Journal of Luminescence 177 (2016) 349–353

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Full Length Article

Luminescent properties and energy transfer of CaO:Ce3 þ , Mn2 þ

phosphors for white LED
Qipeng Liu a,n, Huijun Yin a, Tao Liu a, CuiQing Wang a, Riqiang Liu a, Wei Lü b,
Hongpeng You b,n
a
Lunan Institute of Coal Chemical Industry, Jining 272000, Shandong, PR China
b
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR
China

art ic l e i nf o a b s t r a c t

Article history: We have synthesized yellow–orange CaO:Ce3 þ ,Mn2 þ phosphors by solid-state reaction. Photo-
Received 19 October 2015 luminescence properties and energy transfer mechanism from Ce3 þ to Mn2 þ ions have been investi-
Received in revised form gated. The Ce3 þ activated phosphors exhibit strong absorption in the range of 250–490 nm and a yellow
20 April 2016
emission centered at 554 nm. When Mn2 þ ions were codoped, CaO:Ce3 þ ,Mn2 þ phosphors exhibit yel-
Accepted 4 May 2016
Available online 9 May 2016
low emission band of Ce3 þ as well as orange emission band centered at 600 nm of Mn2 þ . We observed
an efficient energy transfer from Ce3 þ to Mn2 þ ions in CaO:Ce3 þ ,Mn2 þ , which was verified from the
Keywords: lifetime decay curves and was discussed by Dexter's energy transfer theory. The critical distance of the
Phosphor energy transfer from Ce3 þ to Mn2 þ ions has also been calculated to be 12.3 Å by spectral overlap
Luminescence
methods following Dexter's theory and by concentration quenching mechanism to be 15.2 Å. Moreover,
Energy transfer
by combining the synthesized phosphors and InGaN blue chip (460 nm), warm-white light has been
LED
created.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction
White LED, which is so called the next generation lighting, is a
topic of increasing interest due to high luminous efficiency, low
power consumption, environment friendly, reliability, long life, and
so on [1,2]. The most common method is phosphor-converted pc-
LED, which connects blue InGaN LED with the garnet yellow phos-
phor (YAG:Ce3 þ ) [3]. However, compared with the incandescent
lamps and fluorescent lamps, this kind of white LED has a poor color
rendering index and cannot produce warm-white light, due to the
light deficiency in the red range of YAG:Ce3 þ phosphor. Never-
theless, the color rendering index of the white LED should be
improved greatly and the correlated color temperature should be
decreased for the general lamination lighting and special applica-
tion. To overcome these problems, 2-phosphors-converted white
LED with three emission bands was developed, which adds red
phosphor or creates white light by coating green and red phosphors
[4,5]. In this case, commercial sulfide-based phosphors and Mn4 þ -
activated fluoride microcrystals such as K2TiF6, K2SiF6 are considered
to be used as red phosphors [6,7], but they show a short lifetime
because of their low chemistry stability. Then the Ce3 þ or Eu2 þ
doped oxynitride and nitride phosphors have been developed for
white LED in recent years [8–11]. The combination of an InGaN blue
LED with green phosphor Sr2Si2O2N2:Eu2 þ and red phosphor
CaSiN2:Ce3 þ can lead to a white LED with higher color rendering
index [12]. However, to date their luminescent efficiencies are less
than those of single-phase phosphor based white LEDs. Therefore,
single-host phosphors with a road emission band covering green
and red regions have been investigated [13,14].
In the present study, we report our recent investigation results
on the luminescence and energy transfer from Ce3 þ to Mn2 þ ions
of CaO:xCe3 þ , yMn2 þ phosphors. CaO:xCe3 þ phosphors can emit
efficient yellow light with two emission peaks at about 550 and
618 nm under blue excitation. Moreover, there is an efficient
energy transfer from Ce3 þ to Mn2 þ ions in CaO:xCe3 þ , yMn2 þ
which lead to orange emission. Meanwhile, the concentration
quenching of Ce3 þ ions and the energy transfer from Ce3 þ to
Mn2 þ ions were also investigated. By combining these phosphors
and InGaN blue chip (460 nm), the white LEDs can generate warm-
white light.
2. Experimental section

