PAPER www.rsc.

org/materials | Journal of Materials Chemistry

Color-control of long-lasting phosphorescence (LLP) through rare earth

ion-doped cadmium metasilicate phosphors
Yingliang Liu,*a Jinyong Kuang,a Bingfu Leia and Chunshan Shib
Received 1st June 2005, Accepted 13th July 2005
First published as an Advance Article on the web 9th August 2005
DOI: 10.1039/b507774e

We report on a novel luminescent phenomenon in one-component cadmium metasilicate

phosphors doped with various rare earth ions. After irradiation by a 254 nm ultraviolet lamp,
these phosphors emit bright long-lasting phosphorescence (LLP), and their phosphorescence can
be seen with the naked eye (0.32 6 1023 cd m22) in the darkroom clearly for 2–5 hours even after
the irradiation light sources have been removed. Furthermore, color-control of the LLP is also
available in these cadmium metasilicate luminescent materials. By selecting appropriate rare earth
ions single or double doped into cadmium metasilicate, optional three-dimensional image patterns
emitting LLP in various colors, covering most of the visible light region from short wavelength
indigo blue to long wavelength deep red, can be formed under the same wavelength ultraviolet
light excitation. X-Ray diffraction (XRD), photoluminescence (PL), long-lasting
phosphorescence (LLP), and thermostimulated luminescence (TSL) spectra are used to
characterize the synthesized phosphors. PL and LLP spectra reveal that there are two different
kinds of LLP emissions in RE3+-doped CdSiO3 (the y420 nm self-trapped excitation (STE)
emission and the characteristic rare earth ions emissions). It is found that these two kinds of
emissions are the origin of the multi-colored LLP phenomenon in these phosphors. The finding
has enlarged the family of long-lasting phosphors available, and offers a promising approach for
controlling the LLP color of other materials.

1. Introduction and silicate-base luminescent host lattices which can be used

for glass components, have attracted more and more attention
The long-lasting phosphorescence (LLP) phenomenon, the and have been developed rapidly to replace the conventional
persistent emission of light by a material after it has been long-lasting phosphorescent materials.6–14
exposed to ultraviolet light, femtosecond laser, X-rays, or At present, the best performance of long-lasting phos-
some other method of excitation, has fascinated people since phorescent materials is still exhibited by Eu2+-doped alkali-
ancient times. The first record of a long-lasting phosphorescent earth aluminate phosphors, for example, SrAl2O4 : Eu2+,Dy3+
material which was found in nature is in the Song Dynasty (green), CaAl2O4 : Eu2+,Nd3+ (blue), and Eu3+-doped oxysul-
of China (11th century A.D.).1 Around 1600, Galilei was fide yttrium, Y2O2S : Eu3+,Ti4+,Mg2+ (red).5,15 Theoretically,
attracted by the Stone of Bologna, which emits yellow to we can get any color emitting long-lasting phosphorescence
orange LLP when subjected to sunlight. Without knowing by mixing three primary color (RGB) emitting long-lasting
the physical processes, Galilei excluded mystery as the origin phosphors which have similar physical and chemical pro-
of that phenomenon. In 1671, by heating the mineral with perties. Nevertheless, it is very difficult to fabricate these
carbon black, Kirchner was able to intensify the luminescence, persistent phosphors (RGB) which have similar phos-
indicating that impurity-type luminescence of BaS, not BaSO4, phorescence decay ratios to ensure LLP color purity all the
is the origin of the LLP phenomenon.2,3 time. In addition, most of the tricolor long-lasting phosphors
For more than one century, sulfide phosphors have been in currently available cannot be efficiently excited in the same
use as long-lasting phosphors and widely studied as lumines- given wavelength range.
cent host lattices. However, sulfide phosphors are not stable Until now, the LLP phenomenon has been assumed to be
and bright enough for many applications.4 So there has been a due to the thermostimulated recombination of holes and
great demand for new type host lattice substitutes in recent electrons which leave electrons or holes in a metastable
years. In 1996, Matsuzawa et al. firstly reported the green state at room temperature, so long-lasting phosphorescent
and blue emitting LLP phenomenon from Eu2+-doped materials are also called electron–hole trapping materials or
alkaline earth aluminates.5 Since then, oxide-based long- energy-storing materials.16,17 In general, the origin of the LLP
lasting phosphorescent materials, especially aluminate-base processes can be divided into three sequential steps, i.e., energy
storage, energy transfer, and energy release. The electron–hole
a
Department of Chemistry, Jinan University, Guangzhou, 510632, trapping mechanism plays an essential role in these materials.
People’s Republic of China. E-mail: [email protected]
b In our recent work, CdSiO3 was adopted as a luminescent
Key Laboratory of Rare Earth Chemistry and Physics, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences, host lattice,18 the phase structure of which is similar to that of
Changchun, Jilin, 130022, People’s Republic of China pseudo-wollastonite CaSiO3. The crystal structure of CdSiO3

