Optical Materials 66 (2017) 559e566

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

White light emission of dysprosium doped lanthanum calcium

phosphate oxide and oxyfluoride glasses
N. Luewarasirikul a, H.J. Kim b, P. Meejitpaisan a, c, J. Kaewkhao a, c, *
a
Physics Program, Faculty of Science and Technology, Nakhon Pathom Rajabhat University, Nakhon Pathom, 73000, Thailand
b
Department of Physics, Kyungpook National University, Deagu, 702-701, Republic of Korea
c
Center of Excellence in Glass Technology and Materials Science (CEGM), Nakhon Pathom Rajabhat University, Nakhon Pathom, 73000, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: Lanthanum calcium phosphate oxide and oxyfluoride glasses doped with dysprosium oxide were
Received 3 January 2017 prepared by melt-quenching technique with chemical composition 20La2O3:10CaO:69P2O5:1Dy2O3
Received in revised form and 20La2O3:10CaF2:69P2O5:1Dy2O3. The physical, optical and luminescence properties of the glass
16 February 2017
samples were studied to evaluate their potential to using as luminescence materials for solid-state
Accepted 23 February 2017
Available online 12 March 2017
lighting applications. The density, molar volume and refractive index of the glass samples were car-
ried out. The optical and luminescence properties were studied by investigating absorption, excitation,
and emission spectra of the glass samples. The absorption spectra were investigated in the UVeVis
Keywords:
Phosphate glass
eNIR region from 300 to 2000 nm. The excitation spectra observed under 574 nm emission wavelength
Oxyfluoride showed the highest peak centered at 349 nm (6H15/2 / 6P7/2). The emission spectra, excited with
Dysprosium 349 nm excitation wavelength showed two major peaks corresponding to 482 nm blue emission (4F9/
6 4 6
Photoluminescence 2 / H15/2) and 574 nm yellow emission ( F9/2 / H13/2). The experimental lifetime were found to be
Judd-Ofelt theory 0.539 and 0.540 for oxide and oxyfluoride glass sample, respectively. The x,y color coordinates under
w-LEDs 349 nm excitation wavelength were (0.38, 0.43) for both glass samples, that be plotted in white region
of CIE 1931 chromaticity diagram. The CCT values obtained from the glass samples are 4204 K for oxide
glass and 4228 K for oxyfluoride glass corresponding to the commercial cool white light (3100
e4500 K). Judd-Ofelt theory had also been employed to obtain the J-O parameters (U2, U4 and U6),
oscillator strength, radiative transition possibility, stimulated emission cross section and branching
ratio. The U2 > U4 > U6 trend of J-O parameters of both glass samples may indicate the good quality of a
glass host for using as optical device application. Temperature dependence of emission spectra was
studied from 300 K to 10 K and found that the intensity of the emission peak was found to be increased
with decreasing of the temperature. The results of the investigations in this work confirmed that the
present Dy-doped lanthanum calcium phosphate oxide and oxyfluoride glasses perform high potential
for using as efficient luminescence materials for solid-state lighting applications, especially for white
LEDs. Furthermore, the oxyfluoride glass sample provides more luminescence potential than the oxide
glass sample.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Solid-state lighting applications play important role in present
day due to the potential to reduce lighting energy usage, along with
other benefits such as long life, more durability, low temperature
that make the devices generally cool to touch, low voltage and
* Corresponding author. Physics Program, Faculty of Science and Technology,
Nakhon Pathom Rajabhat University, Nakhon Pathom, 73000, Thailand.
E-mail address: mink110@hotmail.com (J. Kaewkhao).
better quality light output (low ultraviolet and infrared radiation)
[1e3]. Nowadays, many researches aim to improve the perfor-
mance, durability and cost-effectiveness of solid-state lighting ap-
plications. In this work, glasses doped with dysprosium ions were
developed to using as luminescence materials for white light solid-
state lighting (w-LEDs). White light LEDs can be produced by
combining the three primary colors (RGB), using a red emitting
light from Y2O2S:Eu,Ti,Mg phosphor, a green emitting light from
SrAl2O4:Eu,Dy phosphor and a blue emitting light form CaA-
l2O4:Eu,Nd phosphor to generate white light [4e7], but this method

