Journal of Alloys and Compounds 735 (2018) 2303e2310

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Eu3þ-doped double perovskite-based phosphor-in-glass color

converter for high-power warm w-LEDs
J.S. Zhong*, H.B. Gao, Y.J. Yuan, L.F. Chen, D.Q. Chen**, Z.G. Ji
College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China

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

Article history: Phosphors-in-glass (PiG), which serves as a potential bi-replacement of both phosphors and organic
Received 7 September 2017 encapsulants in high-power white light-emitting diodes (w-LEDs), has captured much attention due to
Received in revised form its high thermal conductivity and excellent thermal stability. Aiming to tune the correlated color tem-
17 November 2017
perature and color rendering index of YAG:Ce3þ PiG-based LED device, an efficient phosphor play an
Accepted 21 November 2017
important function as red components are in demand to incorporate into the PiG composite. In this
Available online 24 November 2017
study, the Ca2LaSbO6:Eu3þ red phosphor with double perovskite structure has been synthesized through
a high-temperature solid-state reaction. The quantum efficiency of the as-obtained phosphor reaches as
Keywords:
Double perovskite
high as 81%, and its luminescence intensity can remain above 80% at the temperature below of 423 K.
Phosphor-in-glass Subsequently, the high-efficiency Ca2LaSbO6:Eu3þ and commercial YAG:Ce3þ phosphors are incorporated
White LED into the TeO2-based glass to form the PiG composite. Impressively, the original emissive properties of the
embedded phosphor particles are retained. Finally, the PiG encapsulated high-power w-LEDs are fabri-
cated, exhibiting improved chromaticity feature and superior optical performance. By adjusting the mass
ratio of Ca2LaSbO6:Eu3þ red phosphor to YAG:Ce3þ yellow one in the PiG composite, a tunable correlated
color temperature ranging from cool white (6665 K) to warm one (3993 K) and the color rendering index
increasing from 70.6 to 86.7 are achieved. Especially, the structured warm w-LEDs exhibits good color
stability under different drive currents.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, the increasing awareness of energy conservation and
environmental protection, people are urgently searching for a novel
technology to satisfy these demands in display and illumination
[1,2]. In the last few decades, white light-emitting diodes (w-LEDs)
have gained great attentions and been considered as the promising
solid-state lighting source to substitute the traditional fluorescent
and incandescent lamps due to their extraordinary advantages of
energy saving, environmental friendliness (mercury-free), high
luminous efficiency, compact size, fast response time, and long
lifetime [3e6]. Currently, the mainstream method to produce
commercial w-LEDs is through sealing yellow
Y3Al5O12:Ce3þ(YAG:Ce3þ) phosphor on a blue LED chip (eg.InGaN)
with organic resin. Unfortunately, such encapsulation structure
* Corresponding author.
** Corresponding author.
E-mail addresses: jiasongzhong@hdu.edu.cn (J.S. Zhong), dqchen@hdu.edu.cn
(D.Q. Chen).
may age easily and turn yellow and degradation due to the long-
time service and the accompanying heat from the package,
resulting in the shift of chromaticity, reduction of luminous efficacy
and degradation of long-term reliability [7,8]. This degradation LED
performance limited their applied as candidates for high-power
solid state lighting devices in the future.
To overcome the weaknesses of organic resin, there are three
diverse inorganic materials, including transparent ceramics, single
crystals and phosphor-in-glass (PiG), have been developed as
practical alternatives [9,10]. However, transparent ceramics and
single crystals still face some innate problems in the commercially
application, such as high fabrication cost, complex preparation
procedures, and poor reproducibility [9]. Compared with trans-
parent ceramics and single crystals, PiG is attracting widely atten-
tion due to its advantage as the following [11,12]: (1) the low-
temperature (<800  C) co-sintering of inorganic glass frits and
phosphors is beneficial to keep the high performance of doping
phosphors; (2) the luminescence can be elaborately designed and
easily tuned by combining various phosphors and glass types; (3)
the preparation process is simple and reproducible. Therefore, PiG

https://doi.org/10.1016/j.jallcom.2017.11.242
0925-8388/© 2017 Elsevier B.V. All rights reserved.
