R34 ECS Journal of Solid State Science and Technology, 5 (3) R34-R36 (2016)

2162-8769/2016/5(3)/R34/3/$33.00 The Electrochemical Society

CommunicationThermal Quenching Behavior of the Green

Emitting CaSc2 O4 :Ce3+ Phosphor for LED Application
Qiuhong Zhang,z Haiyong Ni, Lingli Wang, and Fangming Xiao
Guangdong Provence Key Laboratory of Rare Earth development and Application, Department of Rare Metals,
Guangzhou Research Institute of Non-ferrous Metals, Guangzhou, Guangdong 510650, Peoples Republic of China

The temperature-dependent luminescence characteristic of CaSc2 O4 :Ce3+ phosphor has been investigated. Huang-Rhys coupling
factor, Stokes shift, activation energy, and quenching temperature of CaSc2 O4: Ce3+ phosphor was determined. The quenching
mechanism of CaSc2 O4: Ce3+ phosphor was also studied. Finally, the bluish green LEDs were fabricated with blue InGaN chip and
this phosphor. It is believed that CaSc2 O4 :Ce3+ is an excellent green phosphor for blue InGaN chip-based white LEDs.
2016 The Electrochemical Society. [DOI: 10.1149/2.0111603jss] All rights reserved.

Manuscript submitted October 21, 2015; revised manuscript received December 23, 2015. Published January 6, 2016.

White light-emitting diodes (LEDs) are expected to be useful as
environmentally friend lighting systems because of their low energy
consumption, long lifetime, mercury-free, and low maintenance.1 The
most widely used white LEDs are combinations of a blue LED and
Y3 Al5 O12 :Ce3+ (YAG:Ce3+ ) yellow phosphor.2 However, this type of
white LED has a low color rendering index. To resolve this problem,
a mixture of green and red phosphors instead of a yellow phosphor
has been proposed.3 This type of white LED requires green and red
phosphors with high quantum efficiencies under blue-light excitation.
CaSc2 O4 :Ce3+ phosphor was proved to be suitable and effective green
emitting phosphor for this purpose.4
The thermal quenching behavior is an important characteristic,
especially in high power LED operation, because the temperature
of LED package rises by heat generation by the LED itself.5 The
phosphors for high power LED are required to emit luminescence
effectively up to 423 K.6 But, surprisingly no systematic research has
been done to understand the temperature quenching phenomena of
the CaSc2 O4 :Ce3+ phosphor. So in this paper, the thermal quenching
properties of CaSc2 O4 :Ce3+ phosphor were investigated in detail. An
intense bluish green emitting LED was fabricated by combining a
455 nm emitting InGaN chip with this phosphor for the purpose of
evaluating its applicability to white LEDs.
Experimental
Syntheses of CaSc2 O4 :Ce3+ .CaCO3 (A. R.), CeO2 (99.99%),
and Sc2 O3 (99.99%) were used as starting materials and BaF2 (A.R.)
was used as flux. Based on our previous work, the optimum concen-
tration of Ce3+ and optimum content of BaF2 were fixed to be 0.01
mol and 0.5 wt%,7 respectively, so that the CaSc2 O4 :Ce3+ in a mo-
lar ratio of 0.99:2:0.01(Ca:Sc:Ce) was chosen with the addition of
0.5 wt% BaF2 (A. R.) throughout our study. All the starting materials
and flux were mixed in an agate mortar. The mixture was pre-fired at
800 C for 1 h under air atmosphere, and then sintered at 1550 C for
6 h under air atmosphere, finally sintered at 1450 C for 4 h under a
reductive atmosphere (25%N2 +75%H2 ).
emission spectra of the LED under different forward-bias direct cur-
rent at room temperature were recorded on a PMS-80 LED spec-
trophotocolorimeter (EVERFINE, China).
Results and Discussion
Fig. 1 shows the temperature dependence of emission spectra of
CaSc2 O4 : 0.01Ce3+ phosphor under 460 nm light excitation. The in-
tense broad peak of the sample is attributed to the 5d4f transition
of Ce3+ ions. The emission intensity decreases slowly with increas-
ing its full width at half maximum (FWHM) values from 97 nm to
103 nm during increasing temperature from 298 K to 523 K.
The temperature dependence of the Ce3+ emission FWHM value
can be described by using the configuration coordinate model and
the Boltzmann distribution expressed by the following equation (as
shown in the inset of Fig. 2):8

