Zn3-xMnxTeO6的晶体结构与吸收光谱和磁性研究

doi:10.15541/jim20190606

摘要/Abstract

摘要：

本工作主要研究Mn ²⁺离子掺杂的类刚玉系氧化物Zn₃TeO₆(0<x≤2.0)的晶体结构与光学性质和磁性的变化。Zn_3-_xMn_xTeO₆粉末样品通过固相反应合成。Mn掺杂量的相图表明, x<1.0时保持单斜(C2/c)结构, 1.0≤x≤1.6为单斜(C2/c)和三方六面体混合相(R-3), x≥1.8时完全转变为R-3相, 且x=2.0时形成ZnMn₂TeO₆, Te-O和Mn/Zn-O键长增大, 八面体发生更大畸变。X射线粉末衍射结构精修也表明R-3相中Zn/MnO₆为畸变八面体。随着Mn ²⁺掺杂含量的增加, Zn_3-_xMn_xTeO₆系列化合物不仅结构发生变化, 其颜色也由浅变深。紫外吸收光谱中随着掺杂浓度的增加, 400~550 nm处的吸收增强, 样品的光学带隙也由3.25 eV (x=0.1)逐渐减小到2.08 eV (x=2.0), 分析表明, 可见区吸收的增强是源于MnO₆八面体中Zn/MnO₆八面体中Mn ²⁺离子的d-d跃迁, 导致样品由浅黄色逐渐变为暗黄色。磁性测试表明, 固溶体的反铁磁转变温度随着Mn ²⁺掺杂量的提高而逐渐增加, 且掺入的Mn ²⁺离子以高自旋态存在。

关键词: Zn₃TeO₆-Mn₃TeO₆, 晶体结构, 磁性, 紫外吸收光谱

Abstract:

The effects of Mn ²⁺ doping on the structural, optical and magnetic properties of the corundum-related oxide Zn₃TeO₆ were investigated. Polycrystalline ceramic samples of the solid solution Zn_3-_xMn_xTeO₆ (0<x≤2.0) were prepared by a solid-state reaction route. Phase diagram as a function of Mn concentration indicates monoclinic (C2/c) structure for x<1.0, disproportionated mixing of both monoclinic (C2/c) and rhombohedral (R-3) structure for 1.0≤x≤1.6, and R-3 structure for x≥1.8. Moreover, when x=2.0, ZnMn₂TeO₆ was formed, in which the bond length of Te-O and Mn/Zn-O increased, and the Mn/ZnO₆ octahedra became more distorted. Rietveld refinements of the crystal structures from the powder X-ray diffraction (XRD) data showed that the Zn/MnO₆ octahedra were highly distorted in R-3 phase. With the increase of Mn ²⁺ doping content, the solid solution Zn_3-_xMn_xTeO₆ demonstrated not only the structure change from C2/c to R-3, but also the color evolution from light yellow to dark yellow. In optical absorption spectroscopy, with the increase of Mn ²⁺ doping concentration, the absorption at 400-550 nm was enhanced, and the optical band gap of the samples gradually decreased from 3.25 eV (x=0.1) to 2.08 eV (x=2.0). Analysis revealed that the color of samples changed from light yellow to dark yellow is due to the d-d transition of Mn ²⁺ ions in Zn/MnO₆ octahedron. Magnetic measurements indicate that the antiferromagnetic transition temperature of the solid solution gradually increased with the increase of the doping amount of Mn ²⁺, and the doped Mn ²⁺ ions exist in a high spin state.

Key words: Zn₃TeO₆-Mn₃TeO₆, crystal structure, magnetism, ultraviolet absorption spectrum

中图分类号:

TQ174

李淑芳,赵爽,周潇,李满荣. Zn_3-_xMn_xTeO₆的晶体结构与吸收光谱和磁性研究[J]. 无机材料学报, 2020, 35(8): 895-901.

LI Shufang,ZHAO Shuang,ZHOU Xiao,LI Manrong. Crystal Structures, Optical, and Magnetic Properties of Zn_3-_xMn_xTeO₆[J]. Journal of Inorganic Materials, 2020, 35(8): 895-901.

图/表 8

图1 化合物Zn3-xMnxTeO6(0<x≤2.0)的粉末衍射图谱

Fig. 1 XRD patterns of Zn3-xMnxTeO6 (0<x≤2.0)

图2 固溶体Zn3-xMnxTeO6 (0<x≤2.0)晶胞参数a, b, c [nm] (a)以及V [nm3] (b)的变化

Fig. 2 Lattice parameters a, b and c [nm] (a), and V [nm3] (b) obtained from Zn3-xMnxTeO6 (0<x≤2.0) solid solutions by XRD measurements at room temperature

图3 ZnMn2TeO6的X射线粉末衍射结构精修结果(a)和基于粉末精修结果得到的ZnMn2TeO6的晶体结构(b)

Fig. 3 Rietveld refined of the PXRD data (a) and crystal structure (b) of ZnMn2TeO6 Zn/Mn: blue spheres; Te: yellow spheres; O: red spheres; TeO6 octahedra: yellow; MnO6 octahedra: blue

表1 精修得到的ZnMn2TeO6的晶体结构参数

Table 1 Crystallographic parameters for ZnMn2TeO6 obtained from the Rietveld refinement of the PXRD data

Atom	Site	x	y	z	B/nm²	Occ.
Mn/Zn	18f	0.0388(1)	0.2240(1)	0.2864(1)	0.00510(1)	0.667/0.333
Te1	3b	0	0	0.5	0.00710(1)	1.0
Te2	3a	0	0	0	0.00320(1)	1.0
O1	18f	0.1773(4)	0.1972(4)	0.3833(1)	0.00510(1)	1.0
O2	18f	0.2061(3)	0.0348(5)	0.1071(2)	0.00550(1)	1.0

图4 化合物Zn3-xMnxTeO6 (0<x≤2.0)在日光下的颜色变化

Fig. 4 Color evolution of the Zn3-xMnxTeO6 (0<x≤2.0) compounds in daylight

图5 化合物Zn3-xMnxTeO6(0<x≤2.0)的紫外光谱

Fig. 5 Optical absorption (UV/Vis) spectra of the Zn3-xMnxTeO6 (0<x≤2.0) compounds

图6 化合物Zn3-xMnxTeO6 (0<x≤2.0)在7.96×104 A/m磁场强度下的从5到300 K的磁化率曲线

Fig. 6 Temperature-dependent susceptibility of Zn3-xMnxTeO6 (0<x≤2.0) measured between 5-300 K under magnetic field of 7.96×104 A/m

图7 化合物Zn3-xMnxTeO6 (0<x≤2.0)在5和300 K时的磁化曲线

Fig. 7 Isothermal magnetization of Zn3-xMnxTeO6 (0<x≤2.0) measured at 5 and 300 K, respectively

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Zn_3-_xMn_xTeO₆的晶体结构与吸收光谱和磁性研究

Crystal Structures, Optical, and Magnetic Properties of Zn_3-_xMn_xTeO₆

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