B掺杂ZnO透明导电薄膜的实验及理论研究

王延峰; 张晓丹; 黄茜; 杨富; 孟旭东; 宋庆功; 赵颖

doi:10.7498/aps.62.247802

摘要

采用脉冲直流磁控溅射技术与基于密度泛函理论的平面波赝势方法对B掺杂ZnO （BZO）薄膜进行了研究. 以B2O3：ZnO陶瓷靶为溅射靶材，制备了低电阻率、可见和近红外光区高透过率的BZO薄膜. 系统地研究了衬底温度对BZO薄膜的结构、光电特性的影响. 结果表明：适当的增加衬底温度可以促进BZO薄膜结晶质量改善，晶粒尺寸增加，迁移率增大，电阻率降低. 在200 ℃时制备了电阻率为7.03×10-4 Ω·cm，400–1100 nm平均透过率为89%的BZO薄膜. 理论模拟结果表明：在BZO薄膜中，以替位方式掺入的B （BZn）的形成能最低，B主要以替位形式掺入ZnO，其次分别为八面体间隙（BIO）和四面体间隙（BIT）的掺杂方式. B 掺入后，费米能级穿过导带，材料表现出n型半导体特性，光学带隙展宽，导电电子主要来源于B 2p，O 2p及Zn 4s电子轨道.

关键词:

Abstract

The properties of boron doped ZnO (BZO) films are investigated by the pulsed DC magnetron sputtering technique and the plane wave pseudo-potential method based on the density-functional theory. Highly conductive and transparent BZO thin films are prepared using a B2O3:ZnO ceramic target. The effects of the substrate temperature on the structureand electrical and optical properties are systematically investigated. The results show that by increasing the substrate temperature appropriately, the crystallinity, grain size, and carrier mobility of BZO film are improved, and the resistivity is reduced. BZO films of low resistivity (7.03×10-4 Ω·cm) and high transmittance (89%) from 400–1100 nm are achieved at an optimal substrate temperature of 200 ℃. The theoretical results show that B is doped in ZnO mainly in three forms, i.e., in the forms of substitutional BZn atoms, octahedral interstitial site (BIO), and tetrahedral interstitial site (BIT). Among them the formation energy of BZn defect is lowest, and its concentration may be the highest in all the sample concentrations. After incorporation of B, the Fermi level goes through the conduction band. The sample shows a typical n-type metallic characteristic and the optical band gap increases significantly. The carriers originate from the orbits of B 2p, O 2p and Zn 4s.

Keywords:

作者及机构信息

1.
河北北方学院理学院, 张家口 075000;

2.
南开大学, 光电子薄膜器件与技术研究所, 南开大学光电子薄膜器件与技术天津市重点实验室, 光电信息技术科学教育部重点实验室, 天津 300071;

3.
中国民航大学理学院, 天津 300300

基金项目: 国家重点基础研究发展计划（批准号：2011CBA00706，2011CBA00707）、国家高技术研究发展计划（批准号：2013AA050302）、天津市科技支撑项目（批准号：12ZCZDGX03600）、天津市重大科技支撑计划（批准号：11TXSYGX22100）和高等学校博士学科点专项科研基金（批准号：20120031110039）资助的课题.

Authors and contacts

1.
College of Science, Hebei North University, Zhangjiakou 075000, China;

2.
Key Laboratory of Photo-Electronic Thin Film Devices and Technology of Tianjin, Key Laboratory of Opto-Electronic Information Science and Technology, Ministry of Education, Institute of Photo-Electronic Thin Film Devices and Technology of Nankai University, Tianjin 300071, China;

3.
College of Science, Civil Aviation University of China, Tianjin 300300, China

Funds: Project supported by the National Basical Research Program of China (Grant Nos. 2011CBA00706, 2011CBA00707), the National High Technology Research and Development Program of China (Grant No. 2013AA050302), the Tianjin Science and Technology Supported Project, China (Grant No. 12ZCZDGX03600), the Major Science and Technology Supported Project of Tianjin, China (Grant No. 11TXSYGX22100), and the Specialized Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20120031110039).

参考文献

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施引文献

[1]	Minami T 2005 Semicond. Sci. Technol. 20 S35
[2]	Hpkes J, Owen J I, Pust S E, Bunte E 2012 Chem. Phys. Chem. 13 66
[3]	Wang Y F, Zhang X D, Bai L S, Huang Q, Wei C C, Zhao Y 2012 Appl. Phys. Lett. 100 263508
[4]	Selvan J A A, Delahoy A E, Guo S Y, Li Y M 2006 Sol. Energy Mater. Sol. Cells 90 3371
[5]	Fäy S, Feitknecht L, Schlchter R, Kroll U, Vallat-Sauvain E, Shah A 2006 Sol. Energy Mater. Sol. Cells 90 2960
[6]	Faÿ S, Steinhauser J, Nicolay S, Ballif C 2010 Thin Solid Films 518 2961
[7]	WangY, Gu Y S, Peng S, Ding W Y, H L Wang, Chai W P 2011 Appl. Surf. Sci. 257 8044
[8]	Palacios P, Sánchez K, Wahnón P 2009 Thin Solid Films 517 2448
[9]	Liu X C, Ji Y J, Zhao J Q, Liu L Q, Sun Z P, Dong H L 2010 Acta Phys. Sin. 59 4925 (in Chinese) [刘小村, 季燕菊, 赵俊卿, 刘立强, 孙兆鹏, 董和磊 2010 59 4925]
[10]	Liu J J 2010 Acta Phys. Sin. 59 6446 (in Chinese) [刘建军 2010 59 6446]
[11]	Özgr , Alivov Y I, Liu C, Teke A, Reshchikov M A, Doğan S, AVrutin V, Cho S J, Morkoç H 2005 J. Appl. Phys. 98 041301
[12]	Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phys.: Condens. Matter 14 2717
[13]	Ceperley D M, Alder B J 1980 Phys. Rev. Lett. 45 566
[14]	Perdew J P, Zunger A 1981 Phys. Rev. B 23 5048
[15]	Vanderbilt D 1990 Phys. Rev. B 41 7892
[16]	Cao F, Wang Y D, Li L, Guo B J, An Y P 2009 Scripta Mater. 61 231
[17]	Lin S S, Huang J L, Šajgalik P 2005 Surf. Coat. Tech. 190 39
[18]	Singh S, Srinivasa R S, Major S S 2007 Thin Solid Films 515 8718
[19]	Kim K H, Park K C, Ma D Y 1997 J. Appl. Phys. 81 7764
[20]	Pei Z L, Sun C, Tan M H, Xiao J Q, Guan D H, Huang R F, Wen L S 2001 J. Appl. Phys. 90 3432
[21]	Wang Y F, Huang Q, Song Q G, Liu Y, Wