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Journal of Luminescence 127 (2007) 650654 www.elsevier.com/locate/jlumin

Synthesis and photoluminescence of CeO2:Eu3+ phosphor powders

Xiaohua Liu, Shaojun Chen, Xiaodong Wang
Department of Physics, Shantou University, Shantou City, Guangdong Province 515063, PR China Received 31 January 2007; received in revised form 29 March 2007; accepted 30 March 2007 Available online 4 April 2007

Abstract The crystalline structure and photoluminescence (PL) properties of europium-doped cerium dioxide synthesized by the solid-state reaction method were analyzed. CeO2:Eu3+ phosphor powders exhibit the pure cubic uorite phase up to 10 mol% doping concentration of Eu3+. With indirect excitation of CeO2 host at 373 nm, the PL intensity quickly increases with increasing Eu3+ concentration, up to about 1 mol%, and then decreases indicating the concentration quenching. While with direct excitation (467 nm), much more stronger PL emissions, especially the electric dipole emission 5D07F2 at 612 nm, are observed and no concentration quenching occurs up to 10 mol% doping concentration of Eu3+. The nature of this behavior and the cause of the concentration quenching were discussed. r 2007 Elsevier B.V. All rights reserved.
PACS: 78.55.m; 78.55.Hx; 78.20.e; 78; 33.50.Dq Keywords: CeO2; Eu3+; Luminescence; Solid-state reaction

1. Introduction Recently, the oxide phosphors with rare-earth photoluminescence (PL) in metal oxide matrices have attracted a great attention because of its potential applications in optoelectronics devices and at panel display [1,2]. The oxide phosphors possess higher chemical and thermal stability than commonly used sulde phosphors such as ZnS:Cu, Al and Y2O2S:Eu3+ [3,4]. This advantage makes these materials more chemically stable in high vacuum and under electron excitation. Therefore, there is a continuous search for new oxide phosphors with high performance for phosphor applications. Cerium dioxide (CeO2) has a cubic uorite crystal structure with a lattice constant a of 0.541 nm. Due to its high refractive index, optical transparency, thermal and chemical stability, and high dielectric constant (26), it has potential applications as an optical coating [5], ionconducting layers [6,7], and ideal buffer layers for fabricating epitaxially grown functional oxides on silicon
Corresponding author. Tel.: +86 13715894729; fax: +86 754 2902767.

substrates [8,9]. Recently, violet/blue luminescence from the CeOx lm [10] and CeO2 lm [11] has been reported. However, few works have been reported on luminescence of CeO2 doped with rare-earth ions. In this study, the solidstate reaction technique was explored to synthesize CeO2:Eu3+ phosphor powders. The luminescence properties and the effects of dopant concentration on PL were investigated by the excitation and emission spectra.

2. Experimental CeO2:xEu3+ phosphors, with x 010 mol%, were synthesized through the solid-state reaction technique. The starting materials were CeO2 (Analytical grade) and Eu2O3 (99.999%) powders. The synthesis was performed at 1360 1C for 8 h in ambient air. X-ray diffraction (XRD) with Cu Ka (l 0.15405 nm) radiation (Bruker axs, type D8 ADVANCE Diffractometer) was used to analyze the crystalline structure of powders. The PL and PL excitation spectra with a resolution of 5 nm were obtained using luminescence spectrometer (Perkin-Elmer, type LS 55) at room temperature.

E-mail address: xhliu@stu.edu.cn (X. Liu). 0022-2313/$ - see front matter r 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jlumin.2007.03.014

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3. Results and discussion Fig. 1 shows the XRD patterns of CeO2:xEu3+ phosphors for doping concentrations x 0.0, 1.0 and 10.0 mol%, synthesized through the solid-state reaction technique. The presence of peaks corresponding to (1 1 1), (2 0 0), (2 2 0), (3 1 1), (2 2 2), (4 0 0), (3 3 1) and (4 2 0) conrms the formation of pure cubic uorite CeO2 structure. The values of lattice constants (a) corresponding to Eu3+ doping concentrations x 0.0, 1.0 and 10.0 mol% are observed to be 0.5416, 0.5418 and 0.5423 nm, respectively. The calculated values of lattice constants are reasonably found to increase with an increase of doping concentration of Eu3+ ions having larger ionic radii. It is also found from Fig. 1 that the XRD lines broaden with increasing x, which is attributable to the increased lattice defect and disorder formation induced by the alloying. The present result indicates that in the doping concentration range of xp10 mol%, the Eu3+ ions substitute Ce4+ ions without changing the crystal structure of cubic CeO2. This is consistent with the work of Shuk and Greenblatt [12], who demonstrated the large solubility of 25 mol% for Eu3+ ions in CeO2. The realization of high Eu doping content in CeO2 is due to the nearness of ion radius for 0.1206 nm sized Eu3+ ions and 0.111 nm sized Ce4+ ions. The luminescence properties were investigated by measuring the PL spectra of CeO2:Eu3+ powders at room

x=10mol% (220) (311)

(222)

