单点缺陷氧化石墨烯电子结构与光学特性的第一性原理研究

doi:10.15541/jim20190588

无机材料学报 ›› 2020, Vol. 35 ›› Issue (10): 1117-1122.DOI: 10.15541/jim20190588 CSTR: 32189.14.10.15541/jim20190588

所属专题：计算材料论文精选(2020)

单点缺陷氧化石墨烯电子结构与光学特性的第一性原理研究

林启民¹(),崔建功²,颜鑫¹,袁学光¹(),陈小瑜¹,芦启超¹,罗彦彬¹,黄雪³,张霞¹(),任晓敏¹

^1. 北京邮电大学信息光子学与光通信国家重点实验室, 北京 100876
^2. 中北大学电子测试技术重点实验室, 太原 030051
^3. 北京市计算中心, 北京 100094

收稿日期:2019-11-20 修回日期:2019-12-09 出版日期:2020-10-20 网络出版日期:2020-01-20
作者简介:林启民, 男, 博士研究生. E-mail:lqm@bupt.edu.cn.
基金资助:
国家自然科学基金(61774021);国家自然科学基金(61911530133);国家自然科学基金(61935003);信息光子学与光通信国家重点实验室(北京邮电大学)自主研究课题(IPOC2019ZT07);山西省青年科技研究基金(201801D221198);山西省高等学校科技创新项目(2019L0541);中央高校基本科研业务费(2018XKJC05)

First-principles Study on Electronic Structure and Optical Properties of Single Point Defect Graphene Oxide

LIN Qimin¹(),CUI Jiangong²,YAN Xin¹,YUAN Xueguang¹(),CHEN Xiaoyu¹,LU Qichao¹,LUO Yanbin¹,HUANG Xue³,ZHANG Xia¹(),REN Xiaomin¹

^1. State Key Laboratory of Information Photonics & Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876, China;
^2. State Key Laboratory of Dynamic Testing Technology, North University of China, Taiyuan 030051, China
^3. Beijing Computing Center, Beijing 100094, China

Received:2019-11-20 Revised:2019-12-09 Published:2020-10-20 Online:2020-01-20
About author:LIN Qimin, male, PhD candidate. E-mail: lqm@bupt.edu.cn
Supported by:
National Natural Science Foundation of China(61774021);National Natural Science Foundation of China(61911530133);National Natural Science Foundation of China(61935003);The Fund of State Key Laboratory of Information Photonics and Optical Communications (Beijing University of Posts and Telecommunications)(IPOC2019ZT07);Natural Science Foundation of Shanxi(201801D221198);STIP(2019L0541);Fundamental Research Business Expenses of Central Universities(2018XKJC05)

摘要/Abstract

摘要：

本研究采用基于密度泛函理论的第一性原理方法, 在局域密度近似和广义梯度近似下, 研究了单点缺陷下不同结构氧化石墨烯的电子结构和光学特性。研究结果表明: 文中四种构型的氧化石墨烯为力学稳定结构, 其中包含不饱和氧原子的氧化石墨烯结构在水裂解及制氢中具有重要应用潜力。能带及分波态密度计算结果表明, 包含不饱和氧原子的构型为间接带隙半导体, 其余构型均为直接带隙半导体, 且掺杂类型和带隙值随结构不同而改变。氧化石墨烯的光学吸收表现为各向异性, 且在垂直于平面方向上的吸收边蓝移到近紫外可见光区。包含sp ³杂化形式的结构光学吸收系数比包含sp ²杂化的结构高, 说明碳氧双键和悬挂键的存在对吸收光谱有重要影响。

关键词: 第一性原理, 氧化石墨烯, 光学性质, 能带, 吸收系数

Abstract:

In this study, the electronic structure and optical properties of graphene oxide in different structures with single point defect are studied under local density of states approximation and generalized gradient approximation by first-principles calculations based on the density functional theory. The results show that four models are mechanically stable, among which the oxide graphene containing unsaturated oxygen atoms shows an important application potential in water cracking and catalysis. The calculated band structures and partial-wave density of states show that the model containing unsaturated oxygen atoms exhibits indirect band gap, while other models exhibit direct band gap, and the doping type and band gap values vary with different models. The absorption spectrum of graphene oxide is anisotropic, and the absorption edge moves to the near-UV and visible region in the direction perpendicular to the plane. The optical absorption coefficient containing sp ³ hybrid is slightly higher than that containing sp ² hybrid, suggesting that the carbon-oxygen double bond and hanging bond have important influence on the absorption spectrum.