2304 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310
has been considered as a promising luminescent converter for
high-power w-LEDs due to its robust, high-temperature and high-
humidity resistant, high thermal conductivity, and low thermal
expansion coefficient [8,13,14]. Consequently, PiG technology is
expected to be a promising way to replace organic resin or silicone
with glassy materials to encapsulate the required phosphors [15].
To date, several studies in regard to YAG:Ce3þ-based PiG used for
blue-excited w-LEDs have been reported [8,12,16,17]. However,
such w-LEDs device still has pending issues of high correlated color
temperature (CCT) and low color rendering index (CRI) due to the
deficiency of the red components, which cannot meet the re-
quirements of display and indoor lighting. Therefore, to improve
the CRI and CCT, multi-component PiG has been developed by
mixing the yellow- and red-emitting phosphors in the glass frits to
complement the red spectrum [18]. Besides, the refractive index
and density matching of the glass and phosphors, and the resis-
tance of the embedded phosphor particles against the melt glass
are important to the luminescent performance of the transparent
PiG composite [19]. Thus, the incorporated phosphor should be
possessing prominent chemical stability and high-temperature
luminescence maintenance, which can be retained the excellent
luminescent performance deriving from phosphors in the PiG
composite. Herein, the synthesized double perovskite Ca2L-
aSbO6:Eu3þ red phosphors with excellent thermal stability and
high quantum efficiency have been successfully introduced into the
YAG:Ce3þ-based PiG, and achieved chromaticity-tunable PiG for
high-power warm w-LED lighting sources by simply changing the
weight ratios of doping red phosphor. Related LED devices yield an
adjustable CCT ranging from 6665 to 3993 K, and a tunable Ra
between 70.6 and 86.7, under a driving current of 300 mA.
2. Experimental section
2.1. Phosphors preparation
A series of Ca2La1-xEuxSbO6 (x ¼ 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 and
0.8) were synthesized through a conventional high-temperature
solid-state method. The starting materials CaCO3 (99.9%),
La2O3(99.99%), Sb2O5(99.99%) and Eu2O3(99.99%) were used as-
received and weighed according to the given stoichiometric pro-
portions. The raw materials were mixed and ground in an agate
mortar thoroughly, and then transferred into alumina crucibles and
calcined at 1500  C for 5 h. The products were slow furnace-cooled
to room temperature and pulverized for further measurements.
2.2. Fabrication of PiG composites
The PiG was fabricated by a simple low-temperature co-sinter-
ing route, and the synthesis process contains the following main
steps: Firstly, the mother glass with the composition of TeO2eZ-
nOeSb2O3eAl2O3eB2O3eNa2O was milled in an agate thoroughly
and melted at 800  C for 30 min. Secondly, the molten glass was
poured into a copper mold at room temperature, cooled, and
grinded to powder. Thirdly, introducing various mass ratios of the
pre-synthesized Ca2LaSbO6:Eu3þ red phosphors and commercial
YAG:Ce3þ yellow phosphors into the precursor glass frit and
grounded thoroughly. Fourthly, sintering the mixture at 600  C for
30 min, then, rapidly poured into a preheated copper mold at
300  C and annealed at 230  C for 5 h to relinquish inner stress.
Lastly, the obtained glass sample was cut and polished into pieces
for the next optical characterizations and further LED devices
experiments.
