氮掺杂对锐钛矿相TiO<sub>2</sub>的电子结构及光学性质的影响研究

尹翔鹭; 滕艾均; 曾泽华; 张东彬; 代宇; 毋伟

doi:10.7513/j.issn.1004-7638.2022.02.001

氮掺杂对锐钛矿相TiO₂的电子结构及光学性质的影响研究

doi: 10.7513/j.issn.1004-7638.2022.02.001

1.
鞍钢集团北京研究院有限公司, 北京 102211
2.
北京化工大学, 北京 100029

详细信息

作者简介:
尹翔鹭（1990—），男，山东潍坊人，研究生，工程师，主要研发方向：纳米功能材料，E-mail：Xiangluyin@163.com

中图分类号: TF823,TQ426
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- 被引次数: 0
出版历程
- 收稿日期: 2021-12-01
- 网络出版日期: 2022-05-11
- 刊出日期: 2022-04-28

Study of electronic structures and optical properties of N-doped anatase TiO₂

1.
Ansteel Beijing Research Institute Co., Ltd., Beijing 102211, China
2.
Beijing University of Chemical Technology, Beijing 100029, China

摘要

摘要: 通过氮原子取代不同位置的Ti或者O原子，构建了三种不同掺杂结构的氮掺杂TiO₂：O-Ti-N、Ti-O-N和N-Ti-N。基于密度泛函理论，第一性原理计算研究了三种氮掺杂结构对于TiO₂的晶体结构、能带结构、态密度和光学性质的影响。研究结果表明：三种掺杂结构都可以稳定地存在于TiO₂中，符合文献报道。氮原子的掺杂显著降低了TiO₂的禁带宽度。由于N 2p和O 2p之间的杂化作用，在禁带区域形成杂质能级，降低了激发电子向导带跃迁所需的能量。Ti-O-N掺杂结构的TiO₂吸收光谱发生了明显的红移现象，说明该结构更有利于提高TiO₂在可见光范围的光催化活性。
- 氮掺杂二氧化钛 /
- 能带结构 /
- 态密度 /
- 光学性质
Abstract: By substituting N atoms for Ti or O atoms at different positions, three doped structures at different positions are constructed, i.e., O-Ti-N, Ti-O-N and N-Ti-N. Based on density functional theory and first-principles calculations, the effects of three kinds of nitrogen doping on the crystal structure, energy band structure, density of states and optical properties of TiO₂ were studied. The research results show that all three doped structures can be stably existed in TiO₂. The doping of nitrogen atoms significantly reduces the band gap of TiO₂. Due to the hybridization between N 2p and O 2p, impurity levels are formed in the forbidden band region, which reduces the energy required to excite the electron to conduction band. In the Ti-O-N structure, the absorption spectrum shows obvious red shift, which proves that this structure is more conducive to improving the photocatalytic activity of TiO₂ in the visible light range.
- N-doped TiO₂ /
- energy band structure /
- density of state /
- optical properties

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图 1 晶体结构示意

（a）纯TiO₂；（b）O-Ti-N；（c）Ti-O-N；（d）N-Ti-N

Figure 1. Schematic diagram of crystal structure

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图 2 纯TiO₂和氮掺杂TiO₂的能带结构

Figure 2. The energy band structure of pure TiO₂ and N-doped TiO₂

(a) TiO₂；(b) O-Ti-N；(c) Ti-O-N；(d) N-Ti-N

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图 3 纯TiO₂和氮掺杂TiO₂的态密度

Figure 3. The density of state of pure TiO₂ and N-doped TiO₂

（a）TiO₂；（b）O-Ti-N；（c）Ti-O-N；（d）N-Ti-N

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图 4 纯TiO₂和氮掺杂TiO₂的介电函数实部

Figure 4. The real part of dielectric function of pure TiO₂ and N-doped TiO₂

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图 5 纯TiO₂和氮掺杂TiO₂的介电函数虚部

Figure 5. The imaginary part of dielectric function of pure TiO₂ and N-doped TiO₂

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图 6 纯TiO₂和氮掺杂TiO₂的吸收光谱

Figure 6. The absorption spectrum of pure TiO₂ and N-doped TiO₂

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表 1 TiO₂和氮元素掺杂TiO₂优化后的晶胞参数和总能量

Table 1. Optimized unit cell parameters and total energy of pure TiO₂ and N-doped TiO₂

类型	a/nm	b/nm	c/nm	V/nm³	E₀/eV
TiO₂	0.778710	0.778710	0.978800	0.593533794	−365.54086917
O-Ti-N	0.781097	0.778549	0.978708	0.595174387	−363.54055310
Ti-O-N	0.777451	0.777451	0.971251	0.587052397	−353.11233872
N-Ti-N	0.782302	0.778209	0.981618	0.597601365	−361.82706653

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