Physics Procedia 13 (2011) 70–73

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Physics Procedia 00 (2010) 000±000
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17th International Conference on Dynamical Processes in Excited States of Solids

Optical properties of Dy3+-doped P2O5 - K2O ± MgO/MgF2 ± Al2O3 glasses

K. Upendra Kumar1, 2 *, Ch. Srinivasa Rao2, C. K. Jayasankar2, S. Surendra Babu3, J.L. Lucio1,
Miguel A. Vallejo H4 and Ma. Alejandrina Martinez Gamez4
1
División de Ciencias e Ingenierías; Campus León; Universidad de Guanajuato. Loma del Bosque 103, Col. Lomas del Campestre 37150, León
Guanajuato, México.
2
Department of Physics, Sri Venkateswara University, Tirupati-517 502, India.
3
Laser Instrumentation Division, Instruments Research & Development Establishment, Dehradun - 248 008, Uttarkhand, India.
4
Centro de Investigaciones en Óptica, Loma del Bosque 115, Col. Lomas del Campestre, León 37150, Guanajuato, México.

Abstract

Optical and fluorescence properties of Dy2O3-doped P2O5 + K2O + MgO + Al2O3 and P2O5 + K2O + MgO + MgF2 +
Al2O3 glasses have been investigated at room temperature. From the optical absorption measurements and using
Judd-Ofelt (JO) theory, JO parameters have been obtained which are used to predict the radiative properties of 4F9/2
level of Dy3+ ion. A strong yellow (Y) and blue (B) emissions corresponding to 4F9/2 ĺ 6H13/2 and 4F9/2 ĺ 6H15/2
transitions of Dy3+ ions were observed in these glasses. A good correlation between the intensity ratio (Y/B) and
:6/:2 was identified. The CIE colour coordinates were evaluated from the emission spectra to simulate white light
emission from the title glasses. Fluorescence decay curves of the 4F9/2 ĺ 6H13/2 transition have been measured and
DQDO\VHG7KHSURGXFWRIıem [IJexp reveals the possibility of using these glasses for yellow laser.

⃝
c© 2011
2010 Published
Published by
by Elsevier
Elsevier B.V.
B.V.Open access under CC BY-NC-ND license.
Keywords: Dysprosium, phosphate glasses, Judd-Ofelt analysis, yellow-blue fluorescence, white light emission.
1. Introduction
Recent developments in the new laser media, particularly glasses, in the visible region have raised the interest
on optical materials based on the Dy3+ ion. The most attractive property of glasses is the ability to produce fiber
amplifier and acts as a laser host. Among different glass systems, magnesium phosphate glasses have interest due to
their low density, high viscous, high polarizability and high field intensity nature while MgF 2 has the strongest
ability to form fluorophosphate glass in the bivalent alkaline earth fluoride and play an important role in the
structure and thermal properties [1,2]. Lasing in visible region in glass hosts has many technological applications in
commercial displays and optical devices. Dy3+ ion has two dominant bands in the visible emission spectrum, yellow
band (574 nm) that corresponds to the hypersensitive transition 4F9/2 ĺ 6H13/2 ¨/ ¨- DQGWKHEOXHEDQG
(480 nm) that corresponds to the 4F9/2 ĺ 6H15/2 transition [3-7]. Obviously the intensity of the hypersensitive
transition varies with the environment, where as the other transition is insensitive to the environment. The
optimization of local environment for Dy3+ ions is a formidable task to get white light from Dy3+-doped glasses.
Although many investigations have been carried out extensively on most rare-earths in different hosts, the available
literature on Dy3+- doped metaphosphate glass hosts is very limited. In this communication a systematic
investigations on the optical and luminescence properties of Dy3+ ions in a phosphate glass system has been
reported.