Key words: first-principles calculation, graphene oxide, optical property, band, absorbance

中图分类号:

O649

林启民, 崔建功, 颜鑫, 袁学光, 陈小瑜, 芦启超, 罗彦彬, 黄雪, 张霞, 任晓敏. 单点缺陷氧化石墨烯电子结构与光学特性的第一性原理研究[J]. 无机材料学报, 2020, 35(10): 1117-1122.

LIN Qimin, CUI Jiangong, YAN Xin, YUAN Xueguang, CHEN Xiaoyu, LU Qichao, LUO Yanbin, HUANG Xue, ZHANG Xia, REN Xiaomin. First-principles Study on Electronic Structure and Optical Properties of Single Point Defect Graphene Oxide[J]. Journal of Inorganic Materials, 2020, 35(10): 1117-1122.

图/表 7

图1 不同构型氧化石墨烯结构

Fig. 1 Different types of graphene oxide structures (a) Graphene oxide adsorbed with hydroxyl; (b) Graphene oxide with single substitution epoxy bond; (c) Graphene oxide with carbon oxygen double bond and sp3 hybrid epoxy bond; (d) Graphene oxide with two carbon-oxygen double bonds and one carbon-oxygen single bond; (e, f) and (e1, f1) Top and side views of the structure in (d) adsorbed with hydrogen on the upper and lower side of the suspended oxygen atom, respectively

表1 不同泛函计算的不同结构中的键长(nm)

Table 1 Bond length in different structures calculated by different pseudopotential functions (nm)

	^*	O₁-C₂	O₂-C₆	O₃-C₁₂
LDA	d₁	0.128	0.128	0.137
	d₂	0.128	0.128	0.136
	e	0.124	0.124	0.138
	f	0.124	0.124	0.137
GGA	d	0.124	0.124	0.133
	e	0.122	0.122	0.139
	f	0.122	0.122	0.138

表2 各氧化石墨烯结构形成能(eV)

Table 2 Formation energy with different structures (eV)

^*	(a)	(b)	(c)	(d)	(e)	(f)
LDA	-12.7	-6.1	-6.5	-13.1	-19.6	-18.6

表3 不同结构形式氧化石墨烯的弹性系数

Table 3 Elastic coefficients of graphene oxide with different structures

^*	C₁₁	C₂₂	C₁₂	C₆₆
a	1738.99	1618.45	282.75	1.03
b	1789.57	1761.01	309.15	1.63
c	1607.47	958.73	163.94	0.99
d	2015.11	1405.41	147.00	1.39
e	1968.65	825.43	148.48	-11.90
f	1846.90	710.38	240.54	-8.83

图2 三种结构中不同原子的电荷数

Fig. 2 The charge number of three kinds of different atoms in three structures showing in Fig. 1(d), (e) and (f) (d) Graphene oxide with two carbon-oxygen double bonds and one carbon-oxygen single bond; (e, f) Structure (d) adsorbed with hydrogen on the upper and lower side of the suspended oxygen atom, respectively

图3 各结构能带结构及态密度图

Fig. 3 Band structures and density of states (DOS) of different structure models (a) Graphene oxide adsorbed with hydroxyl; (b) Graphene oxide with single substitution epoxy bond; (c) Graphene oxide with carbon oxygen double bond and sp3 hybrid epoxy bond; (d) Graphene oxide with two carbon-oxygen double bonds and one carbon-oxygen single bond; (e,f) Structure (d) adsorbed with hydrogen on the upper and lower side of the suspended oxygen atom, respectively

图4 各结构光学吸收系数

Fig. 4 Absorption coefficient of different structure models in which (b-g) the absorption coefficient of graphene and structures in Fig. 1(a-f) (a) Graphene; (b) Graphene oxide adsorbed with hydroxyl; (c) Graphene oxide with single substitution epoxy bond; (d) Graphene oxide with carbon oxygen double bond and sp3 hybrid epoxy bond; (e) Graphene oxide with two carbon-oxygen double bonds and one carbon-oxygen single bond; (f, g) Structure (d) adsorbed with hydrogen on the upper and lower side of the suspended oxygen atom, respectively

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单点缺陷氧化石墨烯电子结构与光学特性的第一性原理研究

First-principles Study on Electronic Structure and Optical Properties of Single Point Defect Graphene Oxide

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