This journal is ß The Royal Society of Chemistry 2005 J. Mater. Chem., 2005, 15, 4025–4031 | 4025
is expected to be one-dimensional chains of edge-sharing SiO4
tetrahedra. In this kind of low dimensional structure, it is
very easy to implant other ions into the host lattice and create
traps located at suitable depths that can store the excitation
energy and emit light at room temperature.19–21 In this study,
the LLP phenomenon is reported in various rare earth ion-
doped cadmium metasilicate phosphors. Moreover, color-
control of the LLP (covering most of the visible light region
from short wavelength indigo blue to long wavelength deep
red) through different rare earth ion-doped one-component
CdSiO3 host lattices is available under the same ultraviolet
light excitation. The luminescent properties and possible
mechanism of this kind of long-lasting phosphorescence were
investigated in detail.

2. Experimental
Powder samples were synthesized using the conventional solid- Fig. 1 XRD patterns of 5% Y3+-doped CdSiO3 phosphor of this
state reaction method. The starting materials were high-purity work (top) and JCPDS Card No. 35-0810 (below).
CdCO3, SiO2, and RE2O3 (.99.9%). The RE3+ ion doping
level of all the samples was fixed as 5 mol% of Cd2+ ions in the By comparing the spectra in Fig. 1, we can conclude that our
CdSiO3 host. After the corresponding raw materials were samples are chemically and structurally CdSiO3. It is expected
taken in a stoichiometric ratio and homogenized thoroughly that the phase structure of CdSiO3 is similar to that of pseudo-
(all the grinding was done with an agate pestle and mortar), the wollastonite CaSiO3. The configurations of both Ca and Cd
mixture was successively heat-treated at several conditions of have very similar outermost shells, 4s2 for calcium and 4d105s2
temperature and duration time using alumina crucibles with for cadmium, and their ionic radii are very close in size, 0.099
alumina lids in an air atmosphere, followed by subsequent air and 0.097 nm for calcium and cadmium, respectively. The
cooling to obtain the products. RE3+ ions (rRE3+ 5 0.085–0.106 nm) are expected to occupy
The structures of all synthesized polycrystalline powder the Cd2+ sites in the CdSiO3 host lattice and no RE3+ ion is
samples were checked by a Rigaku Model D/max-II B X-ray expected to occupy the Si4+ sites (rSi4+ 5 0.041 nm).
diffractometer with Cu Ka1 (l 5 0.15405 nm) radiation at a
0.02u (2h) min21 scanning step. 3.2. PL properties of undoped CdSiO3 and rare earth-doped
The photoluminescence spectra were obtained at room CdSiO3 phosphors
temperature with a Hitachi F-4500 fluorescence spectro-
photometer equipped with a monochromator (resolution: The PL of the undoped CdSiO3 sample is shown in Fig. 2.
0.2 nm) and 150 W Xe lamp as the excitation source. Only one broad band located at 243 nm can be observed in the
Suitable filters were used to correct for the baseline shift due excitation range. In the emission spectrum of the undoped
to any stray light. The long-lasting phosphorescence (LLP) CdSiO3 sample, there are three primary emission bands
emission spectra were measured on the same Hitachi F-4500 located at 380 nm, 467 nm, and 560 nm in the region ranging
fluorescence spectrophotometer.
The luminescent lifetime was measured with a Model 4400
Signal Detection and Analysis System (EG&G) using a 337 nm
nitrogen laser as the excitation source.
Thermostimulated luminescence (TSL) measurements
were performed by heating the irradiated sample from room
temperature to 673 K using a FJ-427A1 TL meter (Beijing
Nuclear Instrument Factory). Samples were first excited for
5 min using a 254 nm UV standard lamp with a power of 15 W.
Then the radiation source was removed and the samples were
heated at a linear rate of 2 K s21.
All measurements were carried out at room temperature
except for the TSL spectra.

