无机化学学报

掺杂和取代对红色荧光材料SrAl₁₂O₁₉:Mn⁴⁺发光性能的影响

Doping and Replacing Effects on the Luminescent Properties of SrAl₁₂O₁₉:Mn⁴⁺ Red Phosphor

作者	单位	E-mail
辛小东	内蒙古大学化学与化工学院, 呼和浩特 010021
魏恒伟	陕西省大分子科学重点实验室, 陕西师范大学化学与化工学院, 西安 710062
赵文慧	稀土材料化学与应用国家重点实验室, 北京大学化学与分子工程学院, 北京100871
刘中仕	欧司朗(中国)有限公司, 上海 200082
李文先	内蒙古大学化学与化工学院, 呼和浩特 010021	nmglwx@163.com
焦桓	陕西省大分子科学重点实验室, 陕西师范大学化学与化工学院, 西安 710062	jiaohuan@snnu.edu.cn
荆西平	稀土材料化学与应用国家重点实验室, 北京大学化学与分子工程学院, 北京100871	xpjing@pku.edu.cn

摘要: SrAl₁₂O₁₉：Mn⁴⁺是一种用于高显色性白光发光二极管的候选红色荧光材料。本论文研究了Mg²⁺、Zn²⁺和Ge⁴⁺离子的掺杂效应以及Ga³⁺、Ca²⁺和Ba²⁺离子的取代效应对SrAl₁₂O₁₉：Mn⁴⁺荧光材料性能的影响。样品通过高温固相反应制备，焙烧温度在1 250~1 500 ℃之间。利用X射线衍射技术表征了材料的相纯度，用荧光激发光谱和发射光谱表征了材料的荧光性能。研究结果指出，与未进行Mg²⁺或Zn²⁺掺杂的样品相比，Mg²⁺或Zn²⁺离子对Al³⁺格位的掺杂可以使材料的发光强度提高~60%，其原因被认为是掺杂促进了激活剂Mn⁴⁺离子进入晶格，其过程可以表示为：MO+MnO₂⇔；M_Al^'+M_Al^·+3O_O^×（M=Mg，Zn），电子顺磁共振谱支持这一结果。Ge⁴⁺离子的掺杂使材料的发光性能明显下降。Ga³⁺离子可以取代Al³⁺离子形成全范围的固溶体，其中少量Ga³⁺离子的掺杂可以使材料的荧光发射强度提高~13%，而掺杂量进一步提高使材料的荧光性能下降。Ca²⁺和Ba²⁺对Sr²⁺的取代仅形成有限范围的固溶体。Ca²⁺的取代使材料的发光性能提高；而 Ba²⁺的取代使材料的发光强度下降。

关键词: 红色荧光粉白光发光二极管 SrAl₁₂O₁₉ Mn⁴⁺掺杂

基金项目: 国家自然科学基金（No.21371015）资助项目。

Abstract: SrAl₁₂O₁₉:Mn⁴⁺ is a potential candidate of red phosphor for high color rendering white LEDs. In this work, doping effects of Mg²⁺, Zn²⁺ or Ge⁴⁺ and replacing effects of Ga³⁺, Ca²⁺ or Ba²⁺ on the SrAl₁₂O₁₉:Mn⁴⁺ red phosphor were investigated. The samples were prepared by conventional solid state reactions at 1 250~1 500 ℃. The phase purities of the samples were investigated by X-ray diffraction and their luminescence properties were characterized by photoluminescence (PL) excitation and emission spectra. The results indicated that compared with the sample without the Mg²⁺ or Zn²⁺ doping, the Mg²⁺ or Zn²⁺ doping enhanced the PL intensity significantly (~60%), since this doping helped Mn⁴⁺ enter the lattice: MO+MnO₂⇔M_Al^'+M_Al^·+3O_O^×(M=Mg, Zn), which was supported by electron paramagnetic resonance spectra. The Ge⁴⁺ doping lead to a decrease of PL intensity clearly. Ga³⁺ could replace Al³⁺ to form whole range solid solutions. When small amount of Ga³⁺ was doped, the PL intensity increased (~13%), however when further increasing the Ga³⁺ content, the PL intensity decreased dramatically. The solid solutions only appeared in limited ranges for the Sr²⁺ replaced systems by Ca²⁺ and Ba²⁺. For the Ca²⁺ replacing system, the PL intensity increased with an increase of Ca²⁺ content, but for the Ba²⁺ replacing system, the PL intensity decreased with Ba²⁺ content.

Keywords: red phosphor white-LEDs SrAl₁₂O₁₉ Mn⁴⁺ doping

投稿时间：2015-09-30 修订日期：2016-06-07

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辛小东,魏恒伟,赵文慧,刘中仕,李文先,焦桓,荆西平.掺杂和取代对红色荧光材料SrAl₁₂O₁₉:Mn⁴⁺发光性能的影响[J].无机化学学报,2016,32(7):1199-1206.

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