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Solgel synthesis and photoluminescence properties of spherical SiO2@LaPO4:Ce3+/Tb3+ particles with a coreshell structure

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2006 Nanotechnology 17 3245 (http://iopscience.iop.org/0957-4484/17/13/028) View the table of contents for this issue, or go to the journal homepage for more

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INSTITUTE OF PHYSICS PUBLISHING Nanotechnology 17 (2006) 32453252

NANOTECHNOLOGY doi:10.1088/0957-4484/17/13/028

Solgel synthesis and photoluminescence properties of spherical SiO2@LaPO4:Ce3+/Tb3+ particles with a coreshell structure
M Yu1,2 , H Wang1,2 , C K Lin1 , G Z Li2 and J Lin1,3
1

Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Peoples Republic of China 2 Department of Chemistry, Northeast Normal University, Changchun 130024, Peoples Republic of China E-mail: jlin@ciac.jl.cn

Received 20 February 2006, in nal form 7 May 2006 Published 7 June 2006 Online at stacks.iop.org/Nano/17/3245 Abstract LaPO4 :Ce3+ and LaPO4 :Ce3+ , Tb3+ phosphor layers have been deposited successfully on monodispersed and spherical SiO2 particles of different sizes (300, 500, 900 and 1200 nm) through a solgel process, resulting in the formation of coreshell structured SiO2 @LaPO4 :Ce3+ /Tb3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microcopy (SEM), transmission electron microscopy (TEM), and general and time-resolved photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO2 @LaPO4:Ce3+ /Tb3+ samples. The XRD results demonstrate that the LaPO4 :Ce3+ , Tb3+ layers begin to crystallize on the SiO2 templates after annealing at 700 C, and the crystallinity increases on raising the annealing temperature. The obtained coreshell phosphors have perfectly spherical shape with a narrow size distribution, non-agglomeration, and a smooth surface. The doped rare-earth ions show their characteristic emission in the coreshell phosphors, i.e. Ce3+ 5d4f and Tb3+ 5 D4 7 F J ( J = 63) transitions, respectively. The PL intensity of the Tb3+ increased on increasing the annealing temperature and the SiO2 core particle size. The energy transfer process from Ce3+ to Tb3+ in SiO2 @LaPO4:Ce3+ , Tb3+ coreshell particles was studied using the time-resolved emission spectra. (Some gures in this article are in colour only in the electronic version)

1. Introduction
In recent years, tremendous effort has been devoted to the design and controlled fabrication of nanostructured materials with functional properties. Among them, coreshell structured materials have been attracting much attention due to the ability to ne-tune their properties [110]. Coreshell materials consist of a core structural domain covered by a shell domain,
3 Author to whom any correspondence should be addressed.

both of which may be composed of a variety of materials including polymers, inorganic solids, and metals. In general, the preparation of coreshell structures involves the surface modication of particles, often accomplished by coating or encapsulating them with a different material having the desired properties [1]. So far, considerable kinds of coreshell structures have been designed and fabricated, including semiconductor/semiconductor [11], semiconductor/dielectric [12], metal/dielectric [13], metal/semiconductor [14], inorganic particle/polymer [1], and polymer or inorganic parti3245

