LI Chang-sheng, REN Jun, GUO Hai-yan， PENG Xing， WANG Jian-long, CAO Duan-lin
(School of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China)
Abstract： The impact of N- and X(X=S, Se, Te)-codoping on electronic properties of anatase TiO2 has been systematically investigated using density functional theory (DFT). The optimized geometry shows that there is large lattice expansion for the codoped anatase TiO2 due to large atomic radius of the codoped atom. The calculated substitution energies indicate that incorporation of X(X=S,Se,Te) into N-doped bulk TiO2 can not promote synergistic effect on N after substituting for Ti, whereas it is better after substituting for O. According to the total density of states (DOS) and corresponding partial DOS (PDOS), it can be seen that substituting X(X=S,Se,Te) for O, N 2p orbital is strongly hybridized with impurity states (S 3p,Se 4p,Te 5p). After substituting X(X=S,Se,Te) for Ti, conduction band is mainly dominated by Ti 3d orbit and S 3p (Se 4p or Te 5p )-N 2p-Ti 3d hybridized states are formed. Based on Bader analysis, it can be indicated that the electron transfer is from N to X(X=S,Se,Te) if substituting X(X=S,Se,Te) for O, but it is opposite if substitute X(X=S,Se,Te) for Ti.
Key words： anatase TiO2; electronic properties; substitution energy; codoping
CLD number： O614.41 Document code： A
Article ID： 1674-8042(2014)01-0088-08 doi： 10.3969/j.issn.1674-8042.2014.01.018
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N和硫属元素X(X=S, Se, Te)共掺杂锐钛矿TiO2电子性质的第一性原理计算
李昌盛， 任君， 郭海燕， 彭兴， 王建龙， 曹端林
（中北大学 化工与环境学院，山西 太原 030051）
摘要:本文运用密度泛函理论系统地研究了 N 和 X(X=S, Se, Te)共掺杂锐钛矿 TiO2 时电子特性所受的影响。 优化后的结构表明， 在锐钛矿TiO2共掺杂时， 由于掺杂原子有较大的原子半径而引起了大的晶格膨胀。 从计算的替换能结果看， 当X(X=S,Se,Te)掺杂到有N原子存在的TiO2时， 若替换Ti原子， 则不能很好地促进与N的协同作用， 若替换O原子， 则相反。 从总态密度图和分态密度图来看， 替换O原子后的N 2p轨道和其他杂质带 S 3p, Se 4p, Te 5p杂化在一起； 同时替换Ti原子后， 导带主要由Ti 3d轨道所占据， 从而形成了S 3p (Se 4p or Te 5p )-N 2p-Ti 3d杂化态。 从Bader电荷的结果可知， 替换O原子， 电子转移是由N到X(X=S,Se,Te)， 而替换Ti原子后， 电子转移是由X(X=S,Se,Te)到N。
关键词:锐钛矿TiO2；电子性质；替换能；共掺杂
引用格式：LI Chang-sheng, REN Jun, GUO Hai-yan， et al. First-principles calculation of electronic properties of N- and X(X=S,Se,Te)-codoped anatase TiO2. Journal of Measurement Science and Instrumentation, 2014, 5(1): 88-95. [doi: 10.3969/j.issn.1674-8042.2014.01.018]
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