2.3. Materials characterization
The crystal structure of the final products was measured by X-
ray diffractometer (XRD, Miniflex 600, Rigaku, Tokyo, Japan) with
Ka radiation (l ¼ 1.5405 Å). The operating voltage was 40 kV and
the tube current equal to 20 mA. The structural morphology of the
obtained PiG sample was observed by scanning electron micro-
scopy (SEM, JEOL-JSM6380A, operated at an acceleration voltage of
15 kV) equipped with an energy dispersive X-ray spectroscopy
(EDS). Luminescence properties were measured using Edinburgh
Instruments FS5 spectrometer equipped with a 150 W continuous
and pulsed Xenon lamp as light source. The temperature-
dependent PL emission spectra of the products were recorded by
the FS5 system with a computer-controlled electric furnace and the
temperature from 303 to 543 K with each target temperature
stayed for 10min. Quantum efficiency (QE) of the phosphor sample
was gained directly using a barium sulfate coated integrating
sphere attached to the FS5. The electroluminescence (EL) spectra,
luminous efficacy (LE), CCT, CRI and Chromaticity coordinate of the
constructed PiG-based w-LEDs were obtained from an integrating
sphere which was connected to a CCD detector with an optical
fiber(HAAS-2000).
3. Results and discussions
3.1. Crystallographic parameters and structural characterizations
The profile of Synchrotron x-ray diffraction (SXRD) structural
refinements of Ca2La0.9Eu0.1SbO6 phosphor is carried out using the
General Structure Analysis System (GSAS) and the corresponding
fitting pattern is presented in Fig. 1. The pink crosses, red and blue
solid lines depict the observed, calculated diffraction patterns and
the differences, respectively. Meanwhile, the position of Bragg re-
flections of the calculated patterns is plotted by the green short
vertical lines. The refinement results are convergent well with the
low residual factors of Rp ¼ 8.79%, Rwp ¼ 9.23% and goodness-of-fit
parameters of c2 ¼ 3.493, indicating that the Ca2La0.9Eu0.1SbO6 is a
single phase without unidentified diffraction peaks. The cell pa-
rameters were obtained to be a ¼ 5.654 Å, b ¼ 5.851 Å, c ¼ 8.141 Å
and V ¼ 269.317 Å3, which is smaller than that of Ca2LaSbO6 host
reported in Ref. [20] (a ¼ 5.6852 Å, b ¼ 5.8781 Å, c ¼ 8.1723 Å,
V ¼ 273.11 Å3). These observations certify that the Eu3þ ions have
been doped into the host lattice effectively. Based on the same
Fig. 1. SXRD profile for Rietveld refinement result of Ca2La0.9Eu0.1SbO6. Inset is the
crystal structure of Ca2LaSbO6.
 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310
charge and similar ionic radius between Eu3þ (r ¼ 1.01 Å, CN ¼ 6)
and La3þ(r ¼ 1.1 Å, CN ¼ 6), the Eu3þ ions will occupy the La3þ sites
preferentially, which is proved by the Rietveld analysis. Besides, the
shorter lattice parameters of Ca2LaSbO6 doped by Eu3þ is due to the
fact that rEu3þ < rLa3þ [20]. Using Diamond software, in view of the
acquired atomic coordinates, the ideal double cell is modeled in
inset of Fig. 1. In this double perovskite structure, La in 2c site is
surrounded by six O and Sb in 2a sites is surrounded by eight O
atoms, which are connected by their shared O atom [21].
The XRD patterns of the obtained Ca2LaSbO6:Eu3þ samples with
different Eu3þ concentrations are displayed in Fig. 2. All the
diffraction peaks of Eu3þ-doped Ca2LaSbO6 phosphors possess the
same monoclinic double perovskite structure Ca2LaSbO6, which are
similar to those of standard Ca2LaTaO6 crystal (JCPDS 70e1157). No
traces of other crystalline phase are observed obviously after
doping Eu3þ ions, illustrating the Eu3þ ions have been successfully
introduced into the Ca2LaSbO6 host lattice and the structure of the
host remains unchanged. Furthermore, the position of the diffrac-
tion peak has shifted slightly to higher angle area with increasing
Eu3þ concentrations, as depicted in Fig. 2(b). This demonstrates
that the lattice experiences a shrinkage attribute to the substitution
of the smaller Eu3þ for La3þ ions, which distribute on the six co-
ordinated cation sites in Ca2LaSbO6. However, as the Eu3þcontents
increased, an extra diffraction pattern at about 31.8 may be orig-
inated from the tetragonal Eu4Sb2O impurity phase.
