (p ) values for this transition. Hence this
glass matrix may be useful for lasing material.

ACKNOWLEDGEMENTS
The author K. Venkata Rao expresses his thanks to the University Grants Commission (UGC) for prov iding the
financial assistance in the form of minor research project F.No. 4161/12 (MRP/UGC-SERO).

REFERENCES
1.

J. Li, Y.Z. Mei, C. Gao, F. Ren, A.X. Lu, J.Non-Cryst. Solids 357 (2011) 17361740.

2.

Petr Moner, Kateina Vosejpkov, Ladislav Koudelka, Lionel Montagne, Bertrand Revel, J. NonCryst. Solids 357 (2011) 26482652

3.

B.R. Judd, Phys. Rev. 127 (1962) 750.

4.

G.S. Ofelt, J. Chem. Phys. 37 (1962) 511.

APPENDICES

Intensity (counts)

Na-K
Ca

Mg
K
Na
10

20

30

40

50

60

70

2 (degree)

Fig 1.

Figure 1
4

G5/2+ G7/2

2.5

F5/2+ H9/2

F7/2+ S3/2

D3/2+ D5/2

Relative absorbance(a.U)

2.0
2

1.5

K13/2+ G7/2

K15/2, G9/2, D3/2

4

G9/2

F3/2

G11/2

1.0

P1/2

F9/2

H11/2

0.5

400

500

600

700

800

900

Wavelength(n.m)

Fig 1. Optical absorption

of Nd doped alkali and alkalin earth potasium posphate glass
Figure 2: Optical Absorp Spectra
of Nd2+spectra
Doped
Alka Li and Alkalin Earth Potassium Phosphate Glass
3+

Impact Factor (JCC): 1.8003

Index Copernicus Value (ICV): 3.0

A Photoluminescence Study of Nd3+ Doped Different Chloro-Phosphate Glasses for Solid State Laser Applications

0.010

27

F3/2 I11/2

0.008
4

Relative Intensity (a.u)

F3/2 I9/2
4

0.006

F3/2 I13/2

Na-Ca

Na-Mg

0.004
Na-K

Ca

0.002
Mg
K

0.000

Na

800

1000

Wavelength(nm)

1200

1400

3+

Fig 3. Luminesence spectra of Nd doped different chloroposphate glass

Figure 3: Lumlnese Spectra of Nd2+ Dopped Different Chloro Phosphate Glass

Table 1: Judd-Ofelt Intensity Parameters ( X10 20 ) (=2, 4, 6) (Cm2 )) of Nd3+ Doped Different Chlorophosphate
Glasses
S.No

Parameter

Na

Mg

Ca

Na-K

Na-Mg

Na-Ca

1
2
3
4

2
4
6
= 4/ 6

15.01
17.01
22.31
0.76

18.60
14.10
26.10
0.54

6.89
2.96
6.43
0.46

3.33
6.41
3.82
1.67

8.70
2.68
10.81
0.24

3.86
3.08
6.82
0.45

3.73
3.01
4.95
0.60

Table 2: Radiative Lifetimes (R ) (S) of Certain Excited States of Nd3+ Ions Doped in Different Chlorophosphate
Glasses
S. No

Excited
Level

3+

Nd
1
2
3
4
5
6
7

G9/2
G7/2
4
G5/2
2
H11/2
4
G9/2
4
F5/2
4
F3/2
4

Na

20.3
19.3
64.3
72.9
52.7
86.1
94.9

22.3
20.7
66.8
81.8
54.2
94.6
101.7

Mg
14.7
13.7
43.7
52.9
36.5
62.0
67.6

Ca

Na-K

Na-Mg

Na-Ca

692.5
634.9
2183.4
2645.5
1724.1
2754.8
3105.6

69.8
62.5
255.9
321.7
168.0
246.8
3226.8

55.4
52.4
217.4
229.8
147.6
208.8
265.5

71.4
68.9
287.5
280.9
202.2
122.0
349.8

Table 3: Certain Fluorescence Properties of Nd3+ Ions Doped in Different Chlorophos phate Glasses
4

S.
N
o

Glass

1
2
3
4
5
6
7

Na
K
Mg
Ca
Na-K
NaMg
Na-Ca

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F3/2 4 I9/2

F3/2 4 I11/2

F11 /2 4 I13/2

P
(nm)

Arad
(s -1 )

(cm-1 )

P
(10 1
cm2 )

P
(nm)

Arad
(s -1 )

(cm-1 )

P
(10 -19
cm2 )

P
(nm)

Arad
(s -1 )

(cm-1 )

P
(10 -21
cm2 )

908.9
908.9
903.7
903.7
903.7
903.7
906.7

5583
5071
1151
1821
1321
2401
1046

42139
42121
42420
42612
42612
42612
42326

5.091
4.362
1.000
1.567
1.075
1.992
0.886

1071.1
1071.1
1071.1
1071.1
1071.1
1071.1
1071.1

7022
7771
1910
1502
2941
4562
1500

30295
30292
30295
30295
30295
30295
30295

15.560
18.559
4.257
3.382
6.451
4.736
3.257

1339.3
1339.3
1339.1
1339.1
1339.1
1339.1
1341.5

1329
1584
397
277
654
1157
299

19384
19384
19381
19384
19384
19384
19327

4.910
4.440
1.310
0.609
2.269
2.043
1.054

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