四面体掺杂尖晶石结构Co1-xRexCr2O4(Re=Li、Na、K、Rb)的电子结构和光学性质

doi:10.15541/jim20150030

无机材料学报 ›› 2015, Vol. 30 ›› Issue (8): 819-824.DOI: 10.15541/jim20150030 CSTR: 32189.14.10.15541/jim20150030

四面体掺杂尖晶石结构Co_1-_xRe_xCr₂O₄(Re=Li、Na、K、Rb)的电子结构和光学性质

杨志怀^{1, 2}, 张云鹏¹, 张美光², 许强², 张亚妮², 张蓉³

(1. 西安理工大学材料科学与工程学院, 西安 710048; 2. 宝鸡文理学院物理与光电技术学院, 宝鸡 721016; 3. 西北工业大学理学院, 西安 710072)

收稿日期:2015-01-11 修回日期:2015-03-23 出版日期:2015-08-20 网络出版日期:2015-07-21
作者简介:杨志怀(1967–), 男, 博士研究生, 讲师. E-mail:yzhihuai@163.com
基金资助:
国家自然科学基金(11204007);陕西省科技攻关计划(2014K08-17);陕西省自然科学基金项目(2012JQ1011);陕西省教育厅科学研究项目(12JK0983);宝鸡市科技攻关计划(14GYGG-5-2);宝鸡文理学院项目(YK1027, ZK14011, ZK15009)National Natural Science Foundation of China (11204007);Key Science and Technology Program of Shaanxi Province (2014K08-17);Natural Science Foundation of Shaanxi Province (2012JQ1011);Department of Education Science Research Project of Shaanxi Province (12JK0983);Key Science and Technology Program of Baoji (14GYGG-5-2);Key Project of Baoji University of Arts and Sciences (YK1027, ZK14011, ZK15009)

The Electronic and Optical Properties of Tetrahedral Doped Co_1-_xRe_xCr₂O₄ (Re = Li, Na, K, Rb) Spinel

YANG Zhi-Huai^{1, 2}, ZHANG Yun-Peng¹, ZHANG Mei-Guang², XU Qiang², ZHANG Ya-Ni², ZHANG Rong³

(1. School of Materials Science and Engineering, Xi'an University of Technology, Xi'an 710048, China; 2. Institute of Physics & Optoelectronics Technology, Baoji University of Arts and Sciences, Baoji 721016, China; 3. Science College, Northwestern Polytechnical University, Xi'an 710072, China)

Received:2015-01-11 Revised:2015-03-23 Published:2015-08-20 Online:2015-07-21
About author:YANG Zhi-Huai. E-mail:yzhihuai@163.com

摘要/Abstract

摘要：

采用基于密度泛函理论(DFT)的平面波超软赝势方法, 计算了CoCr₂O₄及Li、Na、K和Rb四面体掺杂CoCr₂O₄的基态结构、电子结构和光学性质。计算结果表明: 一价离子四面体掺杂都导致晶格有微小的畸变, 使体系的稳定性降低, Rb掺杂的体系最稳定; 电子态密度的计算结果表明: 掺杂体系的导带主要有Co-3d和Cr-3d轨道电子构成, 掺杂离子改变了CoCr₂O₄导带的电子结构, 主要引起了导带Co-3d态密度峰的下移, 随着掺杂浓度的增大, 费米能级进入价带更深; 光学性质计算表明: 掺杂体系的吸收光谱发生红移, 并在低能区有很强的吸收, 表明掺杂能极大地提高CoCr₂O₄对可见光的吸收和光催化效率。

关键词: 尖晶石结构CoCr2O4, 密度泛函理论, 电子结构, 光学性质

Abstract:

The structure parameters, electronic density of states, and optical properties of Re (Re = Li, Na, K and Rb) doped tetrahedral Co_(1-_x₎Re_xCr₂O₄(x=0.125) system were investigated by using plane-wave ultrasoft pseudopotential method with generalized gradient approximation. The obtained data indicate that monovalent ions doping results in a slight tetrahedral lattice distortion, leading to the stability of the system being reduced and the Rb doped system the most stable. The calculated electronic density of states demonstrates that the conduction bands of doping system are mainly dominated by Co-3d and Cr-3d electrons and the peak of Co-3d in conduction band shifts down when compared to the pure CoCr₂O₄. Moreover, the Fermi levels of the doping system get into the deeper valence band along with the doping concentration increases. Finally, the doped systems present a red shift phenomenon and a strong absorption in the low energy region according to the absorption spectral calculations, suggesting that doping system can greatly improve the absorption and photo catalytic efficiency of visible light for CoCr₂O₄.

