离子交换法制备ZrO₂:Eu³⁺纳米晶及其发光特性

来源期刊：金属学报2010年第2期

论文作者：莎仁 王喜贵 李霞

文章页码：179 - 183

关键词：ZrO₂:Eu³⁺纳米晶； 离子交换法； 发光性质

Key words：ZrO₂:Eu³⁺ nanocrystal； ion exchange method； luminescence property

摘    要：以强碱性阴离子交换树脂为沉淀剂,采用离子交换法制备了ZrO₂:Eu³⁺纳米晶,通过XRD,TEM,HRTEM和EDS等对晶体的结构、形貌及化学成分进行了表征,利用3D荧光光谱、激发光谱和发射光谱研究了Eu³⁺在ZrO₂纳米晶中的发光性质。结果表明,焙烧温度在800℃以下所得的ZrO₂:Eu³⁺纳米晶主要为四方结构,晶粒尺寸约为5—20 nm,随着焙烧温度的升高,样品的晶结构发生了细微变化,从900℃开始出现了少量单斜晶,由ZrO₂:Eu³⁺的3D荧光光谱确定了其最佳监测波长和发射波长,在394 nm波长光的激发下观察到纳米ZrO₂中Eu³⁺的590 nm(⁵D₀→⁷F₁)和606 nm(⁵D₀→⁷F₂)特征发射谱,随着相结构细微的变化,发射光谱的形状及强度均发生变化,说明ZrO₂:Eu³⁺纳米晶的发光性质对其结构非常敏感。

Abstract: Eu³⁺ doped luminescent nano-materials have become a research focus due to their outstanding physical and chemical properties in light-emitting,magnetism,thermology,catalysis and chemical activity etc..Furthermore,the relationship between crystal structure and energy levels transition of these nano materials can be easily obtained by measuring the spectra of doped Eu³⁺.Among luminescence nano materials,ZrO₂ nano-crystal as a potential one has been attracted great attention in its higher refractive,good optical transparency and relatively low phonon energy.By now certain materials doped RE ion in the matrix ZrO₂ for ZrO₂:Er³⁺-Y³⁺ ZrO₂:Pr³⁺ and ZrO₂:(Pr³⁺,Sm³⁺) etc.,and mesoporous ZrO₂ nano-crystals doped Eu³⁺ by hydrothermal way have been reported.In present study,the ZrO₂:Eu³⁺ nano-crystal was prepared with high purity and uniform composition by ion exchange method using strong OH-as a precipitant.Its composition,morphology and structure were characterized by XRD,TEM,HRTEM and EDS.The experimental results show that it has a tetragonal crystal structure and its average grain size is 5-20 nm after calcined at 800℃.It is found that the microstructure of ZrO₂:Eu³⁺ changes slightly with the increase of calcining temperature till a small amount of monoclinic phase forms after calcined at higher than 900℃.The luminescent properties of Eu³⁺ in the ZrO₂ nano-crystal were measured by 3D emission and excitation spectra.The characteristic emission bands of 590 nm(⁵D₀→⁷F₁) and 606 nm(⁵D₀→7^F₂) of Eu³⁺ were observed at an excitation spectrum of λ_ex=394 nm.The luminescent properties of ZrO₂:Eu³⁺ are very sensitive to its microstructure change since slight changes in the ZrO₂:Eu³⁺ microstructure cause the changes in the shape and intensity of its emission spectra.