0957-4484/06/133245+08$30.00

2006 IOP Publishing Ltd Printed in the UK

M Yu et al

cle/biomolecule [1] etc. The structure, size, and composition of these particles can easily be altered in a controllable way to tailor their magnetic, optical, mechanical, thermal, electrical, electro-optical, and catalytic properties. A variety of approaches have been employed for the manufacture of core shell structured materials, such as co-precipitation [10, 15], layer-by-layer self-assembly [1, 6, 8, 16], surface reaction [17], solgel processing [5, 18] and metal-organic chemical vapour deposition (MOCVD) [19]. Each of these procedures has its own advantages, disadvantages and applicability. The controlled coating of particles with homogeneous and organized layers without causing aggregation remains a challenge for scientists [1]. Newly developed display technologies such as plasma display panels (PDPs) and eld emission displays (FEDs) have brought forward new requirements for the morphology of phosphor materials [20]. The ideal morphology of phosphor particles includes a perfectly spherical shape, a narrow size distribution (0.52 m), and non-agglomeration. A spherical morphology of the phosphors is good for high brightness and high resolution. Additionally, high packing densities and low scattering of light can also be obtained by using spherical phosphors [21]. So far, many synthetic routes have been developed to control the size and distribution of phosphor particles, such as spray pyrolysis [22] and urea homogeneous precipitation [21a], but the phosphor particles that have been obtained are still far away from the ideal morphology. Silica can be fabricated controllably into a spherical morphology of nano- to micron size [23], and it is frequently used in coreshell structured materials, as either a core or a shell [8, 9, 13, 18]. If the silica spheres are coated with phosphor layers, a kind of coreshell phosphor material with spherical morphology will be obtained, and the size of the phosphor particles can be controlled by the silica core and the number of coating cycles. Furthermore, because silica is cheaper than most phosphor materials (which often employ expensive rare-earth elements as the activators and/or host components), coreshell phosphor materials will be cheaper than pure phosphor materials to some degree. Lanthanum phosphate (LaPO4 , monazite) has been shown to be a useful host lattice for rare-earth ions to produce phosphors emitting a variety of colours [2427]. Ce3+ and Tb3+ -coactivated bulk LaPO4 is a highly efcient and commercially applied green (5 D4 7 F5 of Tb3+ at 543 nm) phosphor in uorescent lamps [27, 28]. The synthesis and optical properties of colloidal nanocrystals and thin lms of LaPO4 :Ce, Tb as well as LaPO4 :Eu3+ (Ce3+ , Tb3+ )/LaPO4 (coreshell) have been reported [29]. These nanocrystals can be conjugated to protein or assembled on polystyrene spheres for potential biological labelling applications [30]. Recently, the surface modication of Al2 O3 and SiO2 particles with Y2 O3 :Eu3+ and YVO4 :Eu3+ red phosphor layers, i.e. the preparation of Al2 O3 @Y2 O3 :Eu3+ , SiO2 @Y2 O3 :Eu3+ (YVO4 :Eu3+ ) coreshell structured phosphor particles via different chemical processes, has been reported by Shis group and by us, respectively [31a, 31b, 31c]. These kinds of coreshell phosphors, which maintain the morphology of the cores (homogeneous submicron spheres) and the luminescence properties of the shells (and can also be tuned by the thickness of the shell), are promising for applications in eld emission 3246

Table 1. Synthesis conditions of SiO2 particles with different sizes, where N is the number of reactions, t is the reaction time (in hours), and C is the concentration (mol l1 ). SiO2 300 nm 500 nm 900 nm 1200 nm

C [TEOS] C [H2 O] C [NH3 ] Seeds

0.17 0.2 0.2 0.2 7.5 5.0 5.0 6.0 1.0 7.0 7.0 2.0

VTEOS / V H2 O N t

500 nm 1/2 500 nm 1/2

2 5

3 3

displays, lamps for lighting, and plasma display panels. However, so far no reports have appeared concerning the surface modication of silica spheres with another important LaPO4 :Ce3+ /Tb3+ green phosphor, nor the effect of the SiO2 core size on the luminescent properties of the nal phosphors. Accordingly, as a continuation of our previous work [31b, 31c], in this paper we select silica spheres (with different sizes, ranging from 300 to 1200 nm) as cores and LaPO4 :Ce3+ /Tb3+ phosphor layers as shells, respectively, to obtain coreshell structured SiO2 @LaPO4 :Ce3+ and SiO2 @LaPO4 :Ce3+ , Tb3+ particles via the solgel process, and characterize their structure, morphology and photoluminescence and energy transfer properties in details.

2. Experimental section
2.1. Synthesis of silica cores The synthesis of highly monodisperse submicron SiO2 spheres was carried out following the well-known St ober method, i.e. the hydrolysis of tetraethoxysilane (TEOS) in an ethanol solution containing water and ammonia [23]. This method yielded the colloidal solution of silica particles with a narrow size distribution in the submicron range, and the particle size of silica depended on the relative concentration of the reactants. To prepare large monodisperse silica particles, it is necessary to grow silica seeds without the formation of new silica particles. In a typical experiment, the mixture containing TEOS (99 wt%, analytical reagent, AR), H2 O, and NH4 OH (25 wt%, AR) was stirred at room temperature for 4 h, resulting in the formation of a white silica colloidal suspension. The silica particles were centrifugally separated from the suspension and washed with ethanol four times. Monosize silica particles larger than 1 m in diameter could not be obtained directly through the St ober process, so seeded growth experiments were used [32]. In the seeded growth experiments, a certain amount of monosize silica particles was seeded into the NH3 H2 O-containing ethanol solution before the TEOS-containing ethanol was added to the reactor. The experimental procedure is similar to that of the St ober process. The experimental conditions for obtaining SiO2 particles with sizes of 300, 500, 900, and 1200 nm are listed in table 1. 2.2. Coating of SiO2 cores with LaPO4 :Ce3+ /T b3+ shells SiO2 coreLaPO4 :Ce3+ /Tb3+ shell particles (denoted as SiO2 @LaPO4 :Ce3+ /Tb3+ ) were prepared using a Pechini sol gel process [33]. Two kinds of samples with compositions of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 and SiO2 @La0.80 Ce0.20 PO4 were prepared [29f]. Stoichiometric amounts of La2 O3

