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PAPER

Cite this: J. Mater. Chem. C, 2013, 1,

5892

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Red, green and blue emissions coexistence in

white-light-emitting Ca11(SiO4)4(BO3)2:Ce3+,Eu2+,
Eu3+ phosphor
Jingshan Hou,a Weizhong Jiang,*a Yongzheng Fang*b and Fuqiang Huang*c
Ce3+, Eu2+ and Eu3+ singly activated and Ce3+/Eu2+/Eu3+-coactivated Ca11(SiO4)4(BO3)2 (CSB) phosphors
were synthesized by novel and ecient aluminium reduction solid state reactions. Under ultraviolet
light excitation, the Ce3+, Eu2+ and Eu3+ singly activated CSB phosphors exhibit intense red, green and

Received 17th May 2013

Accepted 18th July 2013

blue emissions, respectively. The unique host CSB shows its superior advantages in color balance
compared with the widely-used Ca2SiO4, Ca3B2O6 and Y3Al5O12. The red, green and blue colors can be
controlled by the reduction temperature, and a white light emitting phosphor was obtained by
reducing the as-prepared CSB:0.02Ce,0.005Eu powder at 700
C for 8 h. The unique property of CSB in

DOI: 10.1039/c3tc30933a

color balance was proposed to attribute to the group synergy eect. Furthermore, the energy transfer

www.rsc.org/MaterialsC

probability was discussed in detail, and the critical distance was calculated.

Introduction

Solid state light (SSL) using phosphor converted white light

emitting-diodes (pc-WLEDs) to generate white light has caught
much attention due to their advantages of high eciency, long
lifetime, low power consumption and environment-friendly
characteristics. Generally, there are three dierent approaches
to generate white light based on LEDs:1 (1) by mixing reds,
greens, and blues, i.e. redgreenblue (RGB) LEDs, (2) by using
an ultraviolet (UV) LED to stimulate RGB phosphors, and (3) by
using a blue-emitting diode that excites a yellow-emitting
phosphor embedded in the epoxy dome (two methods of
generating white light from LEDs are shown in Fig. 1a and b).
Todays commercially available white LEDs are realized through
combining the blue emitting chips with the yellow phosphors
(YAG:Ce3+).2 However, this combination usually suers from a
low color rendering index (Ra 72) and a high correlated
color temperature (CCT 7756 K) due to the lack of redlight contribution. In the three-converter (RGB) system, the

manufacture cost is high (RGB LEDs require dierent driving

currents for dierent color LEDs, complicating their fabrication) and the blue emission eciency is poor because of the
strong reabsorption of blue light by the red and green-emitting
phosphors. These problems can be avoided by using single
component phosphors with higher luminous eciency and an
excellent color rendering index. Therefore, it is important to

State Key Laboratory for Modication of Chemical Fibers and Polymer Materials,
Dong Hua University, Shanghai 200051, P.R. China. E-mail: jwz@dhu.edu.cn

School of Materials Science and Engineering, Shanghai Institute of Technology,

Shanghai 200235, P.R. China. E-mail: fangyongzheng@gmail.com

c
CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of
Ceramics, Chinese Academy of Sciences, Shanghai 200050, P.R. China. E-mail:
huangfq@mail.sic.ac.cn

Electronic supplementary information (ESI) available: XRD renement analysis

of CSB, XRD patterns of the reference samples, calculation method of quantum
eciency, PL spectra of Al-reduced CSB:0.005Eu calcined at dierent
temperatures and additional PL spectra and chromaticity coordinates of
CSB:0.02Ce,0.001Eu and CSB:0.02Ce,0.005Eu analysis data are given. See DOI:
10.1039/c3tc30933a

5892 | J. Mater. Chem. C, 2013, 1, 58925898

Fig. 1 (a) and (b): two methods of generating white light from LEDs, (c) a
schematic of the reaction device and (d) a picture of a reaction device for sample
preparation.

