Be, Mg, Mn掺杂CuInO<sub>2</sub>形成能的第一性原理研究

莫曼; 曾纪术; 何浩; 张喨; 杜龙; 方志杰

doi:10.7498/aps.68.20182255

摘要

研制开发新型的光电材料对促进社会经济发展具有重要的科学意义和实用价值. 利用宽禁带CuInO₂铟基材料实现全透明光电材料是目前深入研究的热点. 通过基于密度泛函的第一性原理计算方法, 本文计算出掺杂元素Mg, Be, Mn在CuInO₂的形成能. 计算结果表明, 施主类缺陷(如掺杂元素替代Cu原子或进入间隙位置)由于较高的形成能和较深的跃迁能级, 很难在CuInO₂材料中出现N型导电; 而受主缺陷中, 在氧原子化学势极大的情况下, Mg原子替代In能成为CuInO₂理想的受主缺陷. 计算结果可为制备性能优异的CuInO₂材料提供指导.

关键词:

CuInO₂ /
掺杂 /
形成能

Abstract

Exploring new type of optoelectronic materials has fundamental scientific and practical significance in the development of society and economy. Recently, intense research has focused on the use of the wide band-gap bipolarity semiconductor material CuInO₂ which will allow to the fabrication of that total transparent optoelectronic materials. However, the conductivity of CuInO₂ is significantly lower than other n-type conductivity of other TCOs. As a result, one of the key question is how to improve the electric properties of CuInO₂ by doping method. Motivated by this observation, in this paper, using the first-principles methods, the formation energetics properties of dopant (Be, Mg, Mn) in transparent conducting oxides CuInO₂ were studied within the local-density approximation. Substituting dopant (Be, Mg, Mn) for In, substituting dopant (Be, Mg, Mn) for Cu and dopant as interstitial in their relevant charge state are considered. By systematically calculating formation energies and transition energy level of defect, the calculated results show that, substituting Mg for In does not induce the large structural relaxation. in CuInO₂. One can expect that substituting the Mg and Mn for In introduces acceptor because the relative lower formation energies, furthermore, Be atoms would be substitute for In atoms when the E_f move to CBM. In addition, the donor-type extrinsic defects(such as substituting dopant for Cu and dopant as interstitial) have difficulty in inducing n-conductivity in CuInO₂ because of their deep transition energy level or the higher formation energies. Considering the transition energy level position, Be_In, Mg_In, and Mn_In have transition energy levels at 0.06, 0.05, and 0.40 eV above the VBM, respectively. Thus, for all the acceptor-type extrinsic defects, substituting Mg for In is the most prominent doping acceptor with relative shallow transition energy levels in CuInO₂ under O-rich condition. Based on our calculated results and discussion mentioned above, in order to increase p-type conductivity in CuInO₂, we could substitute Mg atoms for In atoms by the sit-selective doping method through atomic layer epitaxy growth or controlling the oxygen partial pressure in the molecular beam epitaxy or metal-organic chemical vapor deposition crystal growth process. The calculation results will not only provide the guide for design of new type In-based optoelectronic materials, but will also further understand the potential properties in CuInO₂.

Keywords:

CuInO₂ /
doping /
formation energy

作者及机构信息

1.
广西科技大学理学院, 柳州　545006

2.
广西科技大学材料科学与工程研究中心, 柳州　545006

通信作者: 方志杰, nnfang@semi.ac.cn

基金项目: 国家自然科学基金(批准号: 11464003, 11864005)、广西自然科学基金(批准号: 2017GXNSFAA198315)、柳州市科技计划项目(批准号: 2016B040202)和广西高校中青年教师基础能力提升项目(批准号: 2018KY0324)资助的课题.

Authors and contacts

1.
College of Science, Guangxi University of Science and Technology, Liuzhou 545006, China

2.
Materials Science and Engineering Research Center, Guangxi University of Science and Technology, Liuzhou 545006, China

Corresponding author: Fang Zhi-Jie, nnfang@semi.ac.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11464003，11864005), the Natural Science Foundation of Guangxi, China (Grant No. 2017GXNSFAA198315), the Key Science and Technology Program of Liuzhou, China (Grant No. 2016B040202), and the Science-Technology Foundation for Middle-aged and Young College Teacher of Guangxi, China (Grant No. 2018KY0324).