(400)

temperature. The light from a xenon lamp through the monochromator was used for the optical excitation. The excitation spectra were measured by monitoring the peak intensity at 612 nm. The excitation spectra of europiumdoped CeO2 phosphors, as shown in Fig. 2, consist of a broad band and some sharp lines. Since the O2Eu3+ charge transfer (CT) states lie in much shorter wavelength region around 250300 nm as reported [13,14] and CeO2 has a band gap around 3.4 eV ($370 nm) [15], the broad excitation band in the UV region peaking around 373 nm should be attributable to the host CeO2. The energy absorbed by the CT from O2 valence band to Ce4+ conduction band is transferred to the Eu3+ and produces the red emission. While the narrow peaks at 386, 396, 417 and 467 nm are assigned to the intra-4f6 transition absorptions of Eu3+. From Fig. 2, we can nd that for CeO2:xEu3+ powders with low concentration of Eu3+ (xp2 mol%), the host excitation band is dominant and has a maximum when x 1 mol%. By increasing the Eu3+ concentration, the intra-4f6 transition bands of Eu3+, especially the one at 467 nm become stronger and gets dominant when xX4 mol%. The PL emission spectra of CeO2:xEu3+ powders excited at a wavelength of 373 nm are shown in Fig. 3. The spectra consist of a series of well-resolved features at 572, 591, 612, 632, 655, 683, 696 and 712 nm, which can be assigned to 5D07FJ (J 0, 1, 2, 3 and 4) transitions of Eu3+ ions, namely, the 5D07F0 (572 nm), 5D07F1 (591 nm), 5D07F2 (612 and 632 nm), 5D07F3 (655 nm), and 5D07F4 (683, 696 and 712 nm), respectively. Herein the multiple structured spectra can be attributed to the splitting of the Eu3+ 4f shell. From Fig. 3, it can be found that for CeO2:xEu3+ powders with low Eu3+ doping concentration (xp2 mol%), the 5D07F1 (591 nm) is dominant. By increasing the Eu3+ concentration, the transition 5D07F2 (612 nm) enhances gradually and

(111) (200)

Intensity (a.u.)

1000 467 450 500 (a) 0.2mol%, (b) 1mol%, (c) 2mol%, (d) 4mol%, (e) 5mol%, (f)10mol%. em=612nm (f) (e) 400 (d) (c) 200 (b) (a) 0 30 40 50 2 (deg.) 60 70 300 350 400 Wavelength (nm)
Fig. 2. Excitation spectra of CeO2:Eu3+ powders with different Eu3+ concentrations, lem 612 nm.

PL Intensity (a.u.)

386 396 373

x=1mol%

800

600

x=0.0

Fig. 1. X-ray diffraction patterns of CeO2:xEu3+ phosphor powders calcined at 1360 1C for Eu3+ concentrations, x 0.0, 1.0 and 10.0 mol%.

417

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800 (a) 0.2mol%, (b) 1mol%, (c) 2mol%, (d) 4mol%, (e) 5mol%, (f) 10mol%. 700
7 0 F0 7 0 F1 5D 7 0 F2 7F 3 5D 0 7F 4

150

591 nm

ex = 373nm

5D

5D

600

PL Intensity (a.u.)

ex = 373nm

125

5D

100

612 nm

(f)

500 PL Intensity (a.u.) (e) 400 (d) 300 (c) 200 (b) 100 (a) 0 550 600 650 Wavelength (nm) 700

75

50

25 0 2 4 6 8 10 Eu3+ concentration (mol%)

Fig. 4. The dependences of PL intensity on the Eu3+ concentration for the 5D07F1 and 5D07F2 transitions, lex 373 nm.

Fig. 3. Emission spectra of CeO2:Eu3+ powders with different Eu3+ concentrations, lex 373 nm.

eventually surpasses the intensity of the 5D07F1 transition when xX4 mol%. Fig. 4 shows the relationship between PL emission intensity and the Eu3+ ion concentration of the CeO2:xEu3+ powders for the transition 5D07F2 at 612 nm and the transition 5D07F1 at 591 nm. It can be seen that the Eu3+ emission intensity initially increases with doping concentration and quickly reaches a maximum value at the doping concentration of 1 mol%. Then a sharp concentration quenching occurs when europium concentration further increases. It is well known that among the 5D07FJ transitions of Eu3+ ions, the 5D07F1 emission at 591 nm is a magnetic dipole transition and scarcely changes with the crystal eld strength around the Eu3+ ions. On the other hand, the emission 5D07F2 at 612 nm is electric dipole allowed. It is dependent on the local electric eld and hypersensitive to the local symmetry around the Eu3+ ions. When the Eu3+ ions locate at sites with inversion symmetry, the 5D07F1 transition dominates the emission spectrum [16]. Otherwise, when the Eu3+ ions locate at sites without inversion symmetry, the 5D07F2 transition dominates the emission spectrum and its intensity increases with increasing distortion of the local eld around the Eu3+ ions [17]. Therefore, the intensity ratio of (5D07F1)/(5D07F2), known also as the asymmetry ratio, can be used to measure the degree of distortion from the inversion