3.2. Luminescence properties of Ca2(La1-xEux)SbO6 phosphors
The room temperature PLE and PL spectra of the Ca2L-
a0.5Eu0.5SbO6 phosphor are illustrated in Fig. 3(a). The PLE spec-
trum, monitoring the emission at 615 nm corresponding to the
5
D0/7F2 transition of Eu3þ ions, consists of a broad absorption
band as well as some sharp lines. The broad absorption band at
250e350 nm is ascribed to the charge transfer (CT) from oxygen to
europium, which corresponds to the electronic transition from the
2p orbital of O2 to the 4f orbital of Eu3þ [22]. Meanwhile, there are
several sharp excitation peaks correspond to the characteristic
inner-4f transitions of Eu3þ ions exist in the range of 350e500 nm.
The two strongest lines absorption centered at 393 nm and 465 nm
are attributed to 7F0/5L6 and 7F0/5D2 transitions, indicating that
the obtained phosphor can be excited by the near-UV and blue
lights. The typical PL spectrum consists of several sharp bands be-
tween 500 and 750 nm, which correspond to 5D0/7FJ (J ¼ 0e4)
Fig. 2. (a) XRD patterns of Ca2La1-xSbO6:xEu3þ (x ¼ 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and
0.8). (b) The enlarged XRD patterns from 30 to 33 .
2305
transition of Eu3þ. Clearly, the PL spectrum is dominated by a strong
red emission band with a center of 615 nm ascribed to the 5D0/7F2
transition. Compared with that of the 5D0/7F1 transition, the in-
tensity of the 5D0/7F2 transition is much stronger, indicating that
Eu3þ occupies a site located at the non-inversion symmetry in the
Ca2LaSbO6 host lattice. Besides, to achieve the optimum doping
concentration of Eu3þ ions in Ca2LaSbO6, a series of Ca2La1-
3þ
xSbO6:xEu (x ¼ 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8) phosphors
as a function of Eu3þ ion concentrations are investigated and dis-
played in Fig. S1. Evidently, with raising the Eu3þ ion concentra-
tions, all the PL emission spectral profiles are almost the same
except the intensity. As seen in Fig. 3(b), the relative emission in-
tensity initially increased and reaches a maximum corresponding
to x ¼ 0.5, and then show a decrement tendency with the further
increase of Eu3þ ion concentration because of the concentration
quenching effect [23]. Such high doping concentration is ascribed
to the double distance between the Eu3þ ions in neighboring layers
which separated by SbO6 octahedrons in one layer, as shown in
inset of Fig. 1. This special double perovskite structure results in the
quenching concentration delayed due to a longer distance between
Eu3þ ions [24]. Thus, in order to explore the concentration
quenching mechanism, the critical distance (Rc) could be estimated
from the Blasse's theory [25], and the Rc value is calculated to be
8.05 Å, which is larger than 5 Å. As a consequence, we can infer that
the concentration quenching mechanism of the Eu3þ ion occurs via
electric multipolar interactions. Furthermore, according to Dexter's
theory, the interaction type can be determined via the following
formula [26]:
I K
¼ (1)
c 1 þ bðcÞq=3
where q ¼ 6, 8, 10 refer to dipole-dipole (d-d), dipole-quadrupole
(d-q) and quadrupole-quadrupole(q-q) interactions, respectively;
I represents the PL emission intensity, and X is the concentration of
Eu3þ ion; K and b are constants. As depict inset of Fig. 3(b), the
correlation between log(x) and log (I/x) can be fitted linearly, and
the slope is equal to 1.51 ¼ -q/3. Thus, the value q is close to 6,
indicating that the concentration quenching mechanism of Eu3þ in
Ca2LaSbO6 host is strongly accounted for by the d-d interaction.