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investigate the single-composition phosphors with blue-to-red
emission bands to realize white-light emission.
Numerous eorts have been made to develop the singlecomposition white-emitting phosphors that are based on the
mechanism of energy transfer from sensitizer to activator, such
as Eu2+/Mn2+,36 Ce3+/Mn2+,7,8 and Ce3+/Eu2+.912 On the other
hand, novel green and blue phosphors with excellent photoluminescence (PL) properties can also provide an alternative
option for LEDs applications. However, for the exposure of 5d
electrons of Ce3+ or Eu2+ to a crystal environment, their emissions, arising from orbitally allowed df electronic transitions,
are wavelength tunable because they are sensitive to the crystal
eld splitting and nephelauxetic eects.13,14 The local crystal
environment, which is critical for luminescence, is an exclusive
property of a host material and can be strongly inuenced by
the coordination or the surrounding groups in the lattice.
Garnet structure-based material, borates and silicates are very
commonly used host materials. The transitions of 5d electrons
of Ce3+ or Eu2+ present a variety of colors in these materials.
Normally, Ce3+ or Eu2+ has some specic photoluminescence
performance in these host materials: Ce3+ usually gives a blue
emission under an UV exaction in a borateoxide,10,1517 while
Eu2+ usually gives a green emission in a sillicaoxide.1822
However, it is dicult to make both Ce3+ and Eu2+ exhibit their
particular emission responding to the same excitation region in
the same kind of single group host material and at the same
time to make them keep sucient emission intensity. Just as
mentioned above, a white light requires the fabrication of two
or more relative colors. Needless to say, in order to balance
these colors well, we need to put these emission centers into a
unique host. A unique host should be a multiperformer, it
should integrate the functions of two or more single group
materials, in order to provide a proper environment for the
transitions of the 5d electrons of Ce3+ or Eu2+ to show their
specic photoluminescence performance in a single group host

Fig. 2 (a) The XRD patterns of CSB, CSB:0.02Ce3+ and CSB:0.005Eu2+. (bd) The
PLE and PL spectra of (b) CSB:0.005Eu3+, (c) CSB:yEu2+ (y 0.0010.02) and (d)
CSB:xCe3+ (x 0.0050.025).

This journal is The Royal Society of Chemistry 2013

Journal of Materials Chemistry C

Fig. 3 XPS survey spectrum of CSB:0.02Ce,0.005Eu by Al reduced at 1000
C.

The inset shows the high resolution XPS spectrum of Ce 3d core levels.

material. Thus, we chose a co-host material as the study object,

and then a group synergy eect is expected.
In this paper, we report such a unique material,
Ca11(SiO4)4(BO3)2 (CSB), as a host. Ce3+, Eu2+ and Eu3+ singly
activated and Ce3+/Eu2+/Eu3+-coactivated Ca11(SiO4)4(BO3)2
phosphors were synthesized for the rst time by aluminium
reduction solid state reactions. In this host, Eu3+, Eu2+ and Ce3+
singly activated CSB phosphors can be excited by UV light
excitation to pump red, green and blue emission, respectively.

Fig. 4 (a) PL spectra of the CSB:0.02Ce3+,yEu phosphors with dierent Eu doping

contents. The insert shows dependence of the energy transfer eciency (hT) on Eu
concentration. (b) Illustration of the energy transfer modes for Ce3+ / Eu2+, and
Ce3+ / Eu3+ in the CSB host.

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Journal of Materials Chemistry C

Fig. 5 PL spectra of the CSB:0.02Ce,0.005Eu (lexc 353 nm), Ca2SiO4:0.02Ce,0.005Eu (lexc 356 nm), Ca3B2O6:0.01Ce,0.001Eu (lexc 357 nm), and
YAG:0.02Ce,0.03Eu (lexc 465 nm) by Al reduced at 700
C.