3. Results and discussion

3.1. X-Ray crystal-structure analysis
The X-ray diffraction patterns of the 5% Y3+-doped CdSiO3 Fig. 2 Emission spectrum (solid line, lex 5 243 nm) and excitation
sample (concentration quenching occurs when Y3+ is doped at spectrum (dot line, lem 5 560 nm) of the undoped CdSiO3 host
above 5%) and JCPDS Card No. 35-0810 are shown in Fig. 1. compared to the human eye color sensitivity curve.

4026 | J. Mater. Chem., 2005, 15, 4025–4031 This journal is ß The Royal Society of Chemistry 2005
Fig. 3 Excitation spectra (lem 5 420 nm, dot line) and emission
Fig. 4 Excitation spectra (lem 5 420 nm, dot line) and emission
spectra (lex 5 243 nm, solid line) of CdSiO3 : RE3+ phosphors. RE 5 Y,
spectra (lex 5 243 nm, solid line) of CdSiO3 : RE3+ phosphors.
La, Gd, Lu.
RE 5 Ce, Nd, Ho, Er, Tm, Yb.

from 300 nm to 700 nm. These three emission peaks are similar
Lu3+-doped samples. Moreover, there are still not any obvious
to those previously reported in the Si+-implanted thermal SiO2
films on crystalline silicon under ultraviolet excitation at room characteristic rare earth ion emissions from these six samples
temperature.22 The above PL spectrum measurement reveals under excitation in the region of 200–400 nm. Is the role of
that CdSiO3 is a new self-activated luminescent host lattice. Ce3+, Nd3+, Ho3+, Er3+, Tm3+, Yb3+ the same as that of Y3+,
For the convenience of the following section discussion, the La3+, Gd3+ and Lu3+ doped into the CdSiO3 host lattice?
human eye color sensitivity curve is also given in Fig. 2. Fig. 5 presents the emission spectra and excitation spectra of
Ions with no 4f electrons, i.e., Y3+, La3+, and Lu3+, have the other five earth ions, as Pr3+, Sm3+, Eu3+, Tb3+ and Dy3+
no electronic energy levels that can induce excitation and single-doped CdSiO3 phosphors under excitation at 243 nm
luminescence processes in or near the visible region. Generally, and monitored at 420 nm. For the excitation spectra, only the
these ions are used as host lattice elements in various 243 nm excitation broad band can be seen when monitored
luminescent materials. Here, we adopted Y3+, La3+, Lu3+, at their y420 nm broad band. However, in this group, these
and Gd3+ ions as ‘‘activator’’ in the CdSiO3 host lattice. Fig. 3 five rare earth ion single-doped CdSiO3 phosphors show their
gives the excitation spectra and emission spectra of CdSiO3 characteristic f–f emission line spectra besides the y420 nm
phosphors doped with Y3+, La3+, Lu3+, and Gd3+ ions, broad band luminescence.
respectively. All of them consist of one broad band located It is known that energy absorption need not necessarily take
at y420 nm in the emission range. The emission band can be place at the activator ions itself but can occur at a random
attributed to a localized electron–hole pair, a self-trapped place in the host lattice. This implies that energy transfer of the
excitation (STE), which is enhanced by the incorporation of absorbed energy to the luminescent center takes place before
RE3+ ions occupying the Cd2+ sites.23,24 It is worth noting that emission can occur.25 The migration of the energy absorbed
the 243 nm excitation broad band also exists in these four by the host lattice can take place through one of the four
phosphors but their emission spectra are different from the processes, i.e. electric charge (electrons, holes), excitons,
above-mentioned undoped CdSiO3 sample, indicating that resonance (overlap), and sensitizer. In our present case, it is
the incorporation of RE3+ (RE 5 Y, La, Gd, Lu) ions into the clear from the PL spectra that in the Pr3+, Sm3+, Eu3+, Tb3+
CdSiO3 host does change their luminescent properties. and Dy3+ single-doped CdSiO3 phosphors, energy transfer
Fig. 4 shows the emission spectra and excitation spectra of from the host to the Pr3+, Sm3+, Eu3+, Tb3+ and Dy3+ activator
Ce3+, Nd3+, Ho3+, Er3+, Tm3+, and Yb3+ single-doped CdSiO3 ions occurs. When illuminated by a UV light excitation source,
phosphors under excitation at 243 nm and monitored 420 nm. excitation energy is absorbed by the host and created the STE
Surprisingly, no obvious characteristic emission of the Ce3+, emission (the y420 nm broad band), meanwhile, the absorbed
Nd3+, Ho3+, Er3+, Tm3+, and Yb3+ ions can be detected in energy from the STE state is transferred to the Pr3+, Sm3+,
the visible light region except the same broad band located Eu3+, Tb3+ and Dy3+ ions and created the typical emission of
at y420 nm, which is similar to those of Y3+, La3+, Gd3+ and these five rare earth ions. To prove that there exists energy