Furthermore, the PL decay curves of Ca2La1-xSbO6:xEu3þ
(x ¼ 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8) phosphors, excited at
465 nm and monitored at 615 nm, are demonstrated in Fig. 3(c). All
the decay curves fitted well with a first-order exponential function,
which further confirms that the Eu3þ ions occupy a single type of
lattice site in the Ca2LaSbO6 host. With increasing Eu3þ concen-
tration from 10 to 80 mol%, the lifetimes decreases monotonously
from 1.034 to 0.616 ms due to the gradual increase in the proba-
bility of energy transfer to quenching sites and the energy transfer
rate between Eu3þEu3þ ions. Besides, the QE, as a crucial
parameter for practical application, has been measured at the
excitation and emission of 465 nm (see Fig. 3(d)). The QE of Ca2L-
a0.5Eu0.5SbO6 is calculated to be 81%, which is higher than that of
commercial oxynitride Ca-a-SiAlON:Eu2þ (~70%) [27] and fluorides
K2SiF6:Mn4þ (~74%) [28]. The above results demonstrate that the
obtained phosphor has a potential application for color conversion
of w-LED consisting of n-UV or blue chip.
3.3. Thermal stability of Ca2LaSbO6:Eu3þ phosphor
As an important index of phosphors applied in LED, especially
for high power LEDs, the thermal stability of the developed phos-
phor is a critical parameter due to the performance of LEDs such as
light output, chromaticity, and lifetime are seriously affected as the
working temperature achieve even more than 150  C [29]. To
2306 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310
Fig. 3. (a) PLE and PL spectra of Ca2La0.5Eu0.5SbO6 exited at 465 nm and monitored at 615 nm. (b) The emission intensity as a function of Eu3þ concentrations. Inset is the
dependence of log(x) on log(I/x) beyond the quenching concentration. (c) PL decay curves of Eu3þ in Ca2La1-xEuxSbO6 phosphors with various Eu3þ concentrations. (d) Excitation
line of BaSO4 and emission spectrum of Ca2La0.5Eu0.5SbO6 phosphor.
evaluate the thermal quenching behavior of Ca2LaSbO6:Eu3þ red
phosphor, the influence of temperature on the PL properties
heating from 303 to 543 K and cooling from 543 to 303 K under the
excitation of 465 nm blue light is investigated and the
Fig. 4. Normalized PL intensity of Ca2La0.5Eu0.5SbO6 phosphor in heating (green dots)
and cooling (red dots) processes under 465 nm excitation. Inset is the temperature-
dependent PL spectra of Ca2La0.5Eu0.5SbO6 phosphor: (a) heated from 303 to 543 K,
and then (b) cooled from 543 to 303 K. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
representative results are shown in Fig. 4. Upon heating, no peak
shifts while the PL intensity gradually decreases with the increase
of temperature; whereas, for the cooling process, the PL intensity
increases with decreasing temperature. The relative intensity at
373 K (100  C), 423 K (150  C) and 523 K (250  C) is about 91%, 83%
and 63% of the initial intensity at room temperature, which is much
better than most of Eu3þ doped oxides phosphors. Besides, it is
clearly observed that no obvious changes existed in their emission
spectra and the temperature-dependent intensity curves could
repeat accurately in the heating and cooling process. These results
demonstrate that the obtained phosphor offers the reversible
thermal behaviors and excellent thermal fatigue resistance
performance.
