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).

文章全文 : translate this paragraph

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
[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

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

[1]	王雪冰, 唐春梅, 谢梓涵, 俞瑞, 严杰, 蒋承乐. Mo掺杂二维VS₂吸附有毒气体的理论研究. 物理学报, 2024, 73(1): 013101. doi: 10.7498/aps.73.20231236
[2]	张冷, 张鹏展, 刘飞, 李方政, 罗毅, 侯纪伟, 吴孔平. 基于形变势理论的掺杂计算Sb₂Se₃空穴迁移率. 物理学报, 2024, 73(4): 047101. doi: 10.7498/aps.73.20231406
[3]	邓晨华, 于忠海, 王宇涛, 孔森, 周超, 杨森. Ti掺杂Nd₂Fe₁₄B/α-Fe纳米双相复合永磁体晶化动力学. 物理学报, 2023, 72(2): 027501. doi: 10.7498/aps.72.20221479
[4]	林洪斌, 林春, 陈越, 钟克华, 张健敏, 许桂贵, 黄志高. 第一性原理研究Mg掺杂对LiCoO₂正极材料结构稳定性及其电子结构的影响. 物理学报, 2021, 70(13): 138201. doi: 10.7498/aps.70.20210064
[5]	袁国才, 陈曦, 黄雨阳, 毛俊西, 禹劲秋, 雷晓波, 张勤勇. Mg₂Si_0.3Sn_0.7掺杂Ag和Li的热电性能对比. 物理学报, 2019, 68(11): 117201. doi: 10.7498/aps.68.20190247
[6]	张梅玲, 陈玉红, 张材荣, 李公平. 内在缺陷与Cu掺杂共存对ZnO电磁光学性质影响的第一性原理研究. 物理学报, 2019, 68(8): 087101. doi: 10.7498/aps.68.20182238
[7]	王泽普, 付念, 于涵, 徐晶威, 何祺, 郑树凯, 丁帮福, 闫小兵. 铟掺杂钨位增强钨酸铋氧空位光催化效率. 物理学报, 2019, 68(21): 217102. doi: 10.7498/aps.68.20191010
[8]	陈东运, 高明, 李拥华, 徐飞, 赵磊, 马忠权. MoO₃/Si界面区钼掺杂非晶氧化硅层形成的第一性原理研究. 物理学报, 2019, 68(10): 103101. doi: 10.7498/aps.68.20190067
[9]	徐晶, 梁家青, 李红萍, 李长生, 刘孝娟, 孟健. Ti掺杂NbSe2电子结构的第一性原理研究. 物理学报, 2015, 64(20): 207101. doi: 10.7498/aps.64.207101
[10]	李宗宝, 王霞, 樊帅伟. Cu/N表面沉积共掺杂TiO2光催化剂作用机理的理论研究. 物理学报, 2014, 63(15): 157102. doi: 10.7498/aps.63.157102
[11]	曹娟, 崔磊, 潘靖. V,Cr,Mn掺杂MoS2磁性的第一性原理研究. 物理学报, 2013, 62(18): 187102. doi: 10.7498/aps.62.187102
[12]	吴木生, 徐波, 刘刚, 欧阳楚英. Cr和W掺杂的单层MoS2电子结构的第一性原理研究. 物理学报, 2013, 62(3): 037103. doi: 10.7498/aps.62.037103
[13]	郝红飞, 王静, 孙锋, 张澜庭. Dy在Nd2Fe14B晶格中的占位及其对Fe原子磁矩影响的第一性原理计算. 物理学报, 2013, 62(11): 117501. doi: 10.7498/aps.62.117501
[14]	徐金荣, 王影, 朱兴凤, 李平, 张莉. N掺杂和N-V共掺杂锐钛矿相TiO2的第一性原理研究. 物理学报, 2012, 61(20): 207103. doi: 10.7498/aps.61.207103
[15]	唐冬华, 薛林, 孙立忠, 钟建新. B在Hg0.75Cd0.25Te中掺杂效应的第一性原理研究. 物理学报, 2012, 61(2): 027102. doi: 10.7498/aps.61.027102
[16]	周传仓, 刘发民, 丁芃, 钟文武, 蔡鲁刚, 曾乐贵. 钶铁矿型MnNb2O6的熔盐法合成、钒掺杂与磁性研究. 物理学报, 2011, 60(4): 048101. doi: 10.7498/aps.60.048101
[17]	李虹, 王绍青, 叶恒强. Nb掺杂对γ-TiAl抗氧化能力影响的第一性原理研究. 物理学报, 2009, 58(13): 224-S229. doi: 10.7498/aps.58.224
[18]	杜丽萍, 陈抱雪, 孙蓓, 陈直, 邹林儿, 浜中广见, 矶守. 掺杂As2S8非晶态薄膜波导的光阻断效应. 物理学报, 2008, 57(6): 3593-3599. doi: 10.7498/aps.57.3593
[19]	金胜哲, 黄祖飞, 明星, 王春忠, 孟醒, 陈岗. 二价金属元素掺杂对LiCoO2体系电子输运性质的影响. 物理学报, 2007, 56(10): 6008-6012. doi: 10.7498/aps.56.6008
[20]	王先杰, 隋郁, 千正男, 刘志国, 苗继鹏, 黄喜强, 吕喆, 朱瑞滨, 程金光, 苏文辉. Fe位Al掺杂对Sr2FeMoO6磁结构和磁输运性质的影响. 物理学报, 2006, 55(2): 849-853. doi: 10.7498/aps.55.849

计量

文章访问数: 14972
PDF下载量: 859
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板

Be, Mg, Mn掺杂CuInO₂形成能的第一性原理研究