n
Corresponding authors. Tel.: þ 86 537 3291338; fax: þ 86 537 3291067. A series of powder samples of CaO:xCe3 þ , yMn2 þ were syn-
E-mail addresses: dadi0314@163.com (Q. Liu), hpyou@ciac.ac.cn (H. You). thesized by a conventional solid-state reaction. CaCO3 (G.R.), MnO2

http://dx.doi.org/10.1016/j.jlumin.2016.05.014
0022-2313/& 2016 Elsevier B.V. All rights reserved.
350 Q. Liu et al. / Journal of Luminescence 177 (2016) 349–353

(A.R.), and CeF3(G.R.) were used as the raw materials, and were
weighed with a certain stoichiometric ratio and homogenized in
an agate mortar. The mixtures were heated at 1300 °C for 3 h in a
weak reducing atmosphere of active carbon. A mixture of the
prepared phosphors and transparent epoxy resin were dropped on
the blue InGaN LED chip with an emission peak at about 460 nm.
The x-ray diffraction patterns of the samples were collected on a
Rigaku-D X-ray powder Diffractometer with Cu Ka radiation
(λ ¼1.5418 Å). The excitation and emission spectra of the samples
were measured using a Hitachi F-4500 fluorescence spectro-
photometer with a 450 W xenon lamp as the excitation source.
The emission spectra of the white-light LEDs under a 20 mA drive
current were obtained by a Hitachi F-4500 Fluorescence spectro-
photometer. The emission spectra were corrected by taking into Fig. 2. Excitation and emission spectra of the sample CaO:0.007Ce3 þ (λem ¼ 554 nm,
account the combined effect of the spectral response of the λex ¼ 472 nm ) .
detector and the transmission of the monochromator. The lumi-
nescence decay curve was obtained from a Lecroy Wave Runner
6100 digital oscilloscope (1 GHz) using a tunable laser (pulse
width ¼4 ns, gate¼ 50 ns) as the excitation source (Continuum
Sunlite OPO). All the measurements have been performed at room
temperature.

3. Results and discussion

Fig. 1 shows the x-ray diffraction patterns of CaO:0.007Ce3 þ ,

CaO:0.012Mn2 þ , and CaO:0.007Ce3 þ ,0.012Mn2 þ samples. The
reflection peaks of the different compositions agree with that
reported in JCPDS file 37-1497, indicating the formation of cubic
CaO phase. When only the Mn2 þ ions doping the powder the
pattern has a single phase, however when the Ce3 þ concentration
is 0.007, a small amount of CeO2 phase exists. The cubic CaO has a
unit cell with a¼ 4.811 Å and space group Fm3m. The Ca ions are
six-fold (octahedral) coordination and have an Oh symmetry.
Therefore, the larger Ce3 þ (r ¼1.03 Å) ions and smaller Mn2 þ ions
(r ¼0.83 Å) substituted in the Ca2 þ (r ¼0.99 Å) ions would have a
six-fold coordination in the cubic lattice.
Fig. 2 depicts the excitation and emission spectra of the phos-
phor CaO:0.007Ce3 þ . The excitation spectrum consists of two
bands peaking at about 270 and 470 nm. The excitation band
centered at 472 nm is ascribed to the transitions from the 4f1
ground state to the 5d1 excited states of Ce3 þ , another band is
assigned to host-lattice excitation. The emission spectrum shows a
broadband peaking at 554 nm under the excitation of 472 nm,
which is due to the allowed 5d-4f transition of Ce3 þ ions. The
emission spectrum of CaO:Ce3 þ , which can be divided into two
Gaussian-shaped bands peaking at 550 and 618 nm and the energy
difference of two peaks is about 2000 cm  1, is attributed to the
Fig. 1. The XRD patterns of the samples of CaO:0.007Ce3 þ , CaO:0.012Mn2 þ , and
CaO:0.007Ce3 þ ,0.012Mn2 þ .
Fig. 3. Emission intensity of the phosphors CaO:xCe3 þ (x¼ 0.002, 0.005, 0.007,
0.010,0.015).
transition from the lower excited state T2g(5d) to 2F5/2 and 2F7/2
levels, respectively[15].
As shown in the Fig. 3, the emission intensity of the CaO:xCe3 þ
increases initially and then decreases with a maximum at 0.007
Ce3 þ -concentration when under the excitation of 472 nm. This
result reveals that the critical concentration is about 0.007. The
concentration quenching of the luminescence occurs because the
distance of Ce3 þ ions becomes smaller due to the replacement of
Ca2 þ ions, which leads to the energy transfer between Ce3 þ
centers in the CaO host lattice. The critical distance (Rc) for the
energy transfer between Ce3 þ centers can be estimated by the
formula suggested by Blasse [16,17]:

1=3
3V
RC ¼ 2 ð1Þ
4π xc N
where xc is the critical concentration, N is the number sites that
Ce3 þ ions can occupy in per unit cell, and V is the volume of the
unit cell. For the CaO host, xc ¼0.007, N ¼4, V ¼111.15 Å3, the esti-
mated value Rc is approximately 19.6 Å. Energy transfer mechan-
ism from one Ce3 þ ion to another may occur by exchange inter-
action, radiation reabsorption, or multipole–multipole interaction.
The exchange interaction accounts for the energy transfer of for-
bidden transitions and the typical critical distance is about 4 Å
between different activate ions [16], which is far less than that of
the calculation result (RC) 19.6 Å of the CaO:Ce3 þ . The mechanism
of radiation reabsorption occurs when there is abroad overlap of
the PL spectra of the sensitizer and the PLE of the activator, and in
the view of the excitation and emission spectra of the CaO:Ce3 þ
there is little overlap. Therefore the exchange interaction and
radiation reabsorption are unlikely to come to effect. The process
of the energy transfer between Ce3 þ ions in the CaO:Ce3 þ should
occur as a result of multipole–multipole interaction. Since the
 Q. Liu et al. / Journal of Luminescence 177 (2016) 349–353
Fig. 4. The PL and PLE spectra of CaO:Mn2 þ (λem ¼ 600 nm, λex ¼ 243 nm).
Fig. 5. Spectral overlap between the emission spectra (λem ¼ 472 nm) of CaO:Ce3 þ
(red line) and excitation ((λem ¼600 nm)) spectra of the sample CaO:Mn2 þ (black
line). (For interpretation of the references to color in this figure legend, the reader
is referred to the web version of this article).
absorption transition of Ce3 þ ions is electric dipole allowed, it is
expected that energy transfer mechanism between Ce3 þ ions is an
electric dipole–dipole type.
Fig. 4 shows the emission and excitation spectra of CaO:Mn2 þ .
The emission spectrum exhibits one broad band at about 600 nm
which is assigned to the 4T1(4G)-6A1(6S) transition of Mn2 þ . The
Mn2 þ emission strongly depends on the substituted site in host,
locates at a longer wavelength when it occupies an octahedron
site, and it used to emit red or yellow light [18,19]. While located
in the tetrahedron sites, the Mn2 þ emission band lies in a shorter
wavelength, and it used to be green emission, such as in some
aluminate phosphors [20]. The CaO:Mn2 þ shows orange emission
centered at 600 nm, so we consider that Mn2 þ ions prefer to
substitute octahedral coordination. The excitation spectra presents
several weak absorption bands at about 360, 383, 423, 478, and
562 nm and one strong absorption band at about 243 nm. These
weak bands are due to the transitions from 6A1(6S) to 4Eg(4D),
4
T2g(4D), 4Eg(4G), 4A1g(4G)), 4T2g(4G), and 4T1g(4G) levels of Mn2 þ ,
respectively. The absorption in the range from 200 to 300 nm is
very strong, compared with other absorption bands, and can not
be attributed to the transition of the d5 configuration because the
transitions between the 3d levels are forbidden by the selection
rules. This absorption behavior is quite similar to that of the Mn2 þ
ions doped Zn2SiO4:Mn [21].
A significant spectra overlap between the emission band of
Ce3 þ centered at 554 nm (monitored at 472 nm) and the Mn2 þ
excitation transitions of 6A1(6S)-4T1g(4G), which is showed in
Fig. 5. Therefore, it is expect that an efficient energy transfer can
occur from Ce3 þ to Mn2 þ ions, the Ce3 þ and Mn2 þ ions act as
energy donor and energy acceptor, respectively. Fig. 6 shows the
351
Fig. 6. Emission (λex ¼ 472 nm) spectra of the sample CaO:0.007Ce3 þ , yMn2 þ
(y ¼0, 0.002, 0.006, 0.012, 0.016).
Fig. 7. The decay curves for Ce3 þ in CaO:0.007Ce3 þ , yMn2 þ ( excited at 420 nm,
monitored at 540 nm).
emission spectra of CaO:0.007Ce3 þ , yMn2 þ with different Mn2 þ
doping content under 472 nm excitation. The emission spectra of
the samples through the Ce3 þ -excitation contain both Ce3 þ and
Mn2 þ emissions. The yellow emission intensity of Ce3 þ is
decreased, whereas the orange emission of Mn2 þ is increased with
Mn2 þ content, indicating that the Ce3 þ –Mn2 þ energy transfer is