Furthermore, to better understand the origin of temperature
dependence of emission intensity, the activation energy (DE) for
thermal quenching can be expressed based on Arrhenius equation,
as follows:
I0
IT ¼ (2)
1 þ expðDE=kTÞ
where IT and I0 are the intensity of Ca2La0.5Eu0.5SbO6 at a given
temperature (303e543 K) and room temperature, respectively; k
equals the Boltzmann constant. The graph of ln(I0/IT-1) vs. 1/kT is
plotted and presented in Fig. 5. Evidently, the experimental data
can be fitted linearly with the slope of 0.211. Hence, the DE value
of Ca2La0.5Eu0.5SbO6 phosphor is 0.211 eV, which is higher than
some of recently reported popular phosphors [30,31], even the
 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310
Fig. 5. The activation energy graph for thermal quenching of Ca2La0.5Eu0.5SbO6
phosphor.
same with that of the commercial phosphor CaAlSiN3:Eu2þ
(~0.2 eV). The relative high energy barrier confirms that the as-
prepared phosphor possess good thermal stability and suitable
for LED applications.
3.4. Microstructure and photoluminescence properties of PiG
sample
To overcome the luminescent degradation and color aberration
issues of the high-power w-LED products after the long-term ser-
vice, the all-inorganic phosphor-in-glass (PiG) is considered to be a
feasible substitute [32e34]. Furthermore, for the harvest of the red
component, Eu3þ activated Ca2LaSbO6 red phosphors incorporated
into the YAG:Ce3þ-based PiGs. As given in Fig. 6(a), the XRD
diffraction peaks of YAG:Ce3þ-Ca2LaSbO6:Eu3þ PiG composite are in
good agreement with those of YAG:Ce3þ phosphor and Ca2L-
aSbO6:Eu3þ phosphor, which demonstrate that both the yellow and
red phosphors particles have been successfully incorporated into
the TeO2-based glass matrix. To deeply study the distribution and
microstructure of the embedded YAG:Ce3þ and Ca2LaSbO6:Eu3þ
phosphor particle in the PiG, the SEM and EDX images are depicted
in Fig. 6(beh). The average sizes of embedded red and yellow
phosphor particles are 1.1 mm and 2.4 mm, labeled by red and yellow
circles in Fig. 6(b), respectively. Furthermore, it can be clearly seen
that the phosphor particles distribute homogeneous in the glass
matrix. Then, the energy dispersive X-ray spectroscopy (EDX) line
scans across one particle to another of the selected area of Fig. 6(b),
marked by a purple frame, are used to distinguish the doping
particles. As seen from Fig. 6(ceh), the profiles of Y and Al signals
are ascribed to the YAG:Ce3þ phosphor particles, marked by a yel-
low circle, while Ca, La, and Eu signals are detected in another
particle, as denoted with red circle. In addition, Te signal, originated
from the TeO2-based glass matrix, is absent on the two phosphor
particles. These results demonstrate that the YAG:Ce3þ and Ca2L-
aSbO6:Eu3þ phosphor particles are successfully incorporated into
the glass matrix.
The emission and excitation spectra of the Ca2LaSbO6:Eu3þ
doped PiG composite, YAG:Ce3þ doped PiG composite, and Ca2L-
aSbO6:Eu3þ and YAG:Ce3þ co-doped PiG composite are illustrated
in Fig. 7(a). Under 465 nm excitation, the PL spectra of the YAG:Ce3þ
doped PiG composite and Ca2LaSbO6:Eu3þ ones demonstrate a
typical Ce3þ: 5d/4f broadband emission and the characteristic
intra-configuration 4f-4f transitions of Eu3þ, respectively, which is
similar to that of YAG:Ce3þ and Ca2LaSbO6:Eu3þ powders. However,
2307
it should be noticed that the excitation intensity of these PiG
composite in the ultraviolet region reduced greatly due to the
strong absorption of the TeO2-based glass matrix in the short
wavelength region [18,35,36]. From the PLE spectrum of the Ca2L-
aSbO6:Eu3þ and YAG:Ce3þ co-doped PiG, two dominant absorption
bands assigned to 7F0/5L6 and 7F0/5D2 located on the broad
excitation of band of Ce3þ can be observed. Besides, under 465 nm
blue light excitation, the Eu3þ: 5D0/7F2 red-emitting and Ce3þ:
4f/5d yellow-emitting can be found simultaneously in the PL
spectrum, indicating that the obtained PiG sample would be a
promising inorganic color converter for warm w-LEDs. In addition,
compare to the Ca2LaSbO6:Eu3þ phosphors, the profiles of decay
curve and lifetime value of the corresponding PiG composite is
almost constant.