http://dx.doi.org/10.1016/j.optmat.2017.02.049
0925-3467/© 2017 Elsevier B.V. All rights reserved.
560 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566
have low luminescence efficiency because of re-absorption of blue
light. Another method, that have higher luminescence efficiency, is
to use a blue emitting InGaN blue LED pumping a yellow YAG:Ce3þ
phosphor to generate white light, this method called phosphor
converted w-LEDs (pc w-LEDs) [1,8]. Unfortunately, phosphors in
the both methods are need to encapsulated in the epoxy resin that
have some disadvantages such as the yellow color of epoxy resin
impacts to the color of emitting light of w-LEDs and the cracking
and delamination of epoxy resin encapsulation [1]. Moreover, sili-
cones, that have been the materials used as the encapsulants and
also use as the polymer matrix for phosphors to convert blue LEDs
to white LEDs due to their good transparency and high thermal
resistance, lead to the decreasing of luminescence efficiency.
Thermal shrinking property is another problem of silicone-based
materials too [1,9,10].
Glasses doped with dysprosium ions, studied in this work, are
the alternate materials for using as the more effective w-LEDs.
Glasses are the most investigated materials for using as host ma-
terials because of their advantages like ease of fabrication, ease in
forming to any shape, high thermal stability, low production cost
and flexibility to add chemical substances for improve or modify
some properties of the glasses [11e14]. The Glasses doped with rare
earth (RE) ions are important materials that have wide range of
potential applications in solid-state lasers, solid-state lighting, color
display devices, optical amplifiers, optical sensors, etc., because of
the luminescence property of RE-doped glasses, so when exciting
RE-doped glasses with appropriate excitation wavelength, they can
emit intense radiations in the visible, near infrared and infrared
spectral regions. Dysprosium (III) ion (Dy3þ), with 4f9 electronic
configuration, is one of the most interesting rare earth ions for
doping in glasses because of its good emission in white region with
high luminescence efficiency [7,15e17]. The Dy-doped glasses
provide two major emission transitions that corresponding to
4
F9/2 / 6H15/2 transition for blue emission light and 4F9/2 / 6H13/2
transition for yellow emission light. By combining the blue and
yellow emission light, the white light can be generated.
Among several of optical materials from oxide glasses, phos-
phate glass system exhibits many good properties for using as
optical devices like low melting point, high chemical durability,
good thermal stability, high transparency, low dispersion, relatively
high refractive indices (compared with silicate-based optical glass)
and especially good solubility of rare earth ions, which allows the
large concentrations of rare earth ions contain in the glass matrix
[18e21]. Calcium oxide and lanthanum oxide are often added to
modify the glass structure, which improve strength and chemical
stability of glasses, lanthanum oxide also improves optical prop-
erties of glasses too [22,23]. However, oxide glasses have high
phonon energy (1200-1350 cm1 for phosphate glass), fluoride
addition in glass system causes fluoride reacts with the OH group to
form HF, so this can reduces OH absorption and make this oxy-
fluoride glasses have low phonon energy [18,24]. Glass hosts with
low phonon energy are good for doping RE ions because they can
reduce multi-phonon relaxation rates of the emission transitions,
that enhancing the luminescence efficiency [25,26]. Many re-
searches [2,7,12,13,16,25,27e30] had report the concentration
quenching of photoluminescence in Dy-doped glasses at 1.0 mol%
of Dy2O3 doped in glasses and/or select only 1.0 mol% of Dy2O3 to
study, then 1.0 mol% of Dy2O3 concentration had been chosen in
this research to study the present Dy-doped glasses. In this work,
lanthanum calcium phosphate oxide and oxyfluoride glasses doped
with Dy3þ had been fabricated. The physical, optical and lumines-
cence properties of the glass samples were studied to determine
the potential of the glass samples for using as luminescence ma-
terials for solid-state lighting applications.
2. Experimental
Dy-doped lanthanum calcium phosphate oxide and oxyfluoride
glasses were prepared by melt-quenching technique with chemical
composition 20La2O3:10CaO:69P2O5:1Dy2O3 and 20La2O3:10-
CaF2:69P2O5:1Dy2O3. The raw materials such as lanthanum oxide
(La2O3), calcium oxide (CaO), calcium fluoride (CaF2), ammonium
dihydrogen phosphate (NH4H2PO4) and dysprosium (III) oxide
(Dy2O3) were weighted by stoichiometric ratio and thoroughly
mixed and ground by grinding in a high purity alumina crucible for
30 g total weight of the glass samples. The chemical mixtures were
melted in an electric muffle furnace at 1400  C for 3 h, then the melt
samples were poured into preheated stainless steel mould and
annealed in an annealing furnace at 500  C for 3 h for eliminated
internal mechanical stress before slowly cooled down to room
temperature. The glass samples were cut and polished as shown in
Fig. 1.
The density (r) was measured by Archimedes' principle at room
temperature, the molar volume (VM) was carried out by dividing
the total molecular weight (MT) of each sample by its density (r),
VM ¼ MT/r. The refractive index (n) was measured by Abbe
refractometer with a sodium-vapor lamp as a light source and using
mono bromonaphthalene (C10H7Br) as a contact liquid. The
chemical bonds inside the glass matrix were investigated by FTIR
spectrometer. The absorption spectra were recorded by
UVeViseNIR spectrophotometer (Shimadzu, UV-3600) in the
range of 300e2000 nm. The photoluminescence excitation spectra,
emission spectra and luminescence decay time measurements
were measured by fluorescence spectrophotometer (Agilent Tech-
nologies, Cary Eclipse) with xenon lamp as a light source. CIE 1931
chromaticity diagram (the diagram that defined quantitative links
between physical pure color in the electromagnetic visible spec-
trum and physiological perceived color in human color vision) was
used to determine color of the emission light obtained from the
emission spectra. The quality of the emitting light can be evaluated
by correlated color temperature (CCT) values.
Judd-Ofelt theory was employed to analyzed the radiative
properties of the glass samples by calculated the J-O parameters
(U2, U4 and U6), experimental and calculated oscillator strength
(fexp and fcal), radiative transition possibility (AR), stimulated
emission cross section (s) and branching ratio (BR). From the ab-
sorption spectra, the experimental oscillator strengths of absorp-
tion transition of Dy3þ ions had been calculated, and then obtained
experimental oscillator strengths had been used to evaluate the J-O
Fig. 1. Photograph of G1 and G2 glasses.
 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566 561