 
h
F W H M (T ) = 8 ln 2 h S coth [1]
2kT
where h is the phonon energy, k is the Boltzmann constant and S
is the Huang-Rhys coupling factor that measures the strength of the
electron-phonon coupling. If S < 1, the coupling is weak, if 1 < S <
5, the coupling is intermediate, and if S > 5, the coupling is strong.
So a larger value for S indicates a larger electron-lattice coupling.9
It is assumed that h is the same as that for the 4f1 ground state and
the 4f0 5d1 excited state of Ce3+ ions. The best fit was obtained with
S = 1.950 and h = 0.126 eV with R2 = 0.99123.

Characterization of CaSc2 O4 :Ce3+ .The phase purity of the

sample was investigated by using X-ray powder diffraction (XRD)
spectroscopy with a Rigaku D/max 2200 vpc diffractometer with Cu
K radiation at 40 kV and 30 mA. The XRD patterns show that the
CaSc2 O4 :0.01Ce3+ phosphor is nearly a single phase of CaSc2 O4 and
is consistent with JCPDS 20-0234. The temperature dependent pho-
toluminescence emission spectra were measured by a Hitachi F7000
spectrofluorometer equipped with a 450W xenon lamp.

LED fabrication.LED was fabricated by combining InGaN-

based blue LED (em = 455 nm) with the phosphor sample. The

Figure 1. The temperature dependence of emission spectra of CaSc2 O4 :

z
E-mail: wszqh@163.com 0.01Ce3+ phosphor (ex = 460 nm).

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 ECS Journal of Solid State Science and Technology, 5 (3) R34-R36 (2016) R35

Figure 3. The electroluminescence spectra of the green emitting pc-LED un-

Figure 2. The temperature dependence of emission intensity of CaSc2 O4 : der different forward-bias direct currents.
0.01Ce3+ phosphor (ex = 460 nm). The inset shows the temperature effect
on the FWHM of the Ce3+ emission band in CaSc2 O4 :0.01Ce3+ phosphor.