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参考文献

[1]	Ginley D S, Bright C 2000 MRS Bull. 25 8
[2]	Wang L J, Wang W Z, Chen Y L, Yao L Z, Zhao X, Shi H L, Cao M S, Liang Y J 2018 ACS Appl. Mat. Interfaces 10 11652 Google Scholar
[3]	Cao M S, Wang X X, Cao W Q, Fang X Y, Wen B, Yuan J 2018 Small 14 1
[4]	Chen Y L, Wang L Y, Wang W Z, Cao M S 2017 Appl. Catal. B 209 110 Google Scholar
[5]	Kawazoe H, Yasukawa M, Hyodo H 1997 Nature 389 939 Google Scholar
[6]	Yanagi H, Inoue S, Ueda K, Kawazoe H, Hosono H 2000 J. Appl. Phys. 88 4159 Google Scholar
[7]	Nakanishi A, Katayama-Yoshida H, Ishikawa T, Shimizu K 2016 J. Phys. Soc. Jpn. 85 094711 Google Scholar
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[10]	Hamada I, Katayama-Yoshida H 2006 Physsica B 377 808
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[12]	Shimode M, Sasaki M, Mukaida K 2000 J. Soli. Stat. Chem. 151 16 Google Scholar
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[28]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
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施引文献

图 1 CuInO₂晶体结构图, 图中红色原子为O原子, 灰色原子为In原子, 棕色原子为Cu原子　(a)黄色掺杂原子替代Cu原子的情况; (b)绿色掺杂原子替代In原子的情况

Fig. 1. The crystal structure of the CuInO₂, the red atoms are O atoms, the brown atoms are Cu atoms, the purple atoms are In atoms: (a) Substituting yellow dopant atom for Cu atom; (b) substituting green dopant atom for In atom.

下载: 全尺寸图片幻灯片

图 2 掺杂形成能在cation-poor, anion-rich的变化图

Fig. 2. The change of doping formation energies under cation-poor, anion-rich condition.

下载: 全尺寸图片幻灯片

图 3 掺杂形成能在cation-rich, anion-poor的变化图

Fig. 3. The change of doping formation energies under cation-rich, anion-poor condition.

下载: 全尺寸图片幻灯片

图 4 掺杂元素在CuInO₂的缺陷跃迁能级

Fig. 4. The calculated transition energy levels of the extrinsic defects in CuInO_2.

下载: 全尺寸图片幻灯片

表 1 CuInO₂晶格常数理论计算值与实验值

Table 1. Theoretical values and experimental values of lattice constants in CuInO_2.

CuInO₂ 晶格常数理论计算值		晶格常数实验值
a	3.297 Å	a	3.292 Å
c	17.192 Å	c	17.388 Å
u	0.1047 Å	u	0.1061 Å
c/a	5.214	c/a	5.282

下载: 导出CSV

表 2 掺杂元素周围的弛豫变化情况, 键距后括号为掺杂原子的近邻原子种类和个数

Table 2. The surrounding atoms of dopant, kinds and numbers of dopantxs nearest neighbor atoms in parentheses.

掺杂种类	最近邻键距	掺杂种类	最近邻键距	掺杂种类	最近邻键距
Be_Cu	1.49 Å(O, 2)	Mg_Cu	1.85 Å(O, 2)	Mn_Cu	1.77Å(O, 2)
Be_In	1.96 Å(O, 6)	Mg_In	2.12 Å(O, 6)	Mn_In	1.93Å(O, 6)
Be_i	1.62 Å(O, 3)	Mg_i	2.04 Å(O, 3)	Mn_i	1.99Å(O, 3)

下载: 导出CSV

表 3 CuInO₂的掺杂元素形成能

Table 3. The calculated formation energies of dopants in CuInO₂.