parameters by least-square fitting between the experimental and

the calculated oscillator strengths. The branching ratio and radia-
tive transition possibility were obtained by the calculation from
integral intensity area under the emission peaks and the J-O pa-
rameters, and the stimulated emission cross section can be calcu-
lated from radiative transition possibility via Judd-Ofelt relation
[31]. Temperature dependence of emission spectra was also stud-
ied from room temperature (300 K) down to 10 K with compressed
helium gas in vacuum chamber by exciting with 266 nm laser
excitation.

3. Result and discussion

3.1. Physical and optical properties

The density, molar volume and refractive index of the glass

samples are shown in Table 1. The density of the oxyfluoride glass
(G2) is higher than the oxide glass (G1) because of higher relative
molecular weight of CaF2 in G2 glass than CaO in G1 glass. The
molar volume and refractive index of G2 glass are also higher than
G1 glass too. The two fluoride atoms of CaF2 in S2 glass may
occupied more space than the one oxygen atom of CaO in S1 glass Fig. 2. The FTIR transmittance spectra of G1 and G2 glasses.
cause the increasing of the molar volume. While the increasing of
the refractive index can be explained by the classic dielectric the-
ory, the refractive index of a glass increases with the increasing of
its density.
Fig. 2 shows the FTIR transmittance spectra of G1 and G2 glasses
in the region 650 to 4000 cm1, which consist of the bands at about
682 and 821 cm1 (due to symmetric and asymmetric stretching
vibrations of PeOeP groups, respectively), 1297 cm1 (due to PO2
asymmetric stretching vibrations), 1653, 2097, 2861 and 2927 cm1
(due to stretching vibrations of PeOeH groups) and the broad band
at 3327 cm1 belongs to stretching of OeH or HeOeH groups
[14,18,25,32e34]. The reduction of the peaks at 1653, 2097, 2861,
2927 and 3327 cm1, that related to OH groups, of G2 glass compare
with G1 glass, may confirm that fluoride in oxyfluoride G2 glass
reacts with the OH groups to form HF groups.
Fig. 3 and Fig. 4 show the absorption spectra of G1 and G2
glasses recorded in the range of 300e2000 nm. The peaks shown in
the absorption bands corresponding to the transitions originated
from 6H15/2 state to the various excited state, i.e., 6P3/2 (322 nm),
6
P7/2 (349 nm), 4P3/2 (363 nm), 4F7/2 (386 nm), 4G11/2 (424 nm), 4I15/2
(452 nm), 6F3/2 (748 nm), 6F5/2 (798 nm), 6F7/2 (896 nm), 6F9/2
(1089 nm), 6H9/2 (1266 nm) and 6H11/2 (1672 nm) [25,35,36]. The
highest peak centered at 349 nm (corresponding to the 6H15/ Fig. 3. The absorption spectra of G1 and G2 glasses in UVeVis region.
6
2 / P7/2 transition) in UVeVis region and centered at 1266 nm
(corresponding to the 6H15/2 / 6H9/2 transition) in NIR region, this
transition is the hypersensitive transition (The 4f transition that transition possibility (AR), stimulated emission cross section (s) and
very sensitive to the environment) that obey the selection rule, branching ratio (BR) of the glass sample. All parameters obtained
jDJ≪2j, jDL≪2j and DS ¼ 0). So these transitions are very sensitive from Judd-Ofelt analysis are shown in Table 2e5.
to the environment around Dy3þ ions that made these transitions The experimental (fexp) and calculated (fcal) oscillator
found to be more intense than the other transitions [37]. strengths (see Table 2.) of the 6H15/2 / 6H9/2 transition are the
highest for both G1 and G2 glasses due to the best absorption at
1266 nm in NIR region. The root-mean-square deviation (RMSD)
3.2. Judd-Ofelt analysis
between fexp and fcal found to be ±0.193  106 for G1 glass and
±0.033  106 for G2 glass. The small value of the RMSD in-
Judd-Ofelt theory is employed in this work to calculate the J-O
dicates the good fit between the experimental and calculated
parameters (U2, U4 and U6), oscillator strength (f), radiative

Table 1
Density, molar volume and refractive index of the glass samples.

Composition Symbol Density (g/cm3) Molar volume (cm3/mol) Refractive index

20La2O3:10CaO:69P2O5:1Dy2O3 G1 3.2657 52.8032 1.5883

20La2O3:10CaF2:69P2O5:1Dy2O3 G2 3.2824 53.2046 1.5914
562 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566

Table 3
Comparison of J-O parameters of G1 and G2 glasses compared with other Dy-doped
system.