Paper
concentrations of Eu2+ and Ce3+ were chosen as 0.12 mol% and
0.52.5 mol% of Ca2+ in Ca11(SiO4)4(BO3)2, respectively. CaCO3
(A.R.), SiO2 (99.99%), H3BO3(A.R.), Eu2O3 (99.99%) and CeO2
(99.99%) were used as starting materials. Stoichiometrical
reagents were thoroughly mixed with acetone in agate mortar,
and then transferred to an alumina crucible and calcined in a
furnace at 1250
C for 24 hours under ambient atmosphere. The
obtained products were placed in a semi-closed quartz tube and
then sited in a larger quartz tube with excess Al powder (99%)
acting as an oxygen-getter in the bottom. The outer quartz tubes
were sealed under vacuum and then heated to 3001000
C for
8 h. The schematic of the equipment is shown in Fig. 1c and d
(Fig. 1c and d were designed from the same theory and the
device shown in Fig. 1c can be used for mass production).
Reference samples of Ca2SiO4:Ce,Eu, Ca3B2O6:Ce,Eu, and
YAG:Ce,Eu were synthesized by solid state reactions (the original Ca2SiO4:Ce,Eu samples were calcined at 1250
C for
24 hours, Ca3B2O6:Ce,Eu were calcined at 1100
C for 2 hours,
YAG:Ce,Eu were calcined at 1500
C for 12 hours) and the nal
products were optimized followed by the same method as
CSB:Ce,Eu phosphors.
2.2

Characterization

The phase purity of the samples was characterized and evaluated by powder X-ray diraction (XRD) analysis on a Bruker

D8 Focus diractometer with Cu Ka radiation (l 1.5418 A)

operated at 40 kV and 40 mA. The photoluminescence (PL) and
PL excitation (PLE) spectra of the phosphors were analyzed by
using a FluoroMax-4 uorescence spectrometer at room
temperature. X-ray photoelectron spectroscopy (XPS) data was
obtained using ESCAlab250 X-ray Photoelectron Spectroscopy
for surface analysis. An integrating sphere (F-3018) attached
to the Spectrouorometer was used to carry out the measurements of the Commission Internationale de L'Eclairage (CIE)
chromaticity coordinates and photoluminescence quantum
eciency.
Fig. 6 PL intensities of Ce3+, Eu2+ and Eu3+ in the CSB host with raised
temperatures. The inset shows PL spectra of the CSB:Ce3+,Eu2+,Eu3+ phosphor
excited at 353 nm with dierent temperatures.

In Ce3+/Eu2+/Eu3+-coactivated Ca11(SiO4)4(BO3)2 phosphors, the

trichromatic colors were well balanced by controlling the
aluminium reduction temperature and an UV light excitation
white light emission was achieved. Furthermore, the energy
transfer mechanism between Ce3+ and Eun+ (n 2, 3) was
systematically investigated, and the critical distance was
calculated.

Experimental details

2.1

Sample preparation

Ca11(1xyz)(SiO4)4(BO3)2:xCe3+,yEu2+,zEu3+ (abbreviated as
CSB:xCe3+,yEu2+,zEu3+; x, y and z are the percentage in mol)
were synthesized by solid state reaction. The doping

5894 | J. Mater. Chem. C, 2013, 1, 58925898

Results and discussion

3.1

X-Ray diraction analysis

The powder XRD patterns of CSB, CSB:0.02Ce3+, CSB:0.005Eu2+

are shown in Fig. 1a. (An XRD renement analysis of the asprepared CSB sample is performed in Fig. S1.) The similar
patterns indicate that the doped Ce3+, Eu2+ and Eu3+ ions or codoped Ce3+/Eu2+/Eu3+ ions were completely dissolved in the
Ca11(SiO4)4(BO3)2 host without inducing signicant changes of
the crystal structure. Ca11(SiO4)4(BO3)2 was suggested to have a
close structural relationship to b-Ca10(SiO4)4(CO3)2 (space group
b 15.974(9) A,
c 6.874(8) A,

P21/a (no. 14)), a 28.61(2) A,

a b 90
, and g 104.1(1)
.23 In b-Ca10(SiO4)4(CO3)2, Ca2+,
Si4+ and C4+ ions occupy ve, two and one crystallographic
sites, respectively. The linkage pattern of the CO3 and SiO4
groups by the Ca atoms is quite irregular. Three of the Ca atoms
have seven neighbouring oxygen atoms and the other two have

eight neighbours.24 The radius of Ca2+ (CN 7: r 1.06 A;

CN 8: r 1.12 A) is similar to that of the substitutional Eu3+

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Table 1

Journal of Materials Chemistry C

Quantum eciencies (h) and the chromaticity coordinates (x, y) of phosphors CSB:Ce3+,Eu2+,Eu3+

Sample no.

