混合尖晶石型Zn6Ga8TiO20:Cr3+荧光粉的合成、结构表征与发光性能

doi:10.15541/jim20170113

无机材料学报 ›› 2018, Vol. 33 ›› Issue (1): 9-13.DOI: 10.15541/jim20170113 CSTR: 32189.14.10.15541/jim20170113

混合尖晶石型Zn₆Ga₈TiO₂₀:Cr³⁺荧光粉的合成、结构表征与发光性能

郑遗凡, 张露露, 王锴, 潘再法

浙江工业大学1. 化学工程学院;
2. 分析测试中心, 杭州 310014

收稿日期:2017-03-13 修回日期:2017-04-26 出版日期:2018-01-23 网络出版日期:2017-12-15
作者简介:郑遗凡(1964-), 男, 博士, 教授. E-mail: zhengyifan@zjut.edu.cn
基金资助:
国家自然科学基金重点项目(10804099);浙江省自然科学基金(Y4110536);浙江省重点科技创新团队(2009R50002)

Microstructure Characterization and Luminescent Property of Mixed Spinel Zn₆Ga₈TiO₂₀:Cr³⁺ Phosphors

ZHENG Yi-Fan, ZHANG Lu-Lu, WANG Kai, PAN Zai-Fa

1. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China;
2. Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, China

Received:2017-03-13 Revised:2017-04-26 Published:2018-01-23 Online:2017-12-15
Supported by:
National Natural Science Foundation of China (10804099);The Natural Science Foundation of Zhejiang Province (Y4110536);The Key Science and Technology Innovation Team of Zhejiang Province (2009R50002)

摘要/Abstract

摘要：

采用高温固相法合成新型红色荧光粉Zn₆Ga_8-_xTiO₂₀:xCr³⁺。用XRD、XRF和TEM对样品的成分和晶体结构进行表征, 发现所合成的荧光粉为单一的混合尖晶石结构, Cr³⁺能有效地掺杂进入基质Zn₆Ga₈TiO₂₀中, 并占据八面体格位。荧光光谱分析表明, 激发谱由四个峰组成, 峰值分别为281、337、420和555 nm, 其中281 nm对应Cr³⁺离子的⁴A₂→⁴T₁(4P)跃迁, 337 nm来自O^2-的2p轨道电子向Ga³⁺的4s4p轨道迁移跃迁, 420和555 nm分别对应Cr³⁺离子的⁴A₂→⁴T₁和⁴A₂→⁴T_2g的跃迁。发射光谱是由²E→⁴A₂的跃迁辐射零声子线(689 nm, R锐线)、处于畸变的环境中Cr³⁺发射的N线(696 nm)以及由晶格振动导致的声子伴随发射峰组成。这种荧光粉是一种可能应用在白光LED上的红色荧光粉。

关键词: Zn6Ga8-xTiO20:xCr, 红色荧光粉, 微结构, 荧光

Abstract:

A novel red phosphor Zn₆Ga_8-_xTiO₂₀:xCr³⁺ was prepared via a high temperature solid-state method. The as-prepared phosphors were examined by means of X-ray diffraction, X-ray fluorescence and transmission electron microscopy. The results showed that the synthesized phosphor had a single mixed spinel structure and Cr³⁺ could be effectively doped into the host Zn₆Ga₈TiO₂₀by occupation of octahedral sites. It was showed that the excitation spectrum was composed of four bands located at 281, 337, 420 and 555 nm, respectively. The band at 281 nm corresponded to the ⁴A₂-⁴T₁(4P) transition of Cr³⁺ and that at 337 nm originated from the charge transfer from 2p orbitals of O^2-to the 4s4p orbital of Ga³⁺, while the bands at 420 and 555 nm were related to the transitions of ⁴A₂-⁴T₁ and ⁴A₂-⁴T_2gof Cr³⁺ ions, respectively. The emission spectrum was composed of the zero-phonon lines corresponding to the ²E-⁴A₂ transition of Cr³⁺(689 nm, R sharp line), the N-line (696 nm) of Cr³⁺ locating at distorted sites, and the phonon-side bands. Therefore, this phosphor can be used as a red phosphor material in white LED.

Key words: Zn6Ga8-xTiO20:xCr, red phosphor, microstructure, emission

中图分类号:

TQ174

郑遗凡, 张露露, 王锴, 潘再法. 混合尖晶石型Zn₆Ga₈TiO₂₀:Cr³⁺荧光粉的合成、结构表征与发光性能[J]. 无机材料学报, 2018, 33(1): 9-13.

ZHENG Yi-Fan, ZHANG Lu-Lu, WANG Kai, PAN Zai-Fa. Microstructure Characterization and Luminescent Property of Mixed Spinel Zn₆Ga₈TiO₂₀:Cr³⁺ Phosphors[J]. Journal of Inorganic Materials, 2018, 33(1): 9-13.