Solgel synthesis and photoluminescence properties of spherical SiO2 @LaPO4 :Ce3+ /Tb3+ particles with a coreshell structure
OH HO HO HO OH OH

22.8

(a)
SiO2
OH OH

SiO2
200 120 012

SiO 2

Intensity (a.u.)

111

(b)
SiO2

SiO 2@La0.45Tb 0.15Ce0.40PO 4

PEG Citric acid

La3+

Ce3+,Tb3+

PO43:Polymer chains

(c)

La0.45Tb 0.15Ce 0.40PO 4

JCPDS 32-493A LaPO 4

(d)
O2POO OPO2 OPO2 O2PO O Ce O O O La OPO La O2PO O 2 O O O O OPO2 O2PO SiO2 O Ce O O Ce O OPO2 O2PO O O O O O La OPO2 La O2PO O O Tb O OPO2 O O2PO O2POO OPO2

10

20

30

40

50

60

70

2 (degree)

Figure 1. X-ray diffraction patterns for as-formed SiO2 (a), 1000 C-annealed SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell particles (b), pure La0.45 Tb0.15 Ce0.40 PO4 powders (c), and the JCPDS card 32-493A for LaPO4 (d).

2.3. Characterization
Surface SiO2 reaction 800oC

LaPO4:Ce3+,Tb3+

SiO2

Scheme 1. Formation process of SiO2 @LaPO4 :Ce3+ , Tb3+ coreshell particles.

(99.99%), Tb4 O7 (99.99%), and Ce(NO3 )3 6H2 O (99.99%), all from Shanghai Yuelong New Materials Co. Ltd, were dissolved in nitric acid (HNO3 , AR), and were then mixed with a waterethanol (v/v = 1:7) solution containing citric acid (AR) as chelating agent for the metal ions. The molar ratio of metal ions to citric acid was 1:2. The pH value of the solution was adjusted to 1 with HNO3 followed by the addition of a stoichiometric amount (NH4 )2 HPO4 (99%, AR). Then a certain amount of polyethylene glycol (PEG, molecular weight = 10 000, AR) was added as a cross-linking agent. The solution was stirred for 1 h to form a sol and then the silica particles were added under stirring. The suspension was further stirred for another 3 h, and then the silica particles were separated by centrifuging. Immediately, the samples were dried at 100 C for 1 h. The dried samples were annealed at 500 C for 2 h in a furnace with a heating rate of 60 C h1 . The preheated samples were annealed to the desired temperature (7001100 C), at a heating rate of 1 C min1 , and held there for 2 h in a reducing atmosphere of H2 (5%V) + N2 (95%V) mixture. The above process was repeated several times to increase the thickness of the LaPO4 :Ce3+ /Tb3+ shells. In this way, coreshell structured SiO2 @LaPO4 :Ce3+ /Tb3+ materials were obtained; the whole process is shown in scheme 1. For the purpose of comparison, the coating sol was evaporated to form powders, which were annealed using a similar process to produce pure LaPO4 :Ce3+ /Tb3+ powder phosphors.

X-ray diffraction (XRD) of the powder samples was examined on a Rigaku-Dmax 2500 diffractometer using Cu K radiation ( = 0.154 05 nm). FT-IR spectra were measured on a Perking-Elmer 580B infrared spectrophotometer using the KBr pellet technique. The morphology of the samples was inspected using a eld-emission scanning electron microscope (FE-SEM, the XL30 from Philips) and a transmission electron microscope (the JEOL-2010, 200 kV). The excitation and emission spectra were taken on a Hitachi F-4500 spectrouorimeter equipped with a 150 W xenon lamp as the excitation source. Time-resolved photoluminescence spectra and luminescence decay curves were obtained from a Lecroy Wave Runner 6100 Digital Oscilloscope (1 GHz) using a 286 nm laser (pulse width = 4 ns; gate = 50 ns) as the excitation source (Continuum Sunlite OPO). All measurements were performed at room temperature (RT).

3. Results and discussion

3.1. Formation and morphology of coreshell particles The formation and morphology of studied coreshell particles were performed representatively on SiO2 @La0.45 Tb0.15 Ce0.40 PO4 sample by XRD, FT-IR, FE-SEM and TEM, respectively. The results for SiO2 @La0.8 Ce0.2 PO4 are similar to those of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 and will not be performed further or shown here. 3.1.1. XRD. The XRD study revealed that both the asformed silica particles and the 500 C-annealed coreshell particles are amorphous, and that the coreshell particles begin to crystallize after annealing at 700 C. Figure 1 shows XRD patterns for (a) the as-formed SiO2 , (b) 1000 C-annealed SiO2 @La0.45 Tb0.15 Ce0.40 PO4 , (c) and pure La0.45 Tb0.15 Ce0.40 PO4 samples, as well as (d) JCPDS Card 32493A for LaPO4 as a reference. For SiO2 particles annealed at 1000 C (gure 1(a)), no diffraction peak is observed, except for a broad band centred at 2 = 22.80 , which is the 3247

M Yu et al

SiO2@La0.45Tb0.15Ce0.40PO4

(c)

La0.45Tb0.15Ce0.40PO4
950

(b)

OH

Si-OH

H2O

1100

807

SiO2

1643

(a)
Si-O
500 0
471

Si-O-Si
4000 3500 3000 2500 2000 1500 1000

Wavenumber (cm -1)

Figure 2. FT-IR spectra of the as-formed SiO2 (a), 1000 C-annealed La0.45 Tb0.15 Ce0.40 PO4 (b), and SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell samples (c).

characteristic peak for amorphous SiO2 (JCPDS 29-0085). For the SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell sample red at 1000 C (gure 1(b)), besides the broad band at 2 = 22.80 from amorphous SiO2 , peaks at 2 = 18.82 , 21.74 , 27.32 , 29.10 , 42.60 , 46.5 , and 48.96 are present, which are due to the (011), (101), (200), (120), (221), (312), and (132) reections of the crystalline lanthanum phosphate (monazite structure) respectively; all the diffraction peaks belonging to crystalline LaPO4 are present, suggesting that the coatings of La0.45 Tb0.15 Ce0.40 PO4 have crystallized well on the surfaces of amorphous silica particles. This is in good agreement with the situation for the pure La0.45 Tb0.15 Ce0.40 PO4 powder sample annealed at 1000 C (gure 1(c), in which highly crystalline LaPO4 is observed). No other phase is detected for SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell samples, even after annealing at 1100 C (which only increases the intensity of the diffraction peaks of LaPO4 to some extent, due to the improvement in crystallinity). Note that the diffraction peaks of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell sample are a little broader than those of the pure La0.45 Tb0.15 Ce0.40 PO4 powder, indicating that the size of the crystalline grains of La0.45 Tb0.15 Ce0.40 PO4 on the surfaces of the silica particles in the coreshell particle is smaller than that in the pure La0.45 Tb0.15 Ce0.40 PO4 powder. In general, the nanocrystallite size can be estimated from the Scherrer equation, D = 0.941/ cos , where D is the average grain size, is the x-ray wavelength (0.154 05 nm), and and are the diffraction angle and full-width at half-maximum (FWHM, in radians) of an observed peak, respectively [34]. The strong peaks from (200), (120) and (012) were used to calculate the average crystallite size ( D ) of La0.45 Tb0.15 Ce0.40 PO4 on the surfaces of silica particles and in the pure La0.45 Tb0.15 Ce0.40 PO4 powders. The estimated average crystallite sizes are 29 nm for the former and 50 nm for the latter, respectively. 3.1.2. FT-IR. FT-IR spectra were recorded for the as-formed SiO2 , 1000 C-annealed pure SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell sample, and pure La0.45 Tb0.15 Ce0.40 PO4 powder, 3248