Sample composition

lexc
(nm)

h (%)

CIE (x, y)

1
2
3
4
a
b
c
w
d
e
f
g

CSB:0.02Eu3+
CSB:0.02Ce3+
CSB:0.005Eu2+
Al-Re CSB:0.02Ce, 0.005Eu at 700
C
Al-Re Ca2SiO4:0.02Ce, 0.005Eu at 700
C
Al-Re Ca3B2O6:0.01Ce, 0.001Eu at 700
C
Al-Re YAG:0.02Ce, 0.03Eu at 700
C
White-light LED
XCJ-R Y2O3:Eu3+
XCJ-G CeMgAl10O19:Tb3+
XCJ-B BaMgAl10O17:Eu2+
Hongda YAG:Ce3+

394
353
365
353
356
357
465

394
365
365
465

9.7
15.9
5.3
2.4

9.6
11.3
94.3
39.8

(0.624, 0.375)
(0.154, 0.082)
(0.247, 0.478)
(0.267,0.348)
(0.198, 0.274)
(0.175, 0.044)
(0.401, 0.579)
(0.314, 0.348)34

Fig. 7 1931 CIE chromaticity diagram of CSB:0.02Ce3+ (lexc 353 nm),

CSB:0.005Eu2+ (lexc 365 nm), and CSB:0.02Eu3+ (lexc 394 nm). The inset
shows the PL spectrum of CSB:0.02Ce,0.005Eu by Al reduced at 700
C under
353 nm UV light excitation. The pictures were taken in a dark room by using a
365 nm ultraviolet lamp as the excitation source.

CN 8: r 1.07 A),
Eu2+ (CN 7: r 1.2 A;

(CN 7: r 1.01 A;
3+
and Ce (CN 7: r 1.07 A;
CN 8: r
CN 7: r 1.25 A)
In view of the similar ion radius and valence, the Ce3+,
1.14 A).
2+
Eu and Eu3+ ions are expected to substitute in the Ca2+ sites in
Ca11(SiO4)4(BO3)2.
3.2 Luminescence properties of Eu3+, Eu2+ and Ce3+ singly
activated Ca11(SiO4)4(BO3)2
The PLE and PL spectra of the CSB:0.005Eu3+ phosphor are
shown in Fig. 2b. In the PLE spectrum, the wide excitation band
appearing below 310 nm is assigned to the charge-transfer band

This journal is The Royal Society of Chemistry 2013

(CTB) between Eu3+ and the surrounding oxygen anions.25 The

major emission peaks are observed at 587, 613, 623, 650, and
702 nm. All these are characteristic emission peaks of the Eu3+
ion and are corresponding to 5DJ (J 0, 1) / 7FJ (J 1, 2, 3, 4)
transitions.
Fig. 2c illustrates the PLE and PL spectra of CSB:yEu2+ (y
0.0010.02). Upon excitation of 365 nm, the CSB:yEu2+ phosphor exhibits an intensive green luminescence centered at
502 nm. This was imputed to the electric-dipole-allowed transition from the lowest level of the 5d excited state to the 4f
ground state of the Eu2+ ions. The optimal Eu2+ dopant content
was found to be 0.005 mol. For those samples with higher Eu2+
dopant content, concentration quenching was observed and the
PL/PLE intensity was found to decrease with an increase of
doped Eu2+ content.
The concentration dependence of the relative PLE and PL
intensities of CSB:xCe3+ (x 0.0050.025) are shown in Fig. 2d.
The excitation spectra (lem 430 nm) of CSB:xCe3+ shows a
broad band from 230 nm to 450 nm, which is assigned to the
allowed 4f1 / 5d1 transition. The dominant bands in the PLE
spectrum are dicult to resolve due to the Ce3+ 5d1 multiplet
excited states and the serious overlap between 5d1 levels. Under
353 nm UV-light excitation, CSB:xCe3+ show an intensive blue
emission from 360 to 600 nm with the maximum at 430 nm
caused by the transition of Ce3+ from the 5d1 excited state to the
2
F5/2 and 2F7/2 ground states. The optimal Ce3+ dopant content
was found to be x 0.02. For samples with higher Ce3+
concentration, PL/PLE intensity decreases due to the concentration quenching eect.
3.3