In a further experiment, a series of PiG composite with various
Ca2LaSbO6:Eu3þ contents (0e10 wt%) and a constant of 3 wt%
YAG:Ce3þ are investigated, as presented in Fig. 8(a). Obviously, the
luminescence intensity of red emission band at 615 nm, attributed
to 5D0/7F2 transition of Eu3þ, gradually enhanced with the doping
concentrations increased from 0 wt% to 10 wt%. Furthermore, the
influence of different Ca2LaSbO6:Eu3þ doping concentrations on the
decay behaviors of Ce3þ is also studied, as exhibited in Fig. 8(b).
Evidently, with increasing of Ca2LaSbO6:Eu3þ contents, the decay
curves of Ce3þ keep almost unchanged, indicating that the Eu3þ
emitting has no effect on those of Ce3þ in the PiG composites. All
the results demonstrate the Ca2LaSbO6:Eu3þ phosphor particles
have been successfully incorporated into the glass matrix and sta-
ble against glass melting.
3.5. Performance of w-LED devices
To demonstrate the potential application of the fabricated
YAG:Ce3þ and Ca2LaSbO6:Eu3þ co-doped PiG composite and the
availability of Ca2LaSbO6:Eu3þ red phosphor compensate the red
deficiency of YAG:Ce-based PiG, PiGs with varying ratios of
YAG:Ce3þ yellow phosphor to Ca2LaSbO6:Eu3þ red phosphor
(denoted as Y:R) from 3:0 to 3:10 are prepared to find the proper
combination for w-LED fabrication. Therefore, the PiGs with
various Y:R are chosen to fabricate the w-LED device based on
460 nm InGaN blue chip, as illustrated in Fig. 9(a). With increasing
the Y:R from 3:0 to 3:10 in PiG composite, the color coordinates of
the fabricated LEDs devices shift from the cold white to natural
white, and finally to warm white. To clearly see this change, the
color coordinates of these w-LEDs are marked on the CIE 1931
chromaticity diagram and the corresponding photograph of the
PiG-based w-LEDs devices are displayed in the insets of Fig. 9(a).
With increasing the ratios of Y:R from 3:0 to 3:10, the CIE chro-
maticity coordinates shift from (0.3111, 0.3322) to (0.3821, 0.3716).
Correspondingly, the CCT and LE declines from 6665 to 3993 K and
105.6 to 81.2 lm/W, respectively, and the CRI increase from 70.6 to
86.7. All these results indicate that the chromaticity parameters can
be adjusted effectively as the requirement of warm w-LEDs by
tuning the ratios of Ca2LaSbO6:Eu3þ to YAG:Ce3þ in the PiG
composite.
To evaluate the color stability of the fabricated w-LED device,
the chromaticity parameters as a function of various operating
current is presented in Fig. 10. With the increase in applied current
from 20 to 600 mA, the CIE coordinates shifted slightly blue-shifted
from (0.3662, 0.3667) to (0.3606, 0.3550), resulting from the
additional proportion of the blue to yellow components. The vari-
ation of Dx and Dy are estimated to be 0.0056 and 0.0117, while the
CCT increase from 4415 to 4482 K and CRI decrease from 85.2 to
83.2, respectively. These results demonstrate tiny changes, which
further certify that the constructed w-LED has the excellent color
stability. Thus, we believe that such YAG:Ce3þ and Ca2LaSbO6:Eu3þ
2308 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310

Fig. 6. (a) XRD patterns of YAG:Ce3þ phosphor, Ca2LaSbO6:Eu3þ phosphor, and 3 wt% YAG:Ce3þ-Ca2LaSbO6:Eu3þ PiG composite. (b) SEM image of Ca2LaSbO6:Eu3þ (marked by red
circles) and YAG:Ce3þ (marked by yellow circles) phosphor particles in PiG composite. (ceh) EDX line scans curves across two phosphor particles (marked by purple frame in (b)).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 7. (a) PLE and PL spectra of YAG:Ce3þ doped PiG composite, Ca2LaSbO6:Eu3þ doped PiG composite, and Ca2LaSbO6:Eu3þ and YAG:Ce3þ co-doped PiG composite under 465 nm
blue light excitation. (b) Decay curves of the Ca2LaSbO6:Eu3þ phosphor and the corresponding PiG sample.