highly efficient. Thus the energy transfer from Ce3 þ to Mn2 þ ions
occurs, which improves the emission 4T1(4G)-6A1(6S) of Mn2 þ
ions. This kind of energy transfer is special because the absorption
in green range leads to orange emission [22,23].
In order to investigate energy transfer form Ce3 þ to Mn2 þ ions
in more detail, the lifetime of the Ce3 þ emission in
CaO:0.007Ce3 þ , yMn2 þ samples were measured by monitoring at
540 nm with the irradiation of 420 nm. The decay curves are
plotted on a logarithmic intensity scale in Fig. 7. The average
lifetime of CaO:0.007Ce3 þ , yMn2 þ samples can be defined as:
R1
tIðtÞdt
τ ¼ RΟ1 ð2Þ
Ο IðtÞdt
I(t) is the emission intensity of the phosphor at time t. Using
the above equation, the average lifetime τ of Ce3 þ ions were
determined to be 0.04801, 0.03736, 0.03442, 0.03192 and
0.02987 μs for CaO:0.007Ce3 þ , yMn2 þ samples with y¼0.00,
0.002, 0.006, 0.012, and 0.016, respectively. The average lifetime of
Ce3 þ ions decreases monotonously with increase of Mn2 þ con-
tent, which demonstrates that the Ce3 þ to Mn2 þ energy transfer is
of non-radiative nature. The energy transfer efficiency (ηT) can be
352 Q. Liu et al. / Journal of Luminescence 177 (2016) 349–353
Fig. 8. Dependence of IS0/IS of Ce3 þ on (a)C6/3, (b) C8/3 and C10/3, C is the total
concentration of the Ce3 þ and Mn2 þ ions.
calculated using following equation [24]:
τS
ηΤ ¼ 1 
τS0
Here τS and τS0 are the average lifetime of Ce3 þ ions in the pre-
sence and absence of Mn2 þ ions. The energy transfer efficiency ηT
can be calculated to be 20.1%, 28.3%, 33.5%, 37.8, corresponding to
y¼0.00, 0.002, 0.006, 0.012, and 0.016, respectively.
The emission spectrum and the average lifetime properties
indicate the existence of the efficient non-radiative energy transfer
from Ce3 þ to Mn2 þ ions, which may occur as a result of exchange
interaction or multipole–multipole interaction. Blasse suggested
that the average separation RC of the energy transfer can be esti-
mated from the Eq. (1), the critical concentration xc is the total
concentration of Ce3 þ and Mn2 þ ions, where the luminescence
intensity of sensitizer (Ce3 þ ) is half that in the sample in the
absence of activator (Mn2 þ ). The critical distance of energy
transfer RC is estimated to be about 15.2 Å. The exchange inter-
action accounts for the energy transfer of forbidden transitions
and the typical critical distance is about 4 Å between different
activate ions, which is far less than that of the calculation result
Fig. 9. CIE chromaticity diagram for the white LED1 (point 1) and LED2 (point 2)
and the phosphors CaO:0.007Ce3 þ , yMn2 þ (A y¼ 0), (B y¼0.002), (C y ¼0.006), (D
y¼0.012) excited at 472 nm. The corresponding CIE coordinates are A (0.4508,
0.5332), B (0.4839, 0.5021), C (0.5191, 0.4708), D (0.5517, 0.4429), respectively. The
CIE coordinates of the InGaN blue chip is shown as point E (0.15, 0.035). (For
interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article).
ð3Þ Fig. 10. Emission spectra of the LEDs fabricated with CaO:0.007Ce3 þ (LED1),
CaO:0.007Ce3 þ , 0.006Mn2 þ (LED2) and 460 nm blue LED. (For interpretation of the
references to color in this figure, the reader is referred to the web version of this
article).
(RC) 15.2 Å of the CaO:0.007Ce3 þ , yMn2 þ , indicating little possi-
bility of energy transfer comes into effect by exchange interaction.
Therefore it is excepted that the mechanism of energy transfer
from Ce3 þ to Mn2 þ ions in the CaO:0.007Ce3 þ , yMn2 þ should
occur as a result of the multipole–multipole interaction. [25,26] On
the basis of Dexter's energy transfer theory and Reisfeld's
approximation, the following relation also can be obtained [24,27]
I S0
p C n=3 ð4Þ
IS
Where IS0 and IS are the intrinsic luminescence intensity of Ce3 þ in
the absence and presence of Mn2 þ , respectively. C is the total
concentration of Ce3 þ and Mn2 þ ions, n ¼ 6, 8, and 10 are corre-
sponding to dipole–dipole, dipole–quadrupole, and quadrupole–
quadrupole, respectively. The IS0/IS-Cn/3 plots are shown in the
 Q. Liu et al. / Journal of Luminescence 177 (2016) 349–353 353