Key words: CoCr2O4 spine, density functional theory, electronic structure, optical properties

中图分类号:

杨志怀, 张云鹏, 张美光, 许强, 张亚妮, 张蓉. 四面体掺杂尖晶石结构Co_1-_xRe_xCr₂O₄(Re=Li、Na、K、Rb)的电子结构和光学性质[J]. 无机材料学报, 2015, 30(8): 819-824.

YANG Zhi-Huai, ZHANG Yun-Peng, ZHANG Mei-Guang, XU Qiang, ZHANG Ya-Ni, ZHANG Rong. The Electronic and Optical Properties of Tetrahedral Doped Co_1-_xRe_xCr₂O₄ (Re = Li, Na, K, Rb) Spinel[J]. Journal of Inorganic Materials, 2015, 30(8): 819-824.

图/表 8

图1 CoCr2O4的晶体结构及多面体表示

Fig. 1 Crystal structure (a) and polyhedral view of CoCr2O4(b)The grey is octahedron, blue is the tetrahedron, and blue spheres represent Co, red spheres represent O, and purple spheres represent Cr As atoms

表1 CoCr2O4掺杂前后晶格常数及能量的变化

Table 1 Change of lattice constants and energies of pure CoCr2O4 and doping systems

Spcies	Latice/nm a=b=c	Difference ΔV/ %	Energy 10⁴/ eV	Space group
Pure	0.84465	0.0	-6.1828	FD-3M (227)
Li	0.84306	-0.5638	-5.9550	CS-3(8)
Na	0.84644	0.6365	-6.0664	CS-3(8)
K	0.84983	1.8510	-6.0138	CS-3(8)
Rb	0.85318	3.0643	-6.1441	CS-3(8)

表2 CoCr2O4掺杂前后化学键的变化

Table 2 Change of bond of pure CoCr2O4 and doping systems

Spcies	Bond	Population	Spin	Length/nm
Pure	O-Cr	0.28	-0.01	0.20176
Pure	O-Co	0.36	-0.01	0.19940
Li	O-Li	0.0225	0.0075	0.20390
	O-Cr	0.2922	-0.0117	0.20129
	O-Co	0.3429	-0.0185	0.20000
Na	O-Na	0.0775	0.01	0.21740
	O-Cr	0.2952	-0.0031	0.20150
	O-Co	0.3461	-0.0076	0.20034
K	O-K	-0.2075	0.005	0.22993
	O-Cr	0.2974	-0.0117	0.20186
	O-Co	0.3503	-0.0165	0.20082
Rb	O-Rb	-0.0975	0.0025	0.23739
	O-Cr	0.2991	-0.0109	0.20215
	O-Co	0.35	-0.0171	0.20118

图2 Co(1-x)RexCr2O4的分立态密度(PDOS)

Fig. 2 Partial density of states (PDOS) of different doping Co(1-x)RexCr2O4 system(a) Pure; (b) Li doped; (c) Na doped; (d) K doped; (e) Rb doped; (f) Doping of various Re at low PDOS

图 3 纯CoCr2O4及掺杂CoCr2O4的介电常数曲线

Fig. 3 Dielectric function curves of pure CoCr2O4 and doped CoCr2O4 (a) The real parts ε1(ω); (b) The imaginary parts ε2(ω)

图4 纯CoCr2O4及掺杂CoCr2O4的光电导率谱

Fig. 4 Optical conductivity spectra of pure CoCr2O4 and doped CoCr2O4 (a) The real parts; (b) The imaginary parts

图6 纯CoCr2O4及掺杂CoCr2O4的光吸收曲线

Fig. 6 Optical absorption curves of pure and doped CoCr2O4

图 5 纯CoCr2O4及掺杂CoCr2O4的复折射率

Fig. 5 The codex refractive index of pure CoCr2O4 and doped CoCr2O4, (a) Refractive index n; (b) Extinction coefficient k

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四面体掺杂尖晶石结构Co_1-_xRe_xCr₂O₄(Re=Li、Na、K、Rb)的电子结构和光学性质

The Electronic and Optical Properties of Tetrahedral Doped Co_1-_xRe_xCr₂O₄ (Re = Li, Na, K, Rb) Spinel

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