Tel : + 52- 477 788 5100, ext. 8473, fax: +52 ± 477 788 5100 ext. 8410
* Corresponding author: kumarkupendra@yahoo.co.in

1875-3892 ⃝c 2011 Published by Elsevier B.V. Open access under CC BY-NC-ND license.
doi:10.1016/j.phpro.2011.02.017
 K. Upendra Kumar et al. / Physics Procedia 13 (2011) 70–73 71
Author name / Physics Procedia 00 (2011) 000±000

2. Experimental details
Dy2O3 doped glasses with compostions, PKMADy: (59-x/2) P2O5 + 17.0 K2O + (15-x/2) MgO + 9.0 Al2O3
+ x Dy2O3 and PKMFADy: (56-x/2) P2O5 + 14.0 K2O + (15-x/2) MgO + 9.0 Al2O3 + 6.0 MgF2 + x Dy2O3 (where x
= 0.01, 0.1, 1.0 and 2.0 mol %), were prepared by conventional melt quenching technique. To prepare these
samples, reagent-grade of Al(PO3)3, Ba(PO3)2, KH2PO4, MgF2 and Dy2O3 are taken. The procedure of glass
preparation and measurements of physical and spectral properties are similar to our earlier work [7].

3. Results and discussion

3.1. Absorption spectra- Judd-Ofelt analysis

Figure 1 shows the absorption spectra of 1.0 mol % Dy2O3-doped 58.5 P2O5 + 17.0 K2O + 14.5 MgO + 9.0
Al2O3 + 1.0 Dy2O3 (PKMADy10) and 55.5 P2O5 + 14.0 K2O + 14.5 MgO + 9.0 Al2O3 + 6.0 MgF2 + 1.0 Dy2O3
(PKMFADy10) glasses in the UV-VIS-NIR regions. The transition from the ground 6H15/2 state to 6H and 6F terms
are spin-allowed ('S = 0). Moreover, the transitions within the 6H term are also allowed by the orbital angular
moment selection rule, 'L = 0. Hence, these transitions lying in the infra-red are relatively intense.
1.5
UV-VIS (a) PKMADy10 6 6
(a) PKMADy10
(b) PKMFADy10 NIR H + F
9/2 11/2 (b) PKMFADy10

6
P
1.0
Absorbance (a.u)

3/2

4
M 6
19/2 6 6
4 F F
I13/2 4 F 7/2 9/2 6
+ G
11/2 4 4 6
5/2 H
11/2
I F
15/2 9/2 (b) F
3/2
0.5 (b)

(a)
(a)

0.0
375 450 900 1200 1500 1800
Wavelength (nm)

Fig 1. Optical absorption spectra of 1.0 mol% Dy2O3 doped (a) PKMADy10 and (b) PKMFADy10 glasses at room
temperature.

The optical absorption spectra of the title glasses has been analysed in the frame work of Judd-Ofelt (JO)
theory [7]. The oscillator strengths of various absorption transitions are evaluated. A least-square fitting approach is
adopted to determine the JO parameters, which gives the best-fit between the experimental and calculated oscillator
strengths. The Judd-Ofelt (JO) parameters for both PKMADy10 (:2 = 7.55, :4 = 2.30 and :6 = 1.7, x10-20 cm2) and
PKMFADy10 (:2 = 8.04, :4 = 1.84 and :6 = 1.41, x10-20 cm2) glasses follow the trend as :2 > :4 > :6. These JO
parameters are found to be higher than lead-borate [3], oxyfluoride silicate [5] and phosphate [7] glasses. The
decreasing trend of the magnitude of JO parameters (:2 > :4 > :6) for the present studied glasses may be attributed
to the presence of similar sites around the Dy3+ ions, consequently it can be an evidence for the good quality of a
glass host for optical application [8]. In general the JO parameters provide information on the bond between RE ion
and surrounding ligands as well as the symmetry of the environment around the RE ions. The larger value of :2 is
probably a direct consequence of more covalent nature of chemical bonds and environment disorder in the present
studied glasses.