This journal is ß The Royal Society of Chemistry 2005 J. Mater. Chem., 2005, 15, 4025–4031 | 4027
 Fig. 6 a) Long-lasting phosphorescence spectra of CdSiO3 : RE3+
(RE 5 Y, Nd, Eu, Tb) phosphors after the 254 nm UV excitation
source is stopped at 1 min. b) Long-lasting phosphorescence spectra of
CdSiO3 : RE3+ phosphors after the 254 nm UV excitation source is
stopped at different times (t 5 2, 4, 9 min).

Fig. 5 Excitation spectra (lem 5 420 nm, dot line) and emission
spectra (lex 5 243 nm, solid line) of CdSiO3 : RE3+ phosphors.
RE 5 Pr, Sm, Eu, Tb, Dy.

transfer, time-resolved spectra or fluorescence decay measure-

ments are essential. The fluorescence lifetime measurement
revealed that the lifetime of the 580 nm characteristic emission
of Dy3+ (4F9/2–6H13/2) in the CdSiO3 phosphor was 107 ns and Fig. 7 Long-lasting phosphorescence photographs of the rare-earth
that of the 420 nm STE emission was 102 ns.26 ions single and double-doped CdSiO3 phosphors. These photographs
were taken in the darkroom for 5 min after the removal of the 254-nm
3.3. Phosphorescence properties of rare earth-doped CdSiO3 ultraviolet lamp.
phosphors
through different rare earth ions double-doped in a one-
A very important result of our present work is that we have
component CdSiO3 host lattice.
developed multi-color LLP in rare earth ion doped CdSiO3
phosphors. Fig. 6(a) shows the LLP spectra of the Y3+, Nd3+,
3.4. Defects properties of rare earth-doped CdSiO3 phosphors
Eu3+, and Tb3+ single-doped CdSiO3 phosphors for 1 min after
stopping the 254 nm UV excitation source; while Fig. 6(b) It is known that electron–hole trapping centers play an
shows the LLP decay spectra of the Gd3+ and Sm3+ at different essential role for photo-energy storage in persistent, photo-
times (t 5 2, 4, 9 min) after stopping the 254 nm UV excitation stimulable, and thermostimulable phosphors.27,28 Usually,
source. As is shown in Fig. 6(b), the shapes of the LLP decay information of trap depth can be obtained by thermostimu-
curves are similar except for the intensity. These results clearly lated luminescence (TSL) measurements.29 Moreover, the TSL
indicate that the LLP color purity in this kind of phosphor intensity is also proportional to the densities of the trapping
remains the same in the long decay period. carriers. In order to obtain excellent long-lasting phosphores-
By comparing the LLP spectra with the above steady-state cence, the incorporation of auxiliary ions that have different
UV-excited fluorescence spectra (Fig. 3–5), we found that the valences and ionic radii from the host cations is often
shape and bandwidth of the LLP spectra were identical with undertaken (SrAl2O4 : Eu2+,Dy3+; CaAl2O4 : Eu2+,Nd3+;
those steady-state UV-excited fluorescence spectra. These Y2O2S : Eu3+,Ti4+,Mg2+ etc.). This aliovalent incorporation
properties indicate that the radiating centers in both cases can lead to foreign defects in the host lattice, which act as
are identical. trapping centers and have a significant influence on the LLP
Fig. 7 shows the LLP emission color photographs of rare performance.30 To the best of our knowledge, the TSL
earth ion single and double doped CdSiO3 phosphors for 5 min dominant peaks are situated slightly above room temperature
after the removal of the 254 nm ultraviolet lamp. As is shown (323–393 K) if materials show excellent long-lasting phosphor-
in Fig. 7, we can easy get multi-color (covering most of escence performance.5,31 Hence, the trap depth and the trap
the visible light region from short wavelength indigo blue to density will influence the LLP performance of the phosphor.
long wavelength deep red) from RE3+ single-doped CdSiO3 Fig. 8 shows the TSL curves of the undoped CdSiO3 and the