System J-O parameters Order Reference

(1020 cm2)

U2 U4 U6
G1 glass 14.83 4.01 2.87 U2 > U4 > U6 Present work
G2 glass 17.25 4.62 4.6 U2 > U4 > U6 Present work
BiDy0.09OCl 9.27 2.13 4.22 U2 > U6 > U4 [15]
Borosulphate 16.82 9.45 6.50 U2 > U4 > U6 [42]
BPBDy 6.99 2.00 1.44 U2 > U4 > U6 [43]
CFBDy10 5.98 2.33 2.33 U2 > U4 ¼ U6 [30]
Fluoroborate 2.90 1.09 0.98 U2 > U4 > U6 [44]
Fluoroindate 1.78 1.48 1.84 U6 > U2 > U4 [45]
Fluorogermanate 5.41 1.89 1.92 U2 > U4 > U6 [26]
Fluorophosphate 12.34 2.67 2.30 U2 > U4 > U6 [26]
Fluorosilicate 8.14 2.04 2.26 U2 > U6 > U4 [26]
LiTBDy 8.75 2.62 2.07 U2 > U4 > U6 [43]
Oxyfluoride 6.41 1.02 2.25 U2 > U6 > U4 [46]
Oxyfluoroborate 2.68 2.56 0.89 U2 > U4 > U6 [47]
PKAlCaFDy10 13.30 3.38 2.83 U2 > U4 > U6 [35]
PKAZFDy 14.11 3.07 1.95 U2 > U4 > U6 [26]
PKBAFDy10 12.30 2.67 2.30 U2 > U4 > U6 [48]
Fig. 4. The absorption spectra of G1 and G2 glasses in NIR region. PKBFADy10 10.41 2.29 2.07 U2 > U4 > U6 [49]
PKMAFDy10 7.04 1.73 1.57 U2 > U4 > U6 [50]
Sodium zinc phosphate 2.69 0.29 0.12 U2 > U4 > U6 [51]
Tellurite 1.46 2.32 3.60 U6 > U2 > U4 [52]
oscillator strengths and also confirmed the validity of Judd-Ofelt
theory [21].
The J-O parameter U2 is sensitive to the local structure of the
rare earth ions and affected by the covalency of DyeO bonds, so the peaks centered at 322, 349, 363, 386, 424, 452 and 472 nm, cor-
higher value of U2 indicated the higher asymmetry around the rare responding to the transitions from 6H15/2 / 6P3/2 (322 nm), 6P7/2
earth ions and the higher value of the oscillator strength [31,39,40]. (349 nm), 4P3/2 (363 nm), 4F7/2 (386 nm), 4G11/2 (424 nm), 4I15/2
The value of U4 and U6 parameters are found to increase with (452 nm) and 4F9/2 (472 nm) [25,26,38]. Fig. 6 shows the emission
decreasing rigidity of the glass matrix due to the inversion of spectra, excited with 349 nm excitation wavelength. The four
vibrational amplitude and the RE-ligand bond length [31,39]. From emission bands centered at 482, 574, 662 and 752 nm, these peaks
Table 3, the J-O parameters U2, U4 and U6 of G2 glass are higher than were assigned as 4F9/2 / 6H15/2 (482 nm), 6H13/2 (574 nm), 6H11/2
G1 glass, this implies that when oxide glasses are modified with (662 nm) and 6H9/2 (752 nm) [25,26]. The two major peaks of
fluoride content, the DyeO covalency increase, the ligand field emission band for Dy-doped glass are the peaks corresponding to
around Dy3þ ions becomes more asymmetry and the rigidity of the the 4F9/2 / 6H15/2 and 4F9/2 / 6H13/2 transitions. The 4F9/2 / 6H15/2
glass matrix decrease. Furthermore, the higher value of U2 of both transition at 482 nm (blue) is due to the magnetic dipole (MD) that
G1 and G2 glasses indicated relatively higher covalency and higher its intensity is not depend on the local crystal field of the constit-
asymmetry around the Dy3þ ions of the present glasses than the uent atoms in the glass matrix. While the 4F9/2 / 6H15/2 transition
other reported glass systems. The J-O parameters of both G1 and G2 at 574 nm (yellow) is due to the electric dipole (ED) that its in-
glasses follow the trend as U2 > U4 > U6, which is similar to the tensity is very sensitive with the host's local environment. If the
trend observed in many Dy-doped glasses as shown in Table 3. The host glass matrix is more asymmetry, the interaction of the rare
trend U2 > U4 > U6 of RE-doped glass may indicates the good earth ions with host is stronger, so the intensity of the electric
quality of a glass host for using as optical device application [41]. dipole transition becomes more intense (yellow emission peak for
Dy-doped glass) [29]. For both G1 and G2 glasses, the yellow
3.3. Luminescent properties emission peaks of ED transitions are higher than the blue emission
peaks of MD transitions that mean Dy3þ ions in the glass samples
Fig. 5 shows the excitation spectra of the samples observed are located at low symmetry sites, so the glass samples in this work
under 574 nm emission wavelength. The excitation bands show are more asymmetry in nature. From the emission spectra, it found

Table 2
The experimental (fexp) and calculated (fcal) oscillator strengths of G1 and G2 glasses.

