[1]席丽丽,邱雨婷,史讯,等.CoSb3基方钴矿化合物的Ga,In掺杂及相关复杂缺陷的研究[J].中国材料进展,2015,(1):041-49.[doi:10.7502/j.issn.1674-3962.2015.01.04]
　Xi Lili,Qiu Yuting,Shi Xun,et al.Complex Doping of Ga, In and related defect study in caged skuttterudites CoSb3[J].MATERIALS CHINA,2015,(1):041-49.[doi:10.7502/j.issn.1674-3962.2015.01.04]
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CoSb3基方钴矿化合物的Ga,In掺杂及相关复杂缺陷的研究()
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中国材料进展[ISSN:1674-3962/CN:61-1473/TG]

卷:
期数:
2015年第1期
页码:
041-49
栏目:
特约研究论文
出版日期:
2015-01-31

文章信息/Info

Title:
Complex Doping of Ga, In and related defect study in caged skuttterudites CoSb3
作者:
席丽丽1; 邱雨婷1; 史讯1; 杨炯2;  陈立东1; 杨继辉2; 张文清1
1中国科学院上海硅酸盐研究所，上海 200050 中国
 2美国华盛顿大学，西雅图，98195-2120美国
Author(s):
Xi Lili1;  Qiu Yuting1;  Shi Xun1;  Yang Jiong2;  Chen Lidong1;  Yang Jihui2;  Zhang Wenqing1

1Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

2University of Washington, Seattle, WA 98195-2120, USA

关键词:
方钴矿; 第一性原理; 热电材料; 复杂缺陷结构
DOI:
10.7502/j.issn.1674-3962.2015.01.04
文献标志码:
A
摘要:
本文通过第一性原理与热力学结合的方法，研究了Ga, In等元素掺杂的CoSb3基方钴矿化合物中的复杂缺陷问题。详细计算了Ga，In在CoSb3中填充，Co，Sb位置替换以及填充--替换同时共存等缺陷的形成能。研究结果表明, 缺陷形成能与费米能级、化学势等相关，Ga，In等元素在方钴矿中不是单纯的填充，而是填充和Sb位置替换同时共存的复杂缺陷。Ga掺杂以填充--替换比例2:1的缺陷为主，而In元素掺杂，根据不同的条件可形成填充, 替换, 以及不同比例的填充替换复合缺陷, 其中尤其以4:2和2:1的最多。根据巨正则系宗, 研究了Ga, In掺杂系统的载流子浓度和各缺陷的浓度。 发现Ga, In掺杂的方钴矿由于填充和替换电荷的自补偿效应, 其载流子浓度较低，尤其是Ga填充, 具有类似本证半导体的低载流子浓度，且得到实验证实。In掺杂系统由于填充替换的比例偏离2:1, 填充位置的In比Ga的稍高一些，因此具有比Ga掺杂更高的载流子浓度。
Abstract:
Complex doping is one of the challenging problems to be understood in doping and the associated structure tuning in materials science. Here we investigate the single-impurity-induced complex doping behaviors of group 13 elements Ga or In in caged skutterudite CoSb3 through a combination of ab initio total-energy calculations and thermodynamics. Formation energies of void filling, Sb-substitution, and complex dual-site occupancy defects with different charge states, and their dependence on chemical potentials of species are considered. Our results show that Ga atoms predominantly form the dual-site 2GaVF-GaSb defects and substitute for Sb only at very high Fermi levels or electron concentrations. Indium atoms, on the other hand, can play multiple roles in skutterudites, including filling in the crystalline voids, substituting for Sb atoms, or forming dual-site occupancy, among which the fully charge-compensated dual-site defects (2InVF-InSb and 4InVF-2InSb) are dominant. The total defect concentrations are studied by using overall charge neutrality under the grand canonical ensemble. The concentration ratio of impurities at void-filling sites and that at Sb-substitution sites for Ga-doped CoSb3 is very close to be 2:1, while this value visibly deviates from 2:1 for In-doped CoSb3. The 2:1 ratio of Ga-doping in CoSb3 causes low electron concentration (~2*1019cm-3) and makes the doped system a semiconductor. The underlying physics of the doping behavior for group 13 elements in CoSb3 is also analyzed.
更新日期/Last Update: 2014-12-31