samples. Furthermore, color-control of LLP is also available Y3+, Nd3+, Sm3+, Eu3+, Tb3+ single-doped CdSiO3 phosphors.

4028 | J. Mater. Chem., 2005, 15, 4025–4031 This journal is ß The Royal Society of Chemistry 2005
 leave electrons or holes in a metastable state at room
temperature.16 After irradiation by light illumination, free
electrons and holes are formed in the samples. The holes or
electrons were trapped by different defect centers, released by
heat at room temperature, and recombined with electrons or
holes trapped by other defect centers. The released energy due
to the recombination of holes and electrons is transferred to
the rare earth ions and excites the electrons at the ground state
of the rare earth ions to the excited state, finally leading to the
characteristic rare earth ion emissions. Because there are two
different kinds of LLP emissions in RE3+-doped CdSiO3 (the
y420 STE emissions and the characteristic rare earth ion
emissions), two different processes may be required to be taken
into account when trying to explain the LLP phenomenon of
these phosphors.
In order to explain the characteristic emissions of the Eu3+,
Fig. 8 Thermostimulated luminescence curves of CdSiO3 : RE3+
Pr , Sm3+, Tb3+, Dy3+ single-doped CdSiO3 host lattice, some
3+
(RE 5 Y, Nd, Sm, Eu, Tb) and the undoped CdSiO3 host (inset). The
extra work must be carried out. In general, an impurity is
heating rate was 2 K s21.
usually added into luminescent materials as a sensitizer whose
emission band overlaps with the absorption band of the
As shown in the inset of Fig. 8(b), the TSL curve of the
activator, thus the energy transfers from the former to the
undoped CdSiO3 is found to be composed of two peaks
latter.34 For example, all Tb3+-activated phosphors currently
located at 346 and 418 K, respectively. These peaks can be
used in fluorescent lamps are sensitized by Ce3+. It is also
attributed to the intrinsic defects in the CdSiO3 host lattice.
reported that in the CaAl2O4 : Ce3+,Tb3+ long-lasting
Upon the incorporation of the Y3+, Nd3+, Sm3+, Eu3+, Tb3+
ions into the CdSiO3 host lattice, only one predominating phosphor, energy can transfer from Ce3+ to Tb3+ creating the
broad band located at y348 K can be observed, indicating LLP phenomenon of Tb3+ emission.35 In the CdSiO3 : Eu3+
that the trap depth levels in these materials are roughly phosphor, because the emission band of the host overlaps with
the same. the Eu3+ absorption, energy can transfer from the host to the
In our present work, trivalent RE3+ ions not only play the Eu3+ (Fig. 9). However, for the case of Pr3+, Sm3+, Tb3+, Dy3+
role of activator, but also act as an aliovalent auxiliary dopant single-doped CdSiO3 phosphors, obvious overlap bands are
to create defects. When trivalent RE3+ is doped into the not found in the 300–500 nm region, but luminescent lifetime
CdSiO3 host lattice, they would chemically nonequivalently measurements revealed that the lifetime of this rare earth
substitute the Cd2+ sites. Due to these nonequivalent substitu- characteristic emission was 107 ns while the 420 nm STE
tions, an excess of positive charge in the lattice must be emission was 102 ns.
compensated. There are two possible patterns to fulfil the LLP materials are actually a kind of electron–hole trapping/
charge compensation of the RE3+-doped CdSiO3 phosphors. energy-storing materials, whose working processes are similar
One possible way is that two RE3+ ions replace three Cd2+ ions to the rechargeable battery. In general, the LLP processes can
to balance the charge of these phosphors, which create two be divided into three sequential steps, i.e., energy storage,
REuCd positive defects and one V0Cd negative defect.32,33 energy transfer, and energy release. Based on previous reports