Energy transfer between Ce3+ and Eun+ (n 2, 3)

In the Ce/Eu co-doped system, it was found that there is always a

part of the Eu3+ that seems to be fairly stable in the lattice and is
dicult to reduce into divalence. It was reported that Eu3+ could
be stable for excitation in some particular host materials,26
especially in a Ce/Eu co-doped system.27 For the dopant with a
divalent state (Eu2+), overall charge compensation in the lattice
could be required for one-to-one substitution. For the R3+ (R
Ce, Eu) dopant, the charge compensation involves two R3+ ions
substituting for three Ca2+ ions. There are two ways to maintain

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overall charge neutrality in the lattice: one is R3+ ions

substituting for Ca2+ and leaving behind a Ca vacancy:
2Ca2 /2R3 V00Ca to form the dipole complexes of
$
00
2R3
Ca  V Ca , and another involves the interstitial oxygen Oi:
2Ca2 /2R3 O00i to form the dipole complexes of
$
00
2R3
Ca  Oi . Actually, a charge transfer balance between two
conjugate elements, cerium and europium, was supposed to be
excited in the Ce/Eu co-doped system. The reaction equation
can be described as:
Ce3+ + Eu3+ # Ce4+ + Eu2+

(1)

This explains the residual Eu3+ in the Ce/Eu co-doped

system, and it was further conrmed by X-ray photoelectron
spectroscopy (XPS) spectra analysis. The photoelectron survey
spectrum of the pristine CSB:0.02Ce,0.005Eu by Al reduced at
1000
C is plotted in Fig. 3. The doped elements, Ce and Eu,
were detected in the sample. The Eu 3d5/2 (around 1136 eV) and
Ce 3d core-level peaks exhibit weak intensities due to a low
doping concentration. The satellite peaks around 916.7, 905.6
and 887 eV conrmed the trace of Ce4+ in the sample of
CSB:0.02Ce,0.005Eu by Al reduced at 1000
C. Combined with
its PL spectrum, the charge transfer balance is further
conrmed.
Energy transfer was expected to occur from Ce3+ to Eu2+
based on the signicant spectral overlap observed, particularly
between the emission band of the CSB:Ce3+ (5d1 / 4f1) and the
excitation band of the CSB:Eu2+ (4f65d1 / 4f7) transition.
Therefore, an eective resonance-type energy transfer from
Ce3+ to Eu2+ was expected. Fig. 4a shows the emission spectra
for Eun+ (n 2, 3) at dierent values of m (m 00.2 mol%) in
CSB:0.02Ce3+,mEun+ (n 2, 3) phosphors. The intensity of the
Ce3+ emission at 430 nm decreases, and that of the Eu2+
emission at 505 nm increases, with increasing Eu2+ content up
until 1 mol%, at which point concentration quenching appears.
This phenomenon is attributable to the energy transfer from
Ce3+ to Eu2+. The 4f5d transition of Ce3+ and Eu2+ ions is an
allowed one; the energy transfer from Ce3+ to Eu2+ ions will
mainly occur by dipoledipole interaction on the basis of the
theory of energy transfer of Dexter.12,28 Therefore, the critical
distance Rc of the energy transfer can be expressed as
follows:29,30

FS EFA E
Rc 6 3  1012 fd
(2)
E4
where fd z 0.02 is the electric dipole oscillator strength for Eu2+

ions. FS(E)FA(E)/E4dE represents the spectral overlap between

the normalized shapes of Ce3+ emission FS(E) and Eu2+ excitation FA(E), and it is calculated to be about 0.0207 eV5. Therefore, the Rc of the energy transfer was calculated to be about

32.8 A.
Energy transfer was also expected to occur from Ce3+ to Eu3+
and a simplied energy level diagram for demonstrating clearly
the energy transfer mechanisms between Ce3+ and Eu3+ ions
was employed in Fig. 4b. In fact, Ce3+ ions co-doped with Eu3+
will benet the luminescence eciency of the Eu3+ ion by
energy transfer to decrease the nonradiative energy of the Eu3+