symmetry of the local environment of Eu3+ ions in the host lattice. Consulting the data shown in Fig. 4, we can nd that the asymmetry ratio of europium-doped CeO2 powders synthesized here increases with the doping concentration. This result suggests that the symmetry of sites occupied by Eu3+ ions degrade with the increase of Eu3+ doping concentration in CeO2:Eu3+ powder phosphors. As we know, the Ce site in uorite CeO2 host has Oh symmetry with eightfold oxygen coordination. Therefore, the Ce site possesses inversion symmetry, so the electric dipole emission 5D07F2 would be forbidden and could not be observed if Eu3+ ion occupied the Ce site without changing the original inversion symmetry. However, in fact, when Eu3+ replaces Ce4+, it needs charge compensation to make charge equilibrium. Thus, there are two possible kinds of defects formed during charge compensation: interstitial Eu3+ (four Eu3+ replacing three Ce4+) and O2 vacancies (one Eu2O3 replacing two CeO2). These defects induce the symmetry distortion of local environment around the Eu3+ ions, greatly increase the conductivity of material, and act as nonradiative recombination centers. The properties of these defects have been extensively investigated and reviewed in the past as well as successfully applied in CeO2-based ionically conductive materials [12,18]. In addition, because of the different ion sizes between Ce4+ and Eu3+, Eu doping of CeO2 also generates symmetry distortion of local environment around the Eu3+ ions. This is why the emission 5 D07F2 at 612 nm is observed and become dominating for the high Eu doping content. Fig. 5 shows the PL emission spectra of CeO2:xEu3+ powders excited at a wavelength of 467 nm. Fig. 6 shows the intensities of the 591 and 612 nm PL peak as a function of the concentration of Eu3+ in CeO2:Eu3+ powders with the same excitation. Comparing with the PL emission

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1000 900 800 700 600 500 400 300 200 100 0 550

(a) 0.2mol%, (b) 1mol%, (c) 2mol%, (d) 4mol%, (e) 5mol%, (f) 10mol%.
7 0 F2

ex = 467nm

(f) (e) (d) (c) (b) (a) 600 650 Wavelength (nm) 700

tion quenching is observed. It should be noted that this is completely different from the case obtained by the indirect host excitation (lex 373 nm). Based on this result, we can analyze the mechanism of concentration quenching for host excitation, that is presumably with increasing Eu3+ doping concentration, energy transfer from CeO2 host to nonradiative recombination centers generated by the Eu3+ doping increases and gradually hinders the energy transfer from CeO2 host to Eu3+. But the generally admitted mechanisms of concentration quenching such as the cross relaxation between adjacent Eu3+ ions and/or energy transfer from Eu3+ ions to nonradiative recombination centers seem not to be dominant in our samples. That is why the luminescence quenching occurs for the host excitation but not for the direct excitation of Eu3+ in our samples. In addition, we have noted a very interesting phenomenon in our data. As shown in Figs. 4 and 6, the intensity of 612 nm PL emission peak reveals an abnormal change when Eu3+ doping content increasing from 4 to 5 mol%. It is likely related to some abrupt changes in the interactions between defects and Eu3+ ions introduced by Eu doping. The nature behind this phenomenon is not clear and further investigations are performed now. 4. Conclusion CeO2:Eu3+ phosphor powders with various Eu3+ concentrations have been synthesized by the solid-state reaction method. XRD analysis showed the formation of pure cubic uorite phase up to 10 mol% doping concentration of Eu3+. The dependence of PL emission intensity on the Eu3+ concentrations shows the different behavior for direct excitation at 467 nm and indirect excitation of CeO2 host at 373 nm. The nature of this behavior is closely related to the defects and symmetry distortion generated by Eu3+ replacing Ce4+. The cause of the concentration quenching is likely to be due to the nonradiative recombination centers created by the Eu3+ doping, which hinder the energy transfer from CeO2 host to Eu3+. Acknowledgments This work is supported by the Natural Science Foundation of Guangdong Province of China (Grant no. 04010998), the Ministry of Education of China, and the Ministry of Personnel of China. References
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PL Intensity (a.u.)

D07F0

5D

7 0 F1

5D

7 0 F3

Fig. 5. Emission spectra of CeO2:Eu3+ powders with different Eu3+ concentrations, lex 467 nm.

400 ex = 467nm 300 PL Intensity (a.u.) 612 nm

200

5D

100

591 nm

0 0 2 4 6 8 10 Eu3+ concentration (mol%)

Fig. 6. The dependences of PL intensity on the Eu3+ concentration for the 5D07F1 and 5D07F2 transitions, lex 467 nm.

spectra excited at lex 373 nm shown in Fig. 3, it can be seen that at high Eu3+ concentrations (xX4 mol%), the direct excitation of Eu3+ (lex 467 nm) generates much more stronger PL emissions, especially the electric dipole emission 5D07F2 at 612 nm. The PL emission intensity increases with the Eu3+ doping content and no concentra-

5D

7 0 F4

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