Transitions 6H15/2 / Wavelength (nm) fexp (106) fcal (106)

G1 G2 G1 G2
6
P3/2 322 0.1204 0.1927 0.0959 0.1581
6
P7/2 349 5.6761 5.4473 4.1563 5.1717
4
P3/2 363 1.6845 1.6061 0.6002 0.9981
4
F7/2 386 3.1262 3.1608 2.9631 2.4356
4
G11/2 424 0.2063 0.5062 0.1482 0.3097
4
I15/2 452 0.7129 0.9462 0.6390 0.9428
6
F3/2 748 0.7801 0.4027 0.2263 0.3763
6
F5/2 798 1.9958 1.7498 1.2005 1.9963
6
F7/2 896 2.9830 2.8955 2.8089 3.7817
6
F9/2 1089 3.7292 3.4819 3.8941 3.3860
6
H9/2 1266 13.6939 13.5153 13.6664 13.5834
6
H11/2 1672 1.6970 3.2033 1.9473 2.7144
 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566 563

Table 4
The radiative transition possibility (AR), stimulated emission cross section (s), experimental branching ratio (BR) and theoretical branching ratio (BRc) of important lumi-
nescence levels of G1 and G2 glasses.

Transitions of emission 4F9/2 / Wavelength (nm) AR (s1) s (1021 cm2) BR BRc

G1 G2 G1 G2 G1 G2 G1 G2
6
H15/2 482 263.28 365.68 0.4835 0.7278 0.2960 0.3008 0.1298 0.1527
6
H13/2 574 1384.1 1636.4 5.7817 6.2466 0.6683 0.6595 0.6821 0.6832
6
H11/2 662 157.82 180.31 1.0957 1.3177 0.0265 0.0256 0.0778 0.0753
6
H9/2 752 97.53 99.34 2.4599 1.3124 0.0091 0.0141 0.0481 0.0415

Table 5
The laser properties of G1 and G2 glasses compared with other Dy-doped system.

System AR (s1) s (1021 cm2) BR Reference

G1 glass 1384 5.78 0.68 Present work

G2 glass 1636 6.25 0.68 Present work
LBNCaDy10 1460 4.90 0.36 [39]
LBNMgDy10 1442 4.80 0.38 [39]
PKAlCaFDy10 1159 4.77 0.76 [25]
PKBAFDy10 1018 4.70 0.72 [48]
PKAZFDy 1095 4.57 0.69 [26]
BPBDy10 736 4.30 0.62 [42]
PKMAFDy10 595 3.20 0.65 [50]
Silicate e 3.00 e [54]
BiDy0.09OCl 704 2.26 e [15]
SiAlBaGdDy e 1.21 e [12]
PbOePbF2 e 1.19 e [55]
Fluoroborate e 0.27 e [44]

that the emission intensity of oxyfluoride G2 glass is higher than

the oxide G1 glass, because oxyfluoride glasses have lower phonon
energy and also have lower multi-phonon relaxation rates of the
emission than oxide glasses [18,25,26]. The reduction of the peaks Fig. 6. The emission spectra of G1 and G2 glasses excited by 349 nm excitation
related with OH groups of G2 glass compare with G1 glass in the wavelength.
FTIR transmittance spectra (Fig. 2.), because of the reaction that
fluoride in oxyfluoride glass reacts with the OH group to form HF,
make the oxyfluoride glass have higher luminescence intensity
than oxide glass. The energy level scheme of the emission mech-
anism of Dy3þ ions in the glass samples is shown in Fig. 7.
The luminescence decay time of 4F9/2 state of the Dy-doped glass
samples had been measured by exciting the glass samples with
349 nm excitation wavelength and then observing the 4F9/2 / 6H13/