图/表 9

图1 Zn6Ga8-xTiO20:xCr3+(x=0~0.05)系列荧光粉的XRD图谱以及ZnGa2O4标准卡片衍射线(PDF 086-0413)

Fig. 1 XRD patterns of Zn6Ga8-xTiO20:xCr3+(x=0-0.05) phosphors and standard diffraction peaks of ZnGa2O4(PDF 086-0413)

图2 Zn6Ga7.975TiO20:0.035Cr3+的Rietveld精修图谱

Fig. 2 Rietveld refinement pattern of Zn6Ga7.975TiO20: 0.035Cr3+

图3 Zn6Ga7.975TiO20:0.035Cr3+的晶体结构

Fig. 3 Crystal structure of Zn6Ga7.975TiO20:0.035Cr3+

图4 Zn6Ga7.975TiO20:0.035Cr3+的(a)高分辨透射电镜照片和(b)电子衍射图

Fig. 4 (a) HRTEM image and (b) SAED pattern of Zn6Ga7.975 TiO20:0.035Cr3+

图5 Zn6Ga7.975TiO20:0.035Cr3+的元素面分布图

Fig. 5 EDS mapping of Zn6Ga7.975TiO20:0.035Cr3+

图6 Zn6Ga7.975TiO20:0.035Cr3+的激发和发射光谱图

Fig. 6 PLE and PL spectra of Zn6Ga7.975TiO20:3.5%Cr3+

图7 监测696 nm处Cr3+在Zn6Ga7.975TiO20:0.035Cr3+的荧光衰减曲线

Fig. 7 Photoluminescence decay curves of Zn6Ga7.975TiO20: 0.035Cr3+ monitored at 696 nm

图8 Zn6Ga8-xTiO20:xCr3+(x=0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05)的发射光谱图

Fig. 8 PL spectra of Zn6Ga8-xTiO20:xCr3+(x=0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05)

图9 不同温度下Zn6Ga7.975TiO20:0.035Cr3+的发射光谱图插图为该样品在709 nm发射波长下对应的最大发射强度对温度所作的归一化折线图

Fig. 9 Temperature-dependent emission of Zn6Ga7.975TiO20: 0.035Cr3+. The illustration shows the normalized lineup of the maximum emission intensity versus temperature for the sample at the 709 nm emission wavelength

参考文献 16

[1]	CHEN YUN-XIA, HU QI, CAO CHUN-E, et al.Effects of Zn2+ and Cr3+ doping on nano-sized CoAl2O4 spinel pigments by hydrothermal processing.Journal of Inorganic Materials, 2012, 27(12): 1317-1320.
[2]	COSTA V C, LAMEIRAS F S,PINHEIRO M V B, et al..Laser spectroscopy and electron paramagnetic resonance of Cr3+ doped silicate glasses.Journal of Non-Crystalline Solids, 2000, 273(1/ 2/3): 209-214.
[3]	WANG XIAO-XIAO, YANG LING, LIU HONG, et al.Optical properties of ZnS: Co+Cr nanocrystals synthesized by a low temperature hydrothermal process.Journal of Inorganic Materials, 2014. 29(10): 1049-1054.
[4]	BRIAN N,FIGGIS, MICHAEL A H. Ligand Field Thorery and Its Applications. 1. Wiley-VCH Press, 1999: 1-376.
[5]	FEOFILOV P P, TIMOFEEVA V A, TOLSTOI M N, et al.On the luminescence of neodymium and chromium in yttrium aluminum garnet.Optics & Spectroscopy, 1965, 19: 451.
[6]	ALLIX M, CHENU S, VÉRON E, et al. Considerable improvement of long-persistent luminescence in germanium and tin substituted ZnGa2O4.Chemistry of Materials, 2013, 25(9): 1600-1606.
[7]	ZHANG WEI-WEI, ZHANG JUN-YING, CHEN ZI-YU, et al.Spectrum designation and effect of Al substitution on the luminescence of Cr3+ doped ZnGa2O4 nano-sized phosphors.Journal of Luminescence, 2010, 130(10): 1738-1743.
[8]	BESSIÈRE A, JACQUART S, PRIOLKAR K, et al. ZnGa2O4: Cr3+: a new red long-lasting phosphor with high brightness.Optics Express, 2011, 19(11): 10131-10137.
[9]	LI YANG, LI YI-YANG, CHEN RU-CHUN, et al.Tailoring of the trap distribution and crystal field in Cr3+-doped non-gallate phosphors with near-infrared long-persistence phosphorescence.Npg Asia Materials, 2015. 7(5): e180.
[10]	ZERARGA F, BOUHEMADOU A, KHENATA R, et al.ChemInform abstract: structural, electronic and optical properties of spinel oxides ZnAl2O4, ZnGa2O4 and ZnIn2O4.ChemInform, 2011, 13(42): 1638-1648.
[11]	SICKAFUS K E, WILLS J M, GRIMES N W.Structure of spinel.Journal of the American Ceramic Society, 1999, 82(12): 3279-3292.
[12]	SUN XIAO-QIN, WANG SHU-WEI, SHEN CAI, et al.Efficient photocatalytic hydrogen production over Rh-doped inverse spinel Zn2TiO4.ChemCatChem, 2016, 8(13): 2289-2295.
[13]	COGLE T J, MATEUS C A S, BINKS J H, et al.. Solid-solution formation, electrical properties and zero-resistance behaviour in the spinel system Mg2TiO4-MgTi2O4.Journal of Materials Chemistry, 1991, 1(2): 289-291.
[14]	杨小平, 崔瑞瑞, 张弛, 等. 新型近红外超长余辉材料 Zn3Al2Ge2O10: Cr3+的发光性能. 发光学报, 2014, 35(3): 300-305.
[15]	SINGH V, CHAKRADHAR R P S, RAO J L, et al. EPR and photoluminescence properties of combustion-synthesized ZnAl2O4: Cr3+ phosphors.Journal of Materials Science, 2011, 46(7): 2331-2337.
[16]	WANG XIAN-SHENG, WAN MIN-HUA, WANG YIN-HAI, et al.Structure and luminescence properties of GaO;Crby Al doping.Spectroscopy & Spectral Analysis, 2013, 33(11): 2921-2925.

混合尖晶石型Zn₆Ga₈TiO₂₀:Cr³⁺荧光粉的合成、结构表征与发光性能

Microstructure Characterization and Luminescent Property of Mixed Spinel Zn₆Ga₈TiO₂₀:Cr³⁺ Phosphors

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