Fig. 8. The linear relationship was observed only when n is 8. energy transfer from Ce3 þ to Mn2 þ ions takes place in CaO host
Therefore the dipole–quadrupole interaction is dominant in the lattice. Comparing with YAG:Ce3 þ , the CIE of these phosphors
energy transfer mechanism from Ce3 þ to Mn2 þ ions in CaO:Ce3 þ , indicates the red proportion is greatly improved. By combining the
Mn2 þ . For the dipole–quadrupole interaction mechanism, the yellow-orange phosphor and InGaN blue chip (460 nm), the white
critical interaction distance RCe–Mn between Ce3 þ and Mn2 þ ions LED can generate bright warm white light. This investigation
can be given by Dexter as the following relation [24]: indicates that the CaO:xCe3 þ , yMn2 þ phosphors with tuning of
Z the activator content exhibit a potential application for white
f S ðEÞF A ðEÞ
R8Ce  Mn ¼ 3:024  1012 f q λS
2
dE ð5Þ light-emission diodes.
E4
where λs is the wavelength position on Ce3 þ emission, fq ( 10  10)
is the oscillator strength of electric quadrupole transition of Mn2 þ , Acknowledgments
fS(E) represents the normalized emission line shape function of
Ce3 þ ions, FA(E) the normalized absorption line shape function of This work is financially supported by the Natural Science
Mn2 þ ions, E is the energy involved in the transfer (eV), the
R Foundation of Shandong Province (Grant no. ZR2013BQ001).
spectral overlap f S ðEÞF A ðEÞ=E4 dE was obtained to be 0.0551 eV  5.
Using the values mentioned above, the critical interaction distance
RCe–Mn is estimated to be about 12.3 Å, which is approximately References
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confirmed to be a multipole-multipole interaction. The lumines-
cent properties and lifetime of CaO:Ce3 þ ,Mn2 þ reveal that the