Fig. 7. Energy level scheme for the emission mechanism of the Dy-doped glass
Fig. 5. The excitation spectra of G1 and G2 glasses under 574 nm emission wavelength. samples.
564 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566
Fig. 8. The decay time curves of 4F9/2 to 6H13/2 transition of the Dy-doped glass
samples.
2 transition with 574 nm emission [25,53], the decay time curves of
G1 and G2 glasses are shown in Fig. 8, exhibit single exponential.
The experimental lifetime are found to be 0.539 ms for G1 glass and
0.540 ms for G2 glass.
The radiative transition possibility (AR), stimulated emission
cross section (s), experimental branching ratio (BR) and theoretical
branching ratio (BRc) of the observed transitions of G1 and G2
glasses are calculated by Judd-Ofelt theory and presented in Table 4.
The 4F9/2 / 6H13/2 transition (at 574 nm) has the highest stimulated
Fig. 9. (a) The CIE 1931 diagram of the glass samples; (b) White emission excited by 365 nm UV lamp (4 W, 0.16 A) of G1 and G2 glasses.
emission cross section (5.7817  1021 cm2 for G1 glass and
6.2466  1021 cm2 for G2 glass) and this transition also has the
highest branching ratio too.
The laser properties are also calculated from the emission
spectra and Judd-Ofelt theory, and presented for comparing with
other Dy-doped glasses as shown in Table 5. The stimulated emis-
sion cross section is the important parameter indicates the per-
formance of laser application, glass with high stimulated emission
cross section provides high potential to using this glass as laser
application [25,26,31]. As can be seen from Table 5, both G1 and G2
glasses have higher stimulated emission cross section compared
with other Dy-doped glasses, that mean the glass samples in this
work are useful for laser application. The higher stimulated emis-
sion cross section of G2 glass than G1 glass also confirmed more
laser potential of G2 glass than G1 glass. The stimulated emission
cross section of G2 glass is higher that G1 glass because oxyfluoride
glass is the lower phonon energy host glass [18,25].
3.4. CIE 1931 chromaticity diagram and CCT values
To investigate the tunability of the color of light emitted by the
glass samples, the x,y color coordinates of emission spectra have
been analyzed in the framework of CIE 1931 chromaticity diagram.
The results show that the x,y color coordinates of emission spectra
of both G1 and G2 glasses are found to be the same at the point
(0.38, 0.43). Fig. 9 presents the location of x,y color coordinate of
the emission light of the glass samples on CIE 1931 chromaticity
diagram which is fall in the white region, the white light emission
of G1 and G2 glasses are also shown in photograph in Fig. 9 when
exciting the samples by 365 nm UV lamp (4 W, 0.16 A).
The CCT value can be evaluated from CIE color coordinate using
the McCamy formula as follows [1,25]
 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566
Fig. 10. The temperature dependence luminescence spectra of G2 glass.
CCT ¼ 449n3 þ 3525n2  6823n þ 5520:33 (1)
where n ¼ (xe0.332)/(y-0.186). The CCT values obtained from the
glass samples are 4204 K for G1 glass and 4228 K for G2 glass
corresponding to the commercial cool white light (3100e4500 K),
while the CCT values of fluorescent tube and day light are 3935 K
and 5500 K, respectively.
3.5. Temperature dependence luminescence
Temperature dependence of emission spectra is also studied
from 300 K to 10 K by exciting with 266 nm laser excitation. The G2
glass sample with higher light yield is selected to study, G2 glass is
cooled down to 10 K with compressed helium gas in vacuum
environment of 102 - 103 Torr. The emission spectra focused at
the 4F9/2 / 6H15/2 emission peak (574 nm) of the G2 glass at dif-
ference temperatures is shown in Fig. 10 and Fig. 11. The intensity of
Fig. 11. Intensity of the 4F9/2 / 6H15/2 emission peak at 574 nm versus temperature
graph.
565
the emission peak is found to be increased with decreasing of the
temperature, because the non-radiative transitions become
increased at high temperature [56,57].
4. Conclusion
In this work, lanthanum calcium phosphate oxide (G1) and
oxyfluoride (G2) glasses doped with dysprosium (III) oxide were
prepared by melt-quenching technique and investigate their
luminescence properties to determine the potential for using as
luminescence materials. The highest peak in absorption spectra
centered at 349 nm (6H15/2 / 6P7/2) in UVeVis region and
1266 nm (6H15/2 / 6H9/2) in NIR region, this transition is the
hypersensitive transition that found to be more intense than the
other transitions. The J-O parameters (U2, U4 and U6) were
calculated from the oscillator strength of the absorption spectra.
The higher value of U2 indicated relatively higher covalency and
higher asymmetry around the Dy3þ ions of the present glasses
than the other glass systems. The J-O parameters of the present
glasses follow the trend as U2 > U4 > U6, that may indicates the
good quality of a glass host for using as optical device application.
The excitation spectra observed under 574 nm emission wave-
length show the highest peak at 349 nm (6H15/2 / 6P7/2). The
emission spectra, excited with 349 nm excitation wavelength
show two major peaks corresponding to the 4F9/2 / 6H15/2
(482 nm, blue) and 4F9/2 / 6H13/2 (574 nm, yellow) transitions.
The G2 glass has higher emission intensity than G1 glass, because
oxyfluoride glasses have lower phonon energy and also have
lower multi-phonon relaxation rate of the emission than oxide
glasses. The experimental lifetime are found to be 0.539 for G1
glass and 0.540 for G2 glass. The laser properties are also calcu-
lated from the emission spectra. Both G1 and G2 glasses have
higher stimulated emission cross section compared with other
Dy-doped glasses, that mean the present glasses are useful for
laser application. The higher stimulated emission cross section of
G2 glass than G1 glass also confirmed more laser potential of G2
glass than G1 glass. The x,y color coordinates of both G1 and G2
glasses are found to be the same at the point (0.38, 0.43) that be
plotted in white region of CIE 1931 chromaticity diagram. The CCT
values are 4204 K for G1 glass and 4228 K for G2 glass corre-
sponding to the commercial cool white light (3100e4500 K).
Temperature dependence of emission spectra is also studied from
300 K to 10 K by exciting with 266 nm laser excitation. The G2
glass sample with higher light yield is selected to study and found
that the intensity of the emission peak is increased with
decreasing of the temperature, because the non-radiative transi-
tions become increased at high temperature.
The results of the investigations in this work confirmed that the
present Dy-doped lanthanum calcium phosphate oxide and oxy-
fluoride glasses perform high potential for using as efficient lumi-
nescence materials for solid-state lighting applications, especially
for white LEDs. Furthermore, the oxyfluoride G2 glass provides
more luminescence potential than the oxide G1 glass.
Acknowledgements
The authors would like to thanks National Research Council of
Thailand (NRCT) and Nakhon Pathom Rajabhat University (NPRU)
for funding and support this research under project number
GB_60_25. Thanks are also due to Prof. C.K. Jayasankar, Sri Ven-
kateswara University, India for J-O analysis software and Prof. H.J.
Kim, Kyungpook National University, Republic of Korea for low
temperature experiment.
566 N. Luewarasirikul et al. / Optical Materials 66 (2017) 559e566