as shown in gures 2(a)(c), respectively. For the asformed SiO2 particles, the FT-IR spectrum (gure 2(a)) shows the absorption bands of OH (3436 cm1 ), H2 O (1643 cm1 , 807 cm1 ), SiOSi (as , 1100 cm1 ), Si OH (s , 950 cm1 ), and SiO ( , 471 cm1 ) bonds (where as = asymmetric stretching, s = symmetric stretching, = bending), indicating that the as-formed SiO2 particles contain a large amount of OH groups and H2 O on their surfaces [35]. The surface SiOH groups play an important role for bonding the metal ions (La3+ , Ce3+ , Tb3+ ) from the coating sol and forming the La0.45 Tb0.15 Ce0.40 PO4 layers on the SiO2 surfaces in the following annealing process, as shown in scheme 1. In gure 2(b), for pure La0.45 Tb0.15 Ce0.40 PO4 powders the absorption bands at 900 1107 cm1 and 490650 cm1 have appeared, which are groups and the MO attributed to the absorption of PO3 4 (M = La, Tb, Ce) bond, respectively [29f]. This suggests that the crystalline phase (LaPO4 ) has formed after annealing at 1000 C, agreeing well with the results of XRD. For the SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell sample (gure 2(c)), the characteristic absorption peaks of the PO bond (900 1100 cm1 ) for La0.45 Tb0.15 Ce0.40 PO4 (gure 2(b)) and the SiOSi bond (1114 cm1 ) for amorphous SiO2 (gure 2(a)) have been observed clearly, and the weak signal from the MO bond may be covered by the bending vibration of the SiO bond at 471 cm1 . The signal of the OH groups from the as-formed silica particles has almost disappeared in the 1000 C-annealed SiO2 @La0.45 Tb0.15 Ce0.40 PO4 core shell particles. These results are consistent with those of XRD, and further demonstrate the formation of crystalline La0.45 Tb0.15 Ce0.40 PO4 coatings on the silica surfaces via the solgel deposition and annealing process. 3.1.3. SEM and TEM. SEM micrographs of the (a) as-formed SiO2 (900 nm), (b) 1000 C-annealed La0.45 Tb0.15 Ce0.40 PO4 powder, ((c)(f)) the SiO2 spheres (with different particle sizes of 300, 500, 900, and 1200 nm) coated by two layers of La0.45 Tb0.15 Ce0.40 PO4 , and (g) the energy dispersive xray spectrum (EDS) are shown in gure 3. From the SEM micrograph of gure 3(a), we can observe that the asformed SiO2 consists of spherical particles (of average size 900 nm), and these particles are non-aggregated, with a narrow size distribution. In contrast, the pure La0.45 Tb0.15 Ce0.40 PO4 powders contain irregular particles with a wide size distribution (150500 nm), as shown in gure 3(b). After functionalizing the silica particles with La0.45 Tb0.15 Ce0.40 PO4 coatings, the resulting SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell particles still keep the morphological properties of the silica particles, i.e. these particles are still spherical and non-aggregated, with a smooth surface. The size became larger after the coating process (900 nm of SiO2 in gure 3(a) versus 970 nm of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 in gure 3(e)). Moreover, irregular ne particles like the pure La0.45 Tb0.15 Ce0.40 PO4 powders in gure 3(b) cannot be observed in the gures 3(c) (f). This indicates that all of the La0.45 Tb0.15 Ce0.40 PO4 materials have been coated on the surfaces of the silica particles by our experimental process. However, it should be mentioned that the SEM micrographs can only provide basic information on the morphology of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 particles on a large scale (namely, all of the SiO2 particles remain

Transmission (%)

3436

Solgel synthesis and photoluminescence properties of spherical SiO2 @LaPO4 :Ce3+ /Tb3+ particles with a coreshell structure

(a)

(b)

(c)

Figure 4. TEM micrographs of the SiO2 coated with two layers of La0.45 Tb0.15 Ce0.40 PO4 (a), electron diffraction pattern (b) for the selective interface region (as shown in (a)) of the particle in (a), and the bare SiO2 particles (c). Figure 3. SEM micrographs of the as-formed SiO2 (900 nm) (a), 1000 C-annealed La0.45 Tb0.15 Ce0.40 PO4 powder (b), the SiO2 particles with different sizes of 300 nm (c), 500 nm (d), 900 nm (e), 1200 nm (f) coated with two layers of La0.45 Tb0.15 Ce0.40 PO4 , as well as the EDS (g) for the coreshell particles in (e).

spherical and non-aggregated, subjected to the solgel coating of La0.45 Tb0.15 Ce0.40 PO4 layers on them), and the core shell structure of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 particles cannot be resolved from the SEM micrographs due to the low magnication. The EDS (gure 3(g)) shows two strong peaks from Si and O, P and distinct peaks attributed to La, Ce, and Tb. The strong peak from Au is due to an Au paste used for mounting the sample for SEM observations. This provides additional evidence for the formation of coatings of crystalline La0.45 Tb0.15 Ce0.40 PO4 on the SiO2 particles. In order to observe the coreshell structure of SiO2 @La0.45 Tb0.15 Ce0.40 PO4 particles, TEM was performed representatively on the bare 500 nm SiO2 particles (as a reference) and those coated by two layers of La0.45 Tb0.15 Ce0.40 PO4 shells, as shown in gure 4. In gure 4(a), the coreshell structure for the SiO2 @La0.45 Tb0.15 Ce0.40 PO4 particles can be seen clearly due to the different electron penetrability for the cores and shells. The cores are black spheres with an average size of 500 nm (close to the pure SiO2 particles in gure 4(c)) and the shells have a grey colour and an average thickness of 60 nm. Note that the interfaces between the coating and the particle become irregular (while very smooth surfaces are seen in gure 4(c) for bare SiO2 particles). This might be caused by the inhomogeneous crystallization of La0.45 Tb0.15 Ce0.40 PO4 layers on the