co-doped PiG composite would be a potential color converter used 4. Conclusions

in the high-power warm w-LEDs.
In summary, the double perovskite Ca2LaSbO6:Eu3þ red
 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310 2309

Fig. 8. (a) PL spectra of the PiG composites with a constant of 3 wt% YAG:Ce3þ and various Ca2LaSbO6:Eu3þ contents (0e10 wt%). (b) Decay curves of Ce3þ: 5d emitting-state in the x
wt% Ca2LaSbO6:Eu3þ (x ¼ 0, 2, 4, 6, 8, 10) and YAG:Ce3þ co-doped PiG composite excited 465 nm and monitored at 550 nm.

Fig. 9. (a) CIE color coordinates of PiG-based LEDs with a varying YAG:Ce3þ/Ca2LaSbO6:Eu3þ (Y:R) ratio from 3:0 to 3:10. The insets show the photographs of the fabricated w-LEDs
devices and their corresponding electroluminescence driven by 300 mA current. (b) LE, CRI and CCT of the fabricated w-LEDs packaged by the PiGs with a varying Y:R.

Fig. 10. (a) The variation of CIE coordinates of the fabricated w-LED device under various currents from 20 to 600 mA. (b) The corresponding CCT and CRI at different input currents.

phosphor has been successfully synthesized through a traditional bands ranging with 250e500 nm, which matches well with the
solid-state reaction. The host Ca2LaSbO6 has abundant [LaO6] oc- emission of the commercial UV/blue chip. Under excitation at
tahedrons, which is suitable for the substitution of Eu3þ ions in La3þ 465 nm, the phosphors exhibit a dominant peak at 615 nm, results
site. The excitation spectrum shows a broad band and several sharp from the Eu3þ:5D0 /7F2 transition. The optimal concentration
2310 J.S. Zhong et al. / Journal of Alloys and Compounds 735 (2018) 2303e2310
reaches up to 50 mol% and the quenching mechanism of the Eu3þ
ion is confirmed to be the dipole-dipole interaction. Impressively,
these phosphors exhibit excellent thermal stability with the lumi-
nescence only decay of 17% at 423 K and 37% at 523 K, and the QE of
the red phosphor reaches as high as 81%. Importantly, to demon-
strate the suitability of Ca2LaSbO6:Eu3þ in practical applications,
the developed Ca2LaSbO6:Eu3þ was introduced into the YAG:Ce3þ
PiG and then coupled with the InGaN blue chip. As a result, by
adjusting the mass ratio of Ca2LaSbO6:Eu3þ red phosphor to
YAG:Ce3þ yellow one in the PiG composite, the fabricated w-LEDs
devices show a tunable CCT (6665 Ke3993 K) and CRI (70.6e86.7)
under a applied current of 300 mA. Especially, such PiG encapsu-
lated w-LEDs manifest excellent color stability under the operation
currents from 20 to 600 mA, confirming a potential application
prospect in high-power warm w-LEDs.
Acknowledgments
This work was supported by Natural Science Foundation of
Zhejiang Province (LY18E020006 and LR15E020001), National Na-
ture Science Foundation of China (51502066 and 51572065), and
the 151 talent's projects in the second level of Zhejiang Province.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.jallcom.2017.11.242.
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