References [29] A. Balakrishna, D. Rajesh, Y.C. Ratnakaram, J. Lumin. 132 (2012) 2984e2991.
[30] J.S. Kumar, K. Pavani, A.M. Babu, G.N. Kumar, S.B. Rai, L.R. Moorthy, J. Lumin.
130 (2010) 1916e1923.
[1] L. Mishra, A. Sharma, A.K. Vishwakarma, K. Jha, M. Jayasimhadri, B.V. Ratman,
[31] M.P. Hehlen, M.G. Brik, K.W. Kramer, J. Lumin. 136 (2013) 221e239.
K. Jang, A.S. Rao, R.K. Sinha, J. Lumin 169 (2016) 121e127.
[32] B. Lakshmana Rao, Y.N.Ch. Ravi Babu, S.V.G.V.A. Prasad, J. Non Cryst. Solids 382
[2] G. Lakshminarayana, H. Yang, J. Qiu, J. Solid State Chem. 182 (2009) 669e676.
(2013) 99e104.
[3] A. Bergh, G. Craford, A. Duggal, R. Haitz, Phys. Today 54 (2001) 42e47.
[33] F.F. Sene, J.R. Martinelli, L. Gomes, J. Non Cryst. Solids 348 (2004) 30e37.
[4] T. Aitasalo, P. Deren, J. Holsa, H. Jungner, J.C. Krupa, M. Lastusaari,
[34] A.M. Abdelghany, F.H. ElBatal, H.A. ElBatal, F.M. EzzElDin, J. Mol. Struct. 1074
J. Legendziewicz, J. Niittykoski, W. Strek, J. Solid State Chem. 171 (2003)
(2014) 503e510.
114e122.
[35] Y.S.M. Alajeramia, S. Hashima, W.M.S. Hassana, A.T. Ramlia, A. Kasim, Phys. B
[5] T. Matsuzawa, Y. Aoki, N. Takeuchi, Y. Murayama, J. Electrochem. Soc. 143
407 (2012) 2398e2403.
(1996) 2670e2673.
[36] R.S.E. Dawauda, S. Hashima, Y.S.M. Alajeramia, M.H.A. Mhareba, N. Tamchekc,
[6] Z. Ci, Q. Sun, S. Qin, M. Sun, X. Jiang, X. Zhang, Y. Wang, Phys. Chem. Chem.
J. Mol. Struct. 1075 (2014) 113e117.
Phys. 16 (2014) 11597e11602.
[37] S. Tanabe, T. Ohayagi, N. Soga, T. Hanada, Phys. Rev. B 46 (1992) 3305.
[7] Y. Liu, J. Kuang, J. Zhang, J. Solid State Chem. 179 (2006) 266e269.
[38] B. Shanmugavelu, V.V. Kumar, J. Lumin. 146 (2014) 358e363.
[8] C.H. Chiu, C.H. Liu, S.B. Huang, T.M. Chen, J. Electrochem. Soc. 154 (2007)
[39] C.K. Jorgensen, R. Reisfeld, J. Less Common. Met. 93 (1983) 107e112.
J181eJ187.
[40] C. Madhukar Reddy, B. Deva Prasad Raju, N. John Sushma, N.S. Dhoble,
[9] J.S. Kim, S.C. Yang, S.Y. Kwak, Y. Choi, K.W. Paik, B.S. Bae, J. Mater. Chem. 22
S.J. Dhoble, Renew. Sust. Energy Rev. 51 (2015) 566e584.
(2012) 7954e7960.
[41] Y.B. Shin, J. Heo, J. Non Cryst. Solids 253 (1999) 23e29.
[10] E. Vanlathem, A.W. Norris, M. Bahadur, J. DeGroot, M. Yoshitake, Proc. SPIE
[42] M. Vijayakumar, K. Marimuthu, J. Alloy. Comp. 629 (2015) 230e241.
6192 (2006), 619202-1-619202-8.
[43] S.A. Saleem, B.C. Jamalaiah, M. Jayasimhadri, Kiwan Jang, L.R. Moorthy,
[11] L. Shamshad, G. Rooh, K. Kirdsiri, N. Srisittipokakun, B. Damdee, H.J. Kim,
J. Quant. Spectrosc. Rad. Transf. 112 (2011) 78e84.
J. Kaewkhao, Opt. Mater. 64 (2017) 268e275.
[44] Y. Dwivedi, S.B. Rai, Opt. Mater. 31 (2009) 1472e1477.
[12] G. Lakshminarayana, J. Qiu, J. Alloy. Comp. 476 (2009) 470e476.