2RE3+ + 3Cd2+ A 2REuCd + V0Cd

The other possibility of the charge compensation is vacancies of

Cd2+ (V0Cd ) created during the synthesis process, which is also
feasible because of the relatively high vapor pressure of the Cd2+
component. In the present case, the introduction of RE3+ ions into
the CdSiO3 host produces a suitable trap depth at y348 K, which
makes an important contribution to the LLP phenomenon in this
kind of material.

3.5. Possible mechanism of LLP phenomenon in rare earth-

doped CdSiO3 phosphors
On the basis of the above-discussed results, we are trying to
explain the possible mechanism of the LLP phenomenon in all
rare earth-doped CdSiO3 phosphors through a simple model in
the following section.
The LLP phenomenon is assumed to be due to the Fig. 9 Excitation spectra (lem 5 613 nm) and emission spectra
thermostimulated recombination of holes and electrons which (lex 5 243 nm) of CdSiO3 : Eu3+ phosphor.

This journal is ß The Royal Society of Chemistry 2005 J. Mater. Chem., 2005, 15, 4025–4031 | 4029
 the mechanism of these long-lasting phosphors. These novel
one-component long-lasting phosphors, CdSiO3 : RE3+, are
prepared by the conventional high-temperature solid state
method. After irradiation by 254 mm UV light, these phosphors
emit bright long-lasting phosphorescence, and their phosphor-
escence can be seen with the naked eye (0.32 6 1023 cd m22)
in the darkroom clearly for 5 hours even after the irradiation
light sources have been removed.
When rare earth ions such as Y3+, La3+, Gd3+, Lu3+; Ce3+,
Nd3+, Ho3+, Er3+, Tm3+ and Yb3+ are introduced into the
CdSiO3 host lattice, only one broad band located at y420 nm
resulting from the STE trap emission can be observed. In the
cases of other rare earth ions such as Pr3+, Sm3+, Eu3+, Tb3+
and Dy3+ single-doped CdSiO3 host lattices, the characteristic
Fig. 10 An electron–hole recombination model of the possible emissions of these five rare earth ions can be obtained as well
processes of the RE3+-doped CdSiO3 long-lasting phosphors. as the y420 nm STE trap emission. We are confident that, by
selecting different doping ions, changing the host composi-
about the mechanisms of the persistent luminescence of Eu2+- tions, choosing appropriate codoping ions or adding some
doped alkaline earth aluminates,5–8,16 the complex lumines- other energy captor, it is expected that long-lasting phosphors
cence process of CdSiO3 : RE3+ long-lasting phosphor can be possessing more different LLP color even for full colorization
simply illustrated by Fig.10. The band gap of the CdSiO3 can be obtained. Moreover, these rare earth ion-doped CdO–
materials is about 41000 cm21, corresponding to the 243 nm SiO2 materials may be used as a component of silicate-based
host absorption band. Cadmium vacancies V0Cd produced glasses that show long-lasting phosphorescence.
during the high temperature synthesis process may be one of
the hole trapping centers, and the REuCd site impurity trap may Acknowledgements
serve as the electron trap.
As shown in Fig. 10, the different processes resulting in the The authors are grateful to Mr Xuan Li and Miss Meishan Ou
LLP phenomenon of RE3+-doped CdSiO3 can be treated as a of the College of Life Science and Technology, Jinan