3.2. Emission and emission decay properties

Figure 2 shows the emission spectra of the title glasses. The spectra correspond to the emission originated
from the luminescent 4F9/2 level to the ground 6HJ (J = 9/2, 11/2, 13/2 and 15/2) multiplets. From the emission
72 K. Upendra Kumar et al. / Physics Procedia 13 (2011) 70–73
Author name / Physics Procedia 00 (2011) 000±000

spectra, experimental emission peak positions, effective linewidths ('Ȝeff), branching ratios ( E R ) and peak
stimulated emission cross-sections (VȜp)) are determined and are reported in Table 1 along with predicted ER
using the JO theory.
2.0 1.0 4
F9/2 (b) PKMFADy
4 CIE1931 Oexc = 457.9 nm
F9/2 0.8 0.1
Normalised intensity (arb. unit)

Normalised intensity (arb. units)

0.01
y- chromacity coordinates
1.6 6
H13/2 0.6
PKMADy

IH fit 1.0
0.4

S=6
1.2 2.0
PKMFADy
0.2

6
H15/2 0.0
4
F9/2 (a) PKMADy
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Oexc = 457.9 nm
0.8 x- chromacity coordinates
0.1 0.01
6 6
H11/2 H9/2
(b)
0.4 1.0
IH fit
S=6 2.0
(a)

0.0
500 600 700 800 0 500 1000 1500 2000 2500

Time (Psec)
Wavelength (nm)
Fig 2. Emission spectra of 1.0 mol% Dy2O3 in Fig 3. Emission decay of 4F9/2 ĺ6H13/2 transition
(a) PKMADy10 and (b) PKMFADy10 glasses. for 0.01 - 2.0 mol% Dy2O3 doped (a)PKMADy
Inset shows the CIE colour coordinates for 1.0 mol% and (b) PKMFADy glasses. Solid line (-) shows
Dy2O3 doped PKMADy and PKMFADy glasses. IH fit for S=6.

As can be seen from Figure 2, the peak at 574 nm is more intense with a higher branching ratio. Peak stimulated
emission cross-VHFWLRQıOp), x10 -21 cm2) is also largest for the 4F9/2 o 6H13/2 transition with the values of 2.62
and 2.49 for PKMADy10 and PKMFADy10 glasses, respectively. The ıOp) value is found to be lower than
phosphate [7] and lead borate [9] glasses. The mixed anions, fluorine and oxygen in the former network of
phosphate glass involve an important site-to-site variation of the ligand field which affects asymmetry of the Dy 3+
site environments that in turn cause variation in the emission cross section.

Table 1. Emission band positions (Op, nm), effective band width ('Oeff, nm), peak stimulated emission cross
section (V(Op), x 10-21 cm2), experimental and calculated values of branching ratios (ER) for 1.0 mol%
Dy2O3 -doped PKMADy10 and PKMFADy10 glasses.

'Oeff V(Op) ȕR
Transition
4 Op PKMADy10 PKMFADy10
F9/2 o
PKMADy10 PKMFADy10 PKMADy10 PKMFADy10
Exp Cal Exp Cal
6
H9/2 754 6.14 4.91 0.54 0.66 0.01 0.02 0.00 0.02
6
H11/2 663 14.0 11.05 0.60 0.79 0.02 0.08 0.02 0.08
6
H13/2 574 15.36 16.28 2.62 2.49 0.59 0.65 0.58 0.66
6
H15/2 480 22.2 22.72 0.19 0.15 0.38 0.13 0.40 0.11

7KH &RPPLVVLRQ ,QWHUQDWLRQDOH GH ,¶(FODLUDJH &,( FKURPDWLFLW\ FRRUGLQDWHV IRU  PRO '\ 2O3
doped PKMADy10 and PKMFADy10 glasses calculated from the emission spectra at the excited wavelength
457.9 nm line of an Ar+ laser. The chromaticity coordinates of PKMADy10 (x = 0.39, y = 0.44) and PKMFADy10
(x = 0.37, y = 0.41) glasses are located within the white light region, though they are far away from the ideal equal
energy white-light illumination (0.333, 0.333). As can be seen from the inset of Figure 2, the color coordinates tend
more into the white light region in the presence of MgF 2. These CIE chromaticity coordinate values are comparable
to those of Dy3+-doped silicate glass [4]. Further studies on simulation of white-light for these Dy3+-doped
 K. Upendra Kumar et al. / Physics Procedia 13 (2011) 70–73 73
Author name / Physics Procedia 00 (2011) 000±000