掺杂类型	形成能	掺杂类型	总能/eV	形成能	掺杂类型	总能/eV	形成能
Be_Cu	–2.20	Mg_Cu	–650.87	–2.58	Mn_Cu	–654.63	1.76
Be_In	0.79	Mg_In	–651.36	–1.59	Mn_In	–656.54	1.33
Be_i	–1.05	Mg_i	–654.27	–1.27	Mn_i	–657.39	3.71

下载: 导出CSV

[1]	Ginley D S, Bright C 2000 MRS Bull. 25 8
[2]	Wang L J, Wang W Z, Chen Y L, Yao L Z, Zhao X, Shi H L, Cao M S, Liang Y J 2018 ACS Appl. Mat. Interfaces 10 11652 Google Scholar
[3]	Cao M S, Wang X X, Cao W Q, Fang X Y, Wen B, Yuan J 2018 Small 14 1
[4]	Chen Y L, Wang L Y, Wang W Z, Cao M S 2017 Appl. Catal. B 209 110 Google Scholar
[5]	Kawazoe H, Yasukawa M, Hyodo H 1997 Nature 389 939 Google Scholar
[6]	Yanagi H, Inoue S, Ueda K, Kawazoe H, Hosono H 2000 J. Appl. Phys. 88 4159 Google Scholar
[7]	Nakanishi A, Katayama-Yoshida H, Ishikawa T, Shimizu K 2016 J. Phys. Soc. Jpn. 85 094711 Google Scholar
[8]	Jedidi A, Rasul S, Masih D, Cavallo L, Takanabe K 2015 J. Mater. Chem. A 3 19085 Google Scholar
[9]	Nie X, Wei S H, Zhang S B 2002 Phys. Rev. Lett. 88 066405 Google Scholar
[10]	Hamada I, Katayama-Yoshida H 2006 Physsica B 377 808
[11]	Jiang H F, Zhu X B, Lei H C, Li G, Yang Z R 2011 Thin Solids Film 519 2559 Google Scholar
[12]	Shimode M, Sasaki M, Mukaida K 2000 J. Soli. Stat. Chem. 151 16 Google Scholar
[13]	Liu Q J, Liu Z T, Feng L P 2010 Physica B 405 2028 Google Scholar
[14]	Singh M, Mehta B R, Varandani D, Singh V N 2009 J. Appl. Phys. 106 053709 Google Scholar
[15]	Ye F, Cai X M, Dai F P, Zhang D P, Fan P, Liu L J 2011 Adv. Mater. Res. 239 242
[16]	Shin D, Foord J S, Payne D J 2009 Phys. Rev. B 80 233105 Google Scholar
[17]	Varandani D, Singh B, Mehta B, Singh M, Singh V, Nand G D 2010 J. Appl. Phys. 107 103703 Google Scholar
[18]	Roland G, John R 2011 Phys. Rev. B 84 035125 Google Scholar
[19]	Godinho K G, Morgan B J, Allen J P, Scanlon D O, Watson G W 2011 J. Phys.: Cond. Matter 23 334201 Google Scholar
[20]	Yao Y, Xie G, Song N, Yu X H, Li R X 2011 Adv. Mater. Res. 399 401
[21]	Liu L, Bai K W, Gong H, Wu P 2005 Phys. Rev. B 72 125204 Google Scholar
[22]	Blouchl P E 1994 Phys. Rev. B 50 17953 Google Scholar
[23]	Kresse G, Joubert J 1999 Phys. Rev. B 59 1758
[24]	Hohenberg P, Kohn W 1964 Phys. Rev. B 136 864 Google Scholar
[25]	Kohn W, Sham L J 1965 Phys. Rev. A 140 1133 Google Scholar
[26]	Kresse G, Furthmüller J 1996 Phys. Rev. B 54 11169 Google Scholar
[27]	Kresse G, Furthmüller J 1996 Comp. Mater. Sci. 6 15 Google Scholar
[28]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[29]	Pack J D, Monkhorst H J 1977 Phys. Rev. B 16 1748 Google Scholar
[30]	Murnaghan F D, Natl P 1944 Acad. Sci. USA 30 244 Google Scholar
[31]	Chu S, Hollberg L, Bjorkholm J E, Cable A, Ashkin A 1985 Phys. Rev. Lett. 55 48 Google Scholar
[32]	Wei S H 2004 Comput. Mat. Sci. 30 337 Google Scholar

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Be, Mg, Mn掺杂CuInO₂形成能的第一性原理研究