preliminary and qualitative result, and can be summarized as University, for their great help. This present work was
supported by the National Natural Science Foundation of
follows. Upon the exposure to the 243 nm UV light (step 1), a
China (Grant Nos. 50472077 and 20171018), the Natural
hole trap and electron trap are formed in the valence band
Science Foundation of Guangdong Province (Grant Nos.
edge and in the conduction band edge (steps 2a and 2b). The
013201 and 36706).
following process is the formation of a STE, which is shown as
steps 3a and 3b. The electron trap is an energy state of storing
excited electrons; energy can be stored in the excited period. References
Because the electron trap is a metastable state, the electrons 1 E. N. Harvey, A History of Luminescence, American Philosophical
captured by this electron trap can be released thermally at Society, PA, 1957, p. 18.
room temperature and result in the STE trap emission after 2 E. Gubelin, International World of Gemstones, ABC-Verlag,
Zurich, 1974.
stopping the UV excitation source. This is the origin of the 3 C. Feldmann, T. Justel, C. R. Ronda and P. J. Schmidt, Adv.
STE trap LLP emission in the Y3+, La3+, Gd3+ and Lu3+ single- Funct. Mater., 2003, 13, 511.
doped CdSiO3 phosphors (step 4a). 4 S. Shionoya and W. M. Yen, Phosphor Handbook, CRC Press,
Boca Raton, 1999.
For the case of Pr3+, Sm3+,Em3+, Tb3+, Dy3+ single-doped
5 T. Matsuzawa, Y. Aoki, N. Takeuchi and Y. Murayama,
CdSiO3 samples, characteristic LLP emissions of these five J. Electrochem. Soc., 1996, 143, 2670.
rare earth ions can be observed besides the STE trap LLP 6 T. Katsumata, K. Sasajima, T. Nabae, S. Komuro and
emission. It is expected that energy transfer from the STE to T. Morikawa, J. Am. Ceram. Soc., 1998, 81, 413.
7 J. Qiu, K. Miura, H. Inouye, Y. Kondo, T. Mitsuyu and K. Hirao,
these five rare earth ions occur via a direct or non-radiation Appl. Phys. Lett., 1998, 73, 1763.
process (step 4b). The STE trap emission and energy transfer 8 N. Kodama, T. Takahashi, M. Yamaga, Y. Tanii, J. Qiu and
to Pr3+, Sm3+, Eu3+, Tb3+, Dy3+ are the origin of the LLP K. Hirao, Appl. Phys. Lett., 1999, 75, 1715.
phenomenon in these five rare earth ion single-doped CdSiO3 9 J. Fu, Electrochem. Solid-State Lett., 2000, 3, 350.
10 Y. Lin, Z. Tang, Z. Zhang and C. Nan, J. Alloys Compd., 2003,
phosphors. However, for the cases of Ce3+, Nd3+, Ho3+, Er3+, 348, 76.
Tm3+, and Yb3+ single-doped CdSiO3 phosphors, there is no or 11 C. C. Kang, R. S. Liu, J. C. Chang and B. Lee, Chem. Mater.,
low absorption in the STE region, therefore only the STE trap 2003, 15, 3966.
12 T. Aitasalo, P. Deren, J. Holsa, H. Jungner, J. C. Krupa,
LLP emission can be observed in these cases. M. Lastusaari, J. Legendziewicz, J. Nittykoski and W. Strek,
J. Solid State Chem., 2003, 171, 114.
4. Conclusions 13 J. Y. Kuang and Y. L. Liu, Chem. Lett., 2005, 34, 598.
14 Y. H. Lin, Z. L. Tang, Z. T. Zhang, X. X. Wang and J. Y. Zhang,
J. Mater. Sci. Lett., 2001, 20, 1505.
We have developed novel multi-colored long-lasting phos-
15 Y. Murazaki, K. Arai and K. Ichinomiya, Jpn. Rare Earths, 1999,
phorescence in rare earth ion doped CdSiO3 phosphors and 35, 41 (in Japanese).
proposed an electron–hole recombination model to interpret 16 J. Qiu and K. Hirao, Solid State Commun., 1998, 106, 795.