[45] A. Florez, V.A. Jerez, M. Florez, J. Alloys Comp. 303e304 (2000) 355e359.
[13] A.S. Rao, K. Swapna, Sk. Mahamuda, M. Jayasimhadri, T. Sasikala, L.R. Moorthy,
[46] B. Klimesz, G. Dominiak-Dzik, M. Zelechower, W. Ryba-Romanowski, Opt.
J. Lumin 139 (2013) 119e124.
Mater. 30 (2008) 1587e1594.
[14] L. Shamshad, G. Rooh, K. Kirdsiri, N. Srisittipokakun, H.J. Kim, J. Kaewkhao,
[47] K.K. Mahato, Anita Rai, S.B. Rai, Spectrochim. Acta Part A 61 (2005) 431e436.
J. Mol. Struct. 1125 (2016) 601e608.
[48] R. Praveena, R. Vijaya, C.K. Jayasankar, Spectrochim. Acta Part A 70 (2008)
[15] C. Shivakumara, R. Saraf, P. Halappa, Dyes Pigments 126 (2016) 154e164.
577e586.
[16] M. Ilhan, M.K. Ekmekci, J. Solid State Chem. 226 (2015) 243e249.
[49] S.S. Babu, P. Babu, C.K. Jayasankar, Th. Troster, W. Sievers, G. Wortmann, Opt.
[17] C. Tu, X. Lu, Z. You, J. Li, Z. Zhu, G. Jia, B. Wu, J. Phys. Chem. Solids 66 (2005)
Mater. 31 (2009) 624e631.
1801e1805.
[50] Ch. Basavapoornima, C.K. Jayasankar, P.P. Chandrachoodan, Phys. B 404 (2009)
[18] S.N. Rasool, L.R. Moorthy, C.K. Jayasankar, Mater. Express 3 (2013) 231e240.
235e242.
[19] R.K. Brow, J. Non Cryst. Solids 263&264 (2000) 1e28.
[51] G. Tripathi, V.K. Rai, S.B. Rai, Spectrochim. Acta Part A 62 (2005) 1120e1124.
[20] M. Karabulut, E. Melnik, R. Stefan, G.K. Marasinghe, C.S. Ray, C.R. Kurkjian,
[52] V.K. Rai, S.B. Rai, D.K. Rai, Opt. Commun. 257 (2006) 112e119.
D.E. Day, J. Non Cryst. Solids 288 (2001) 8e17.
[53] D. Rajesh, Y.C. Ratnakaram, M. Seshadri, A. Balakrishna, T. SatyaKrishna,
[21] A.E. Marino, S.R. Arrasmith, L.L. Gregg, S.D. Jacobs, G. Chen, Y. Duc, J. Non Cryst.
J. Lumin. 132 (2012) 841e849.
Solids 289 (2001) 37e41.
[54] L. Nagli, D. Bunimovich, A. Katzir, O. Gorodetsky, V. Molev, J. Non Cryst. Solids
[22] G. Kaur, O.P. Pandey, K. Singh, J. Non Cryst. Solids 358 (2012) 2589e2596.
217 (1997) 208e214.
[23] A. Bahari, A. Anasari, Z. Rahmani, J. Eng. Technol. Res. 3 (7) (2011) 203e208.
[55] P. Nachimuthu, R. Jagannathan, V.M. Kumar, D.N. Rao, J. Non Cryst. Solids 217
[24] T. Som, B. Karmakar, Spectrochim. Acta A 79 (2011) 1766e1782.
(1997) 215e223.
[25] L.R. Moorthy, S.N. Rasool, C.K. Jayasankar, Solid State Sci. 22 (2013) 82e90.
[56] M.J. Kim, H.J. Kim, H. Park, S. Kim, J. Kim, Nucl. Instr. Meth. Phys. Res. A 632
[26] C.K. Jayasankar, V.B. Sreedhar, D. Ramachari, Phys. B 408 (2013) 158e163.
(2011) 47e51.
[27] J. Kaewkhao, N. Wantana, S. Kaewjaeng, S. Kothan, H.J. Kim, J. Rare Earth 34
[57] H. Jiang, G. Rooh, H.J. Kim, J.M. Lee, Y.J. Lee, W. Zhang, S. Kim, J. Cryst. Growth
(2016) 583e589.
418 (2015) 163e166.
[28] L. Shamshad, G. Rooh, K. Kirdsiri, N. Srisittipokakun, B. Damdee, H.J. Kim,
J. Kaewkhao, J. Alloy. Comp. 695 (2017) 2347e2355.