bias direct currents of 10, 20, 30, 40, 50, 100, 150, 200, 250, 300
Knowledge of the HuangRhys parameter and phonon energy al-
and 350 mA are depicted in Fig. 3. A broad emission band peaked at
lows us to determine the Stokes shift. S is related to the offset of the
517 nm is observed by excitation with blue light from LED chip,
parabolas in the configuration coordinate diagram and S is equal to:
while the 455 nm emission component from the chip itself remains to
S = (2S 1) h [2] be observable. It is observed that the electroluminescent intensity of
3+ 455 nm and 517 nm emissions simultaneously increase with increas-
For CaSc2 O4 :0.01Ce phosphor, the Stokes shift from Eq. 2 is
ing forward-bias direct current from 10 to 350 mA without showing
0.365 eV (2941 cm1 ). The Stokes shift for the Ce3+ emission in
saturation. This indicates that the CaSc2 O4 :Ce3+ phosphor has excel-
CaSc2 O4 : Ce3+ is smaller than that for the Ce3+ emission in most
lent luminescence properties.
other systems. Typically, Stokes shifts between 1000 and 8000 cm1
Fig. 4 shows the measured Commission International de
are observed.10 In view of the small Stokes shift a high luminescence
IEclairage (CIE) chromaticity of the pc-LED under different forward-
quenching temperature can be expected for the Ce3+ emission.
bias direct currents (IF = 10, 20, 30, 40, 50, 100, 150, 200, 250, 300
The thermal quenching behavior of CaSc2 O4 :0.01Ce3+ phosphor
and 350 mA). Under 350 mA forward-bias direct current, the CIE
under 460 nm light excitation was investigated in the temperature
chromaticity coordinates of the pc-LED is (0.2646, 0.3576). As the
range between 298 K and 523 K as shown in Fig. 2. It can be seen that
current increases from 10 mA to 350 mA, the shift of the coordinates
the emission intensity of Ce3+ starts to dramatically decrease at about
is very slight and negligible. Therefore, the CaSc2 O4 :Ce3+ phosphor
423 K. The thermal quenching temperature at which the emission
converted LED has an excellent stability even though it is operated
intensity is 50% of the emission intensity at room temperature is
under much high driven current. When the forward-bias direct current
about 530 K. The CaSc2 O4 :Ce3+ phosphor is very suitable for high
of 350 mA was driven to the pc-LED, a bright bluish green light was
power white LED.
observed via the naked eye (the inset of Fig. 4).
The mechanism for quenching of the f-d emission of Ce3+ may be
either quenching by thermally activated cross-over from the 4f0 5d1
excited state to the 4f1 ground state, or thermally activated photoion-
ization from the 4f0 5d1 state to conduction band.11 If the Stokes shift
for the f-d emission is small and the quenching temperature for the
phosphor is low, it is clear that photoionization is responsible for tem-
perature quenching of the phosphor.12,13 In the present phosphor the
Stokes shift is small and the luminescence quenching temperature is
relatively high, so both of the two mechanisms cannot be eliminated
in the thermal quenching process of CaSc2 O4 :Ce3+ phosphor.
According to the classical theory of thermal quenching, the
temperature-dependent intensity can be described by the expression14
I (0)
I (T ) = [3]
1 + A exp(E/kT )
where I(0) is the initial intensity at room temperature, I(T) is the
intensity at a given temperature T, A is a constant, E is the activation
energy and k is Boltzmann constant. Using the above equation, A and
E were determined to be about 473.992 and 0.282 eV with R2 =
0.99855, respectively.

Fabricated LED with CaSc2 O4 :Ce3+ phosphor.In order to in-

vestigate the potential application of CaSc2 O4 :Ce3+ phosphor in white
LEDs, phosphor-converted LED (pc-LED) was fabricated by combin-
ing 455 nm LED chip with CaSc2 O4 :0.01Ce3+ phosphor. The electro- Figure 4. The CIE chromaticity of the pc-LED under different forward-bias
luminescence spectra of the green emitting pc-LED under forward- direct currents.

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 R36 ECS Journal of Solid State Science and Technology, 5 (3) R34-R36 (2016)
Summary
3+
The green emitting CaSc2 O4 :Ce phosphor has been synthesized
by solid state reaction method. The temperature-dependent lumines-
cent properties of CaSc2 O4 :Ce3+ phosphor has been investigated from
298 to 523 K. With increasing temperature, the emission band of
CaSc2 O4 :Ce3+ phosphor shows decrease in emission intensity and in-
crease in its peak FWHM value. Huang-Rhys coupling factor, Stokes
shift, activation energy, and quenching temperature of CaSc2 O4: Ce3+
phosphors were determined to be 1.950, 0.365 eV, 0.282 eV and
530 K, respectively. The fabricated LED shows excellent chromatic-
ity without showing saturation as forward-bias current varies up to
350 mA. It is believed to be a good green emitting phosphor candidate
for white LEDs.
Acknowledgments
This work was supported by the Science and Technology Project
of Guangzhou (2013Y200118, 201510010182), the Science and
Technology Project of Guangdong Province (2013B090500114,
2015A030313687, 2015B070701023) and the research and service
platform construction Project of rare earth functional materials of
Guangdong Province.
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