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Luminescent properties of YVO4·xTa2O5:Eu3+ WANG Zhongzhi (⥟ᖴᖫ)1,2, SHEN Leijun (≜䳋)ݯ1,2, LI Bo (ᴢ⊶)1,2, GAO Lele (催ФФ)1,2, ZHOU Yongbo (਼∌)1,2ˈZHANG Guobin (ᓴ᭠)3 (1. National Engineering Research Center of Rare Earth Metallurgy and Performance Meterials, Baotou 014030, China; 2. Baotou Research Institute of Rare Earths, Baotou 014030, China; 3. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China) Received 15 October 2010; revised 21 October 2010
Abstract: The samples of YVO4·xTa2O5:Eu3+ (x=0.45,0.35,0.25,0.15,0.05˅were synthesized by the conventional solid state reaction. The structure of the prepared sample was checked by the X-ray diffraction. XRD measurements at room temperature were confirmed that the prepared YVO4·xTa2O5:Eu3+ consisted of two phasesDŽOne phase was YVO4, which is tetragonal according with the JCPDS-Card (17-0341); the other phase was YTaO4, which is according with the JCPDS-Card (72-2018). The spectrum property of the sample was studied under the VUV. The effects of Ta doped on the luminescent properties of sample were investigated and it was found that some Ta doped could highlight the absorption of matrix in VUV region. The emission spectrum was dominated by the red peaks at 613 and 619 nm due to the electric dipole transition 5D0ĺ7F2 of Eu3+. It indicated that Eu3+ occupied a site lacking inversion symmetry. There was one band peaked at 155 nm in the excitation spectrum of the sample, it could be assigned to the absorption of the host. Keywords: red-lighting; PDP; VUV; rare earths
Plasma panel display PDP (plasma display panel) as one of new century most potential digital display scopes has obvious superiority in 102–152 cm scope large screen display domain comparing with other display technology[1]. The vacuum ultraviolet ray emission of Colored PDP is monitored through the gaseous discharge on the display, which can excitate red, green and blue phosphors for three-primary colour to realize the color display. At present ,the application phosphor in PDP is: (Y,Gd)BO3:Eu3+ (red), Zn2SiO4:Mn2+ (green), BaMgAl10O17:Eu2+ (blue)[2,3]. However they have some deficiency, Namely the red excitation purity is bad[4,5], the green phosphor’s afterglow is excessively long and the blue color is unstable. Therefore, developing new PDP already to become an important research subject into the domain of material, and be expected to improve the PDP phosphor performance and enhance its industrial production and the commercialized level. At present, commercial PDP red phosphors are (Y,Gd)BO3:Eu3+ and Y2O3:Eu3+, but only the (Y,Gd)BO3: Eu3+ is widely used. The reason is that (Y,Gd)BO3:Eu3+ has the fine vacuum ultraviolet absorption characteristic and its luminous efficiency is quite high under excitation of the vacuum ultraviolet ray (147 nm). However, compared with CIE, (Y,Gd)BO3:Eu3+ emission peak has moved to yellow. Therefore studies to the red luminous powder’s focus mainly on solving the chromaticity impure problem. The vanadate has matrix sensitization[6] nearby 150 nm, so peoples have widely studied on it[7–10]. And YVO4:Eu3+ phosphor is one kind of very fine red luminous powder, has
been applied in the plasma panel display (PDP)[11]. This research has used the high temperature solid reaction to synthesize a series of YVO4·xTa2O5:Eu3+ red luminous powder, and researched the effect of different Ta doped on the material structure and the vacuum ultraviolet illumination performance influence.
1 Experimental The red YVO4·xTa2O5:Eu3+ (x=0.45, 0.35, 0.25, 0.15, 0.05) phosphors were prepared by solid-state reaction. a stoichiometric amount of Y2O3 (purity 99.99%), Eu2O3 (99.99%), V2O5 (superior grade pure), Ta2O5 (99.99%) was ground in an agate mortar to mix homogeneously. The mixture was put into an corundum crucible and fired at 1300 ºC for 4 h. The structure of samples was examined with the PW-1700 X-ray diffractometer; Excitation spectrum and emission spectrum of vacuum ultraviolet of sample were detected in the National Synchrotron Radiation Laboratory of the University of Science and Technology of China.
2 Results and discussion 2.1 Analysis of structure X-ray diffraction analysis of the sample test and result is shown in Fig. 1, Fig. 1 shows XRD chart of YVO4·xTa2O5: Eu3+ phosphors with different Ta density substitutes. The result indicated that the products formed by the two-phase.
Foundation item: Projects supported by the Natural Science Foundation of Inner Mongolia Autonomous Region (2009MS0803) Corresponding author: SHEN Leijun (E-mail:
[email protected]; Tel.: +86-472-5179397) DOI: 10.1016/S1002-0721(10)60309-2
WANG Zhongzhi et al., Luminescent properties of YVO4·xTa2O5:Eu3+
Fig. 1 XRD patterns of YVO4·xTa2O5:Eu 3+
One is YVO4 with tetragonal system, body-centered structure, the space grouping is I41/amd, the result is consistent with JCPDS-Card (17-0341). Another one is the YTaO4, the result is consistent with the JCPDS-Card (72-2018).With the Ta content's reduction, YTaO4 gradually reduces in the product, corresponding YVO4 gradually increases. 2.2 VUV spectral properties of YVO4·xTa2O5:Eu3+ Fig. 2 shows the vacuum ultraviolet excitation spectra of YVO4:Eu3+ and YVO4·xTa2O5:Eu3+ (x=0.15) under the 619nm wave length monitor. As can be seen from Figure 2, excitation peak of YVO4·xTa2O5:Eu3+ (x=0.15) than excitation peak of YVO4: Eu3+ has been enhanced. In addition, after mixing in the Ta element, the excitation spectrum of YVO4·xTa2O5:Eu3+ (x=0.15) have traverse phenomenon to the shortwave contrasting to YVO4:Eu3+. Fig. 3 is vacuum ultraviolet excitation spectra of YVO4·xTa2O5:Eu3+ samples of different Ta density under the 619nm wavelength monitor. the excitation band which center is in 155 nm is considered to the VO43– absorption band in excitation spectrum. Obvious excitation band which appears in 200 nm, is very close with the absorption band of Y2O3, may think from transition of 2p(O)ĺ4d(Y)[8]. The excitation band of about 313 nm is the absorption band of matrix. It can be find, with the Ta content's reduction, excitation spectrum's intensity increases at first and then decreases, excitation spectrum intensity is highest in x=0.15 value. And with Ta content's increasing, the excitation spectrum has
Fig. 2 VUV excitation spectra of YVO4:Eu3+ and YVO4·xTa2O5:Eu3+
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traverse phenomenon to the shortwave, specially in 155 nm place. This explained that right amount Ta joined strengthened the matrix absorption in the vacuum ultraviolet. Fig. 4 is the emission spectra of YVO4·xTiO2:Eu3+ under the 147 nm excitate, on the spectrum chart’s emission peak is ascribed to the Eu3+ ion f-f transition. The emission peak is 5 DJ (J=0, 1)ĺ7FJ (J=1,2,3,4) transition emission of the Eu3+ ion, respectively is 537 nm (5D1ĺ7F1), magnetism dipole transition (5D0ĺ7F1) of the 593 nm, electric dipole transitions (5D0ĺ7F2) of the 619, 697 nm (5D0ĺ7F4), electric dipole transition obviously much higher than the magnetic dipole transition, it can be sure that Eu3+ is in the non-centrosymmetric standard position. Obviously, VO43– has transfered energy to the Eu3+ ion through resonance energy transfer[12], which causes it be excited to 5DJ (J=0,1) and has the emission transition. The sample emission main peak is 619 nm, corresponding to the electric dipole transition of Eu3+ ion 5D0ĺ7F2, the light which sends out is red and the color is pure. Luminescent intensity of sample also has changed along with Ta content’s difference. There can be seen obviously from relative position of various samples main peak of Fig. 4 that luminescent intensity of the sample is strongest when x value is 0.15, This indicates that right amount Ta doping will enhance luminescence properties of the material. 2.3 Luminescent properties comparisons of YVO4·xTa2O5: Eu3+ phosphor and the (Y, Gd)BO3: Eu3+ phosphor At present, (Y,Gd)BO3:Eu3+ is a phosphor universal used in domestic and foreign on the PDP rouge. VUV excitation
Fig. 3 VUV excitation spectra of YVO4·xTa2O5:Eu3+
Fig. 4 Emission spectra of YVO4·xTiO2:Eu 3+ excited at 147 nm
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spectrum and emission spectrum of the YVO4·xTa2O5:Eu3+ phosphor and market purchase’s Japanese NICHIA Corporation’s (Y, Gd)BO3:Eu3+ phosphor are shown in Figs. 5 and 6. It can be found that, the excitation spectrum of YVO4·xTa2O5:Eu3+ has an absorption peak of matrix nearby 155 nm, which is higher than the (Y, Gd)BO3:Eu3+ phosphor obviously. It confirmed that the efficiency of YVO4·xTa2O5: Eu3+ phosphor is higher in nearby vacuum ultraviolet's 155 nm. However, (Y,Gd)BO3:Eu3+ phosphor has high efficiency in the entire vacuum ultraviolet. The emission spectra are shown in Fig. 6, (Y,Gd)BO3:Eu3+ phosphor emission main peak is located at 591 nm, but YVO4·xTa2O5:Eu3+ phosphor emission main peak is located at 619 nm. Compared to commercial (Y, Gd) BO3:Eu3+ phosphor, the red luminescence of YVO4·xTa2O5:Eu3+ phosphor sended out is pure.
Fig. 5 VUV excitation spectra of (Y,Gd)BO3:Eu3+ and YVO4·xTa2O5:Eu3+
Fig. 6 Emission spectra of (Y,Gd)BO3:Eu3+ and YVO4·xTa2O5:Eu3+ excited by 147 nm
3 Conclusions (1) YVO4·xTa2O5:Eu3+ (x=0.45, 0.35, 0.25, 0.15, 0.05) phosphor was synthesized by the high temperature solid reaction and the samples were composed of two kind of phases, square zircon YVO4 and YTaO4, respectively; along with the Ta content reducing, YTaO4 phase reduces gradually and
JOURNAL OF RARE EARTHS, Vol. 28, Spec. Issue, Dec. 2010
YVO4 correspondingly increases. (2) Doping right amount of Ta in YVO4 was possible to increase the matrix absorption in 155 nm as well as the 315 nm place, thus enhance luminescence property of the material. (3) Emission main peaks of the samples were at 613 and 619 nm under vacuum ultraviolet excitation in the 147 nm, corresponding to electric dipole transition of the Eu3+ ion (5D0ĺ7F2), Compared with the current commercial red phosphor (Y,Gd) BO3:Eu3+, color of this experiment synthesized phosphor is purer, it can satisfy the PDP plasma demonstration the request.
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