5896 | J. Mater. Chem. C, 2013, 1, 58925898

ion, due to the fact that Ce3+ ions permit the electronic transitions of 4f2 / 4f5d and 4f2 / 4f2 so that they can be eciently
excited in a wide UV range.31 Two paths for energy transfer
between Ce3+ and Eu3+ ions were supposed: energy transfer 1
(marked as ET1 in Fig. 4b). It was suggested that the cross
relaxation of 5D0 + 7F3 (Eu3+) 4 2F5/2 + 2D(5d) (Ce3+) has steadily
happened in the Ce3+ and Eu3+ co-doped system, which would
signicantly increase the emissions of 5D0 levels. On the other
hand, for Energy transfer 2 (marked as ET2 in Fig. 4b), the
2
D(5d) state of Ce3+ can eciently transfer energy to the 5D1
energy level of Eu3+ due to the well matched energy, then
depopulate the 5D1 level of Eu3+ by a multi-phonon relaxation to
the 5D0 level.32 In addition, the compensation of charges, which
decreases the number of Ca vacancies, leads to stronger
emission.
In order to better understand the energy-transfer process,
the energy-transfer eciencies (hT) from Ce3+ to Eun+ (n 2, 3)
of our phosphors were calculated. The energy transfer eciency
(hT) from Ce3+ to Eun+ can be expressed according to Paulose
et al.:33
hT 1 

Is
Iso

(3)

where Is and Iso are the luminescence intensity of the sensitizer

(Ce3+) with and without activator (Eun+). The hT from Ce3+ to
Eun+ is calculated as a function of Eun+ concentration y and is
shown in the inset of Fig. 4a. The hT was found to increase
gradually with increasing Eu content.

3.4 Eect of reduced temperature on the luminescence

properties of Eu2+/Eu3+ or Ce3+/Eu2+/Eu3+ co-doped
Ca11(SiO4)4(BO3)2 phosphors
A white light can be generated by the fabrication of trichromatic
(RGB) color, and the reduction temperature from Eu3+ ions to
Eu2+ ions in a CSB host has been ascertained to occur at about
600
C (as shown in Fig. S3). Thus, as an initial attempt, the
Ce3+/Eu2+/Eu3+ co-doped Ca11(SiO4)4(BO3)2 phosphor was
synthesized. In the CSB:xCe3+,yEu2+.zEu3+ system, Eu3+ ions,
Eu2+ ions and Ce3+ ions act as the red, green, and blue emission
centers, respectively. The intensity of Ce3+/Eu2+/Eu3+ was optimized by changing the reduction temperature and reduction
time. PL spectra of Al-reduced CSB:0.02Ce,0.001Eu and
CSB:0.02Ce,0.005Eu calcined at dierent temperatures were
shown in Fig. S4. A warm white light emitting phosphor was
obtained by reducing the as-prepared CSB:0.02Ce,0.005Eu
powder at 700
C for 8 h. The PL spectra of CSB:0.02Ce,0.005Eu
under 353 nm UV light excitation was shown in Fig. 5, and the
schematic PL spectra from dierent luminescence centers are
also presented in the inset in Fig. 6 by dotted lines. PL spectra of
Al-reduced Ca2SiO4:0.02Ce,0.005Eu, Ca3B2O6:0.01Ce,0.001Eu,
and YAG:0.02Ce,0.03Eu were shown in Fig. 5. Compared with
these three representative single group host materials, the CSB
host shows its superior advantage in balancing the colors from
dierent emission centers. These are attributed to the synergy
eect from [SiO44] and [BO33] groups in CSB. The crystal
environment provided by CSB allows the df electronic

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Journal of Materials Chemistry C

transitions of Ce3+ and Eu2+ to give their specic blue and green
light-emission, and at the same time oers an eective energy
transfer path between Ce3+ and Eu3+, which ensures red emission with a sucient intensity. Trichromatic colors from
dierent luminescence centers are balanced well in the CSB
host, and a white light emission under UV light exaction is then
achieved.

exhibit intensive red, green and blue emission, respectively. The

Ce3+ activated sample exhibits intensive blue emission under
353 nm UV excitation. Under a 365 nm ultraviolet excitation, the
phosphors CSB:Eu2+ exhibit strong blue emission centered at
500 nm, which corresponds to the 4f65d1 / 4f7 transitions of
Eu2+ ions. The Ce3+ / Eu2+ energy transfer was demonstrated
to be attributed to an electric dipoledipole interaction, and the

Rc of the energy transfer was calculated to be about 32.8 A.

3.5

Compared with Ca2SiO4, Ca3B2O6 and Y3Al5O12, the unique host

CSB shows advantages in color balance. The trichromatic colors
were balanced well in it and a white light emitting phosphor
was obtained by reducing the as-prepared CSB:0.02Ce,0.005Eu
powder at 700
C for 8 h. The excellent ability of CSB in color
balance was supposed to be attributed to the group synergy
eect. This work also provides a novel and ecient method in
phosphor preparation and gives a new inspiration for the
exploration and selection of the host materials in the eld of
WLEDs applications.

Thermal stability

The thermal stability of the CSB:Ce3+,Eu2+,Eu3+ phosphors was

investigated. The temperature dependence of luminescence for
CSB:Ce3+,Eu2+,Eu3+ under 353 nm excitation is shown in Fig. 6.
When the temperature was increased to 100
C, the PL intensity
from the three emission centers Ce3+, Eu2+, Eu3+ decreased to
86.3%, 73.4% and 67.7% of the initial value, respectively. The
three emission centers have some dierences in their thermal
stability performance. However, they still show some synchronization and stability. The dierence is considered to be associated with the dierent contributions of the [SiO44] and
[BO33] groups to the three dierent emission centers in CSB
host. However, for the high power LED application, the interactions eect of dierent luminescent centers in a co-host
material still needs further investigation.
3.6 Quantum eciencies and CIE chromaticity coordinates
of Ca11(SiO4)4(BO3)2:Ce3+,Eu2+,Eu3+ phosphors
The quantum eciencies of selected samples are listed in
Table 1. Quantum eciencies of commercial RGB phosphors
under a UV light excitation and yellow phosphor Y3Al5O12:Ce3+
under a blue light excitation (465 nm) are also given as references. The quantum eciencies of CSB:0.02Eu3+ (lexc
394 nm), CSB:0.02Ce3+ (lexc 353 nm), and CSB:0.005Eu2+
(lexc 365 nm) reach 9.7%, 15.9%, and 5.3%, respectively. The
quantum eciency of the white emitting phosphor
CBS:0.02Ce,0.005Eu by Al reduced at 700
C (lexc 353 nm) is
2.4%. However, the quantum eciency can be improved by
controlling the particle size, size distribution, morphology, and
crystalline defects through optimization of the processing
conditions and composition.
The CIE chromaticity diagram of CSB:0.02Ce3+ (lexc
353 nm), CSB:0.005Eu2+ (lexc 365 nm) and CSB:0.02Eu3+
(lexc 394 nm) phosphors under UV light excitation are shown
in Fig. 7. The chemical compositions and the chromaticity
coordinates of the phosphors CSB:Ce3+,Eu2+,Eu3+ are listed in
Tables 1 and S1. The color tone of CSB:Ce, Eu can be tuned
from deep blue (0.154, 0.082) to green (0.162, 0.098) by doping
various concentrations of Ce and Eu. The CIE coordinate position moves controllably towards the white light-emitting region
depending on dierent reduction temperature.

Conclusions

Ce3+, Eu2+ and Eu3+ singly activated and Ce3+/Eu2+/Eu3+-coactivated Ca11(SiO4)4(BO3)2 (CSB) phosphors were synthesized by
aluminium reduction solid state reactions. Under UV light
excitation, Eu3+, Eu2+ and Ce3+ singly activated CSB phosphors

This journal is The Royal Society of Chemistry 2013

Acknowledgements
This work was supported by the National 973 and 863 Program
of China (Grant no. 2011AA050505, 2009CB939903), NSF of
China (Grant no. 91122034, 51125006, 51102263, 61076062,
21101164), and STC of Shanghai (Grant no. 10JC1415800).

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