4030 | J. Mater. Chem., 2005, 15, 4025–4031 This journal is ß The Royal Society of Chemistry 2005
17 C. Y. Li and Q. Su, Appl. Phys. Lett., 2004, 85, 2190. 26 Y. L. Liu, B. F. Lei and C. S. Shi, Chem. Mater., 2005, 17,
18 B. F. Lei, Y. L. Liu, J. Liu, Z. R. Ye and C. S. Shi, J. Rare Earths, 2108.
2004, 22, 443. 27 D. Jia, W. Jia, D. R. Evans, W. M. Dennis, H. Liu, J. Zhu and
19 E. Danielson, M. Devenney, D. M. Giaquinta, J. H. Golden, W. M. Yen, J. Appl. Phys., 2000, 88, 3402.
R. C. Haushalter, E. W. McFarland, D. M. Poojary, C. M. Reaves, 28 H. Yamamoto and T. Mastusuzawa, J. Lumin., 1997, 72, 287.
W. H. Weinberg and X. D. Wu, Science, 1998, 279, 837. 29 S. W. S. Mckeever and R. Chen, Radiat. Meas., 1997, 27, 625.
20 L. Zhang, G. Y. Hong and X. L. Sun, Chin. Chem. Lett., 1999, 10, 30 K. S. Sohn, S. Y. Seo and H. D. Park, Electrochem. Solid-State
799. Lett., 2001, 4, H26.
21 L. Zhang and G. Y. Hong, J. Synth. Crystals, 1999, 28, 204 31 T. Z. Zhang, Q. Su and S. B. Wang, Chin. J. Lumin., 1999, 20, 170
(in Chinese). (in Chinese).
22 L. Liao, X. Bao, N. Li, X. Zheng and N. Xin, J. Lumin., 1996, 68, 32 J. Wang, S. B. Wang and Q. Su, J. Mater. Chem., 2004, 14,
199. 2569.
23 B. F. Lei, Y. L. Liu, Z. R. Ye and C. S. Shi, Chem. Lett., 2003, 32, 33 B. F. Lei, Y. L. Liu, J. Liu, Z. R. Ye and C. S. Shi, J. Solid State
904. Chem., 2004, 177, 1333.
24 P. B. Allen and V. Perebeinos, Phys. Rev. Lett., 1999, 83, 4828. 34 D. L. Dexter, J. Chem. Phys., 1953, 21, 836.
25 T. Justel, H. Nikol and C. Ronda, Angew. Chem., Int. Ed., 1998, 35 D. Jia, R. S. Meltzer and W. M. Yen, Appl. Phys. Lett., 2002, 80,
37, 3084. 1535.

This journal is ß The Royal Society of Chemistry 2005 J. Mater. Chem., 2005, 15, 4025–4031 | 4031