magnesium phosphate glasses are necessary by both varying the glass compositions and enhancing the red emission
part, may be by co-doping. The Yellow to Blue (Y/B) ratio in PKMADy10 glass is 1.99 and is comparable to the
value of 2.28, 2.29, 2.13, 2.11, 1.92 and 2.19 found in fluoroborate glasses containing lithium, zinc and lead [10].
But in PKMFADy10 glass Y/B ratio is 1.55, which shows considerable decrease due to the presence of MgF 2
content. The ratio Y/B decreases with increasing electronegativity of the next-neighbour element M in the complex
oxides Dy±O±M. Higher values of Y/B in PKMADy10 glass indicate that higher degree of covalence between Dy3+
and O2- ions [7]. Obviously the main transitions from 4F9/2 level to the 6H13/2 at 574 nm is dependent on :6 and 6H15/2
at 480 nm is dependent on :2. The value of :6/:2 for PKMADy10 is 0.23 and for PKMFADy10 is 0.18. :2 are
affected by the local asymmetry [11]. Thus the intensity ratio (Y/B) and :6/:2 both are in good correlation and
giving the same information as explained in ref [12].
The fluorescence decay curves of the luminescence originating from the 4F9/2 level of Dy3+ ions were
measured with an excitation of 457.9 nm were shown in Figure 3. With increase in Dy2O3 concentration from 0.01
to 2.0 mol%, the decay curves gradually changes from near exponential to larger non-exponential nature. The
perfect exponential emission decay was found only for 0.01mol% Dy2O3. The measured lifetime (0.96 ms and 1.03
ms for 0.01 mol% Dy2O3 doped in PKMADy and PKMFADy respectively) for this curve is called intrinsic lifetime.
This intrinsic lifetime is used in Inokuti-Hirayama (IH) model fitting, described in our earlier work [13], for non-
exponential emission decay curves to determine the dominant mechanism of interaction for energy transfer between
the active ions. The IH model was best fitted (solid lines) with S = 6 for 1.0 and 2.0 mol% Dy2O3 concentrations,
shown in Figure 3, confirming that the dominant interaction for energy transfer through cross-relaxation between
Dy3+ ions is of dipole-dipole type. Furthermore, the PKMADy10 and PKMFADy10 glass systems have long
IOXRUHVFHQFHOLIHWLPHIJexp), 0.71 ms and 0.79 ms DQGKLJKJDLQFRHIILFLHQWWKHSURGXFWRIı em [IJexp) 1.87x 10-24
cm2s, 1.97x10-24 cm2s, respectively, better than Dy3+ -doped barium fluoroborate glasses [14], which can serve as a
suitable host for Dy3+ ion to attain yellow laser .

3.3. Conclusions
The absorption spectral intensities of Dy3+-doped magnesium phosphate glasses have been analysed with
the help of the Judd-Ofelt theory. The glass samples emit simultaneously visible, blue and yellow lights as well as a
weaker red emission under 457.9 nm excitation. The correlation between Yellow/Blue ratio and JO parameters,
:6/:2, was observed. The systematic analysis of optical properties of title glasses reveals that the MgO/MgF 2 plays
a key role in phosphate glasses to tune the white light emission as well as laser action in yellow region.

Acknowledgement
One of the authors (CKJ) is grateful to the DAE-BRNS, Govt. of India for the award of the Major Research Project
(No. 2007/34/25-BRNS/2415, dt. 18-01-2008). Dr. K. Upendra Kumar is thankful to Prof. J.L. Lucio, Leon campus,
Leon gto, University of Guanajuato, Mexico, for providing partial financial support.

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