surfaces of SiO2 particles, accompanied by the shrinkage of SiO2 particles upon annealing at high temperature (1000 C). Selective-area electron diffraction (gure 4(b)) performed in the interface region of the core and shell of the sample gives point patterns with some disorder (as shown in gure 4(a)), demonstrating the coexistence of crystalline phase (LaPO4 ) and amorphous phase (SiO2 ) in the interface region of the coreshell particles. 3.2. Photoluminescence properties 3.2.1. Spectral and kinetic properties of coreshell phosphors. SiO2 @LaPO4 :Ce3+ . Figures 5(a)(c) give the excitation and emission spectra and the decay curve, respectively, for the luminescence of Ce3+ in SiO2 @La0.8 Ce0.2 PO4 coreshell samples. The emission of Ce3+ includes a broad band with a maximum at 319 nm and a shoulder at 337 nm, which are assigned to the parity-allowed transitions of the lowest component of the 2 D state to the spinorbit components of the ground state, 2 F5/2 and 2 F7/2 of Ce3+ , respectively. The energy difference between the two peaks is 1700 cm1 , basically agreeing with the ground-state splitting of Ce3+ (2000 cm1 , i.e. the energy difference between the 2 F5/2 and 2 F7/2 doublets in the 4f1 conguration of the Ce3+ ion). Independently of the monitored emission wavelengths (319 or 337 nm), the excitation spectrum consists of three broad peaks with maxima at 243, 263, and 286 nm (the strongest), which correspond to the transitions from the ground state 3249

M Yu et al
286 319 337

Intensity (a.u.)

Intensity (a.u.)

263

Tb
264

3+

D4- F6

em = 319 nm

ex= 286 nm

(a)
em= 543 nm

D4- F5

(a)

(b)

286

543

(b)
ex= 286 nm

243

D4- F3

Ce
243

3+

D4- F4

Ce

3+

200

250

300

350

400

450
200 250 300 350 400 450 500 550 600 650

Wavelength (nm)
100

Wavelength (nm)
(c) ex= 286 nm, em = 319 nm
Blank circles: experimental data Solid line: fitted by I(t)= I0exp(-t/)
100 80

80

(c) ex = 286 nm, em = 543 nm

Blank circles: experimental data
Solid line: fitted by I= I0 exp(-t/)

Intensity (a. u.)

Intensity (a.u.)

60

= 16.5 ns

60 40 20

40

t = 1.89 ms

20

0 0 10 20 30 40 50 60 70 80 90 100

0
0 2 4 6 8 10 12 14 16 18 20

Decay time (ns)

Figure 5. Excitation (a) and emission (b) spectra and the decay curve (c) for the luminescence of Ce3+ in SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell particles.

Decay time (ms)

Figure 6. Excitation (a) and emission (b) spectra and the decay curve (c) for the luminescence of Tb3+ in SiO2 @La0.45 Tb0.15 Ce0.40 PO4 coreshell particles.

F5/2 of Ce3+ to the different components of the excited Ce3+ 5d states split by the crystal eld (in the LaPO4 host lattice, the La3+ ion is surrounded by nine oxygen atoms with a site symmetry of C1 [29f]). The intensity patterns and the positions of the peaks are consistent with those observed in the absorption and luminescence excitation spectra of the bulk LaPO4 :Ce3+ [36] and the colloid of LaPO4 :Ce3+ nanocrystals [29a, 29b, 29c, 29d, 29e]. The decay curve (gure 5(c)) of Ce3+ luminescence can be tted well to a single exponential function as I = I0 exp(t / ) (where is the 1/e lifetime of the Ce3+ ion). Through this tting, the lifetime of Ce3+ is determined to be 16.5 ns, which agrees well with the reported results [29, 36].
2

SiO2 @LaPO4 :Ce3+ , Tb3+ . Figures 6(a)(c) exhibit the excitation and emission spectra as well as the decay curve for the luminescence of Tb3+ in SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphor, respectively. The excitation spectrum (gure 6(a)) recorded at the 543 nm (5 D4 7 F5 ) of Tb3+ is composed exclusively of the excitation bands of Ce3+ , which is similar to the excitation spectrum of Ce3+ in SiO2 @La0.8 Ce0.2 PO4 (gure 5(a)). Excitation into the Ce3+ band at 286 nm yields both the weak emission of Ce3+ (300 360 nm) and the strong emission of Tb3+ (370700 nm: 5 D4 7 F J , J = 6, 5, 4, 3), as shown in gure 6(b). This indicates that an efcient energy transfer from Ce3+ to Tb3+ occurs in SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphor, as observed 3250

in the bulk powder materials [36] and colloids of LaPO4 :Ce3+ , Tb3+ [29a, 29b, 29c, 29d, 29e]. All the above spectral properties for the SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphors are basically consistent with the reported bulk [36], nanocrystalline powder and thin lm [29] of LaPO4 :Ce3+ , Tb3+ , further conrming the formation of nanocrystalline layers of LaPO4 :Ce3+ , Tb3+ on SiO2 spheres. Like the single exponential luminescence decay of Ce3+ in SiO2 @La0.8 Ce0.2 PO4 coreshell phosphor, the luminescence decay curve of Tb3+ (gure 6(c)) in SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphors can also be tted to a single exponential function, and the lifetime of Tb3+ is 1.89 ms. The luminescence lifetime of Tb3+ (5 D4 ) is in the range of milliseconds due to the forbidden nature of the ff transition. The strong luminescence of Tb3+ results from efcient energy transfer from the Ce3+ to the Tb3+ in the LaPO4 :Ce3+ , Tb3+ layers of the coreshell phosphors, as reported previously [29, 36]. In order to obtain more information about the energy transfer process from the Ce3+ to the Tb3+ , time-resolved emission spectra of Tb3+ in the SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphors were recorded at room temperature by exciting into the absorption of Ce3+ using a 286 nm laser with a delay time ranging from 0.1 to 1000 s, as shown in gure 7. From t = 0.10 to t = 0.80 s, the broadband emission of Ce3+ , together with the weak emission of Tb3+ from 5 D3 7 F J ( J = 6, 5, 4, 3, 2),

D4- F2

Solgel synthesis and photoluminescence properties of spherical SiO2 @LaPO4 :Ce3+ /Tb3+ particles with a coreshell structure

5d
2

41200 cm -1 37900 cm -1 35000 cm -1

D3/2 ET

L10 D3

D4

hv
EX 286 nm
2

Ce3+ EM 319 nm 337 nm

Tb3+ EM 543 nm
0

F7/2 F5/2 Free ion Crystal field (C1 )

5 6

FJ

Crystal field (C1)

Ce
Wavelength (nm)
3+

3+

Tb3+

Figure 7. Time-resolved emission spectra of Tb in the La0.45 Tb0.15 Ce0.40 PO4 @SiO2 sample (ex = 286 nm laser).

Figure 8. The luminescence and energy transfer process of Ce3+ and Tb3+ in LaPO4 :Ce3+ , Tb3+ .
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can be observed simultaneously, indicating that two processes occur in the excited Ce3+ : radiative transition to its ground state and nonradiative transfer of the excitation energy to the Tb3+ (mainly to high levels: 5 D3 , 5 L10 at around 26 200 cm1 (380 nm)). The competition between these two processes results in both the Ce3+ emission and the Tb3+ emission (mainly directly from the 5 D3 level). When t = 5 s, the emission of Ce3+ cannot be observed due to its short lifetime ( = 16.5 ns depopulation takes place very quickly), and the 5 D4 7 F J ( J = 6, 5, 4, 3) emission of Tb3+ became dominant due to the cross-relaxation effect among the Tb3+ ions, i.e. Tb3+ (5 D3 ) + Tb3+ (7 F6 ) Tb3+ (5 D4 ) + Tb3+ (7 F0 ) [29f]. For t = 20 s and later, the 5 D3 emission of Tb3+ is quenched completely by the cross-relaxation effect, and the 5 D4 emission also begins to decay gradually due to the depopulation of the excited states. Because the 5 D4 emission of Tb3+ has a lifetime of 1.89 ms (1890 s), it can still be observed clearly for t = 1000 s, as shown in gure 7. The luminescence and energy transfer process of Ce3+ and Tb3+ in LaPO4 :Ce3+ , Tb3+ is shown schematically in gure 8 [29a]. First, Ce3+ ions were excited by ultraviolet (UV) light excitation; subsequently, energy transfer takes place from Ce3+ to Ce3+ , and then from 5d (Ce3+ ) to the high excitation levels of Tb3+ (4fn ) followed by cross relaxation to the 5 D4 level of Tb3+ , which decays radiatively to various lower levels of 7 F J ( J = 0, 1, 2, 3, 4, 5 and 6). The energy levels of Tb3+ (4fn ) are suitable for the energy transfer to take place from the allowed Ce3+ emission of (fd) upon excitation with UV light [37]. That the Ce3+ Ce3+ energy diffusion process should play a role in the energy transfer process appears reasonable in view of the involvement of parity-allowed df transition moments [36]. The Tb3+ ion acts as the terminal of the energy transfer processes in the LaPO4 :Ce3+ , Tb3+ system. 3.2.2. Tuning of the PL intensity in the coreshell phosphors. The PL intensity of SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphors can be tuned by several experimental factors, such as the annealing temperature, the number of coatings,

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Pure La0.45Tb0.15Ce0.40PO4 SiO2@La0.45Tb0.15Ce0.40PO4

PL Intensity (a.u.)

50000 40000 30000 20000 10000 0 200

400

600

800

1000

1200

SiO2 particle size (nm)

Figure 9. The PL emission intensity of Tb3+ in the SiO2 @La0.45 Tb0.15 Ce0.40 PO4 sample as a function of SiO2 particle size (the same experimental and instrumental measurement conditions were employed in obtaining the emission intensity).

and the template particle size. Normally, the PL intensity increases on raising the annealing temperature from 700 to 1100 C. This is a common phenomenon due to the improvement in the crystallinity of La0.45 Ce0.40 Tb0.15 PO4 shells on raising the annealing temperature [29f]. The effects of shell thickness on the PL intensity in the core shell phosphor particles were thoroughly investigated in SiO2 @Y2 O3 :Eu3+ and SiO2 @YVO4 :Eu3+ systems, and it is revealed that, in both, the PL intensity increases with the increase in the shell thickness [31b, 31c]. The same situation is expected to hold for the current SiO2 @La0.45 Ce0.40 Tb0.15 PO4 system. Here, we focus mainly on the effects of SiO2 core size on the PL intensity of the SiO2 @La0.45 Ce0.40 Tb0.15 PO4 particles. It is shown that the PL intensity of the SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphors varies with the size of the SiO2 cores, as shown in gure 9. From gure 9, it can be seen that the PL intensity basically increases with the increase in SiO2 core particle size. It is well known that bigger particle size is good for improving the PL intensity 3251

M Yu et al

of phosphors [21a]. Here, it is believed that the amount of emitting Tb3+ ions per SiO2 particle will increase with the increase in SiO2 cores, resulting in an enhancement of the PL intensity. The PL intensity of La0.45 Ce0.40 Tb0.15 PO4 -coated 1200 nm SiO2 coreshell phosphor can reach about 65% that of the pure La0.45 Ce0.40 Tb0.15 PO4 powder phosphor.

4. Conclusions
An effective and simple solgel process has been developed to deposit La0.45 Ce0.40 Tb0.15 PO4 layers on SiO2 spheres. The obtained SiO2 @La0.45 Ce0.40 Tb0.15 PO4 coreshell phosphors have spherical morphology, submicron size, and a narrow size distribution. The spectral and kinetic properties of the core shell phosphors are similar to those of the reported bulk and nanocrystalline SiO2 @La0.45 Ce0.40 Tb0.15 PO4 phosphors. The PL intensity of the coreshell phosphors can be tuned by the annealing temperature and the SiO2 particle size. The kind of coreshell structured phosphors have possible applications in photoluminescence areas, such as lamps for lighting and plasma display panels (PDP). The current method can also be extended to prepare various other coreshell phosphors with homogeneous morphology and to decrease the cost of phosphors to some degree.

Acknowledgments
This project is nancially supported by the Bairen Jihua foundation of the Chinese Academy of Sciences, the National Natural Science Foundation of China (50225205, 50572103, 20431030, 00310530) and the Ministry of Science and Technology (MOST) of China (No 2003CB314707). Dr M Yu is grateful for the special starting research fund for the Awardees of President Prize of the Chinese Academy of Sciences (20052007). We are grateful to Professor Yingnimg Yu and Mr Liaohai Ge for measuring the time-resolved emission spectra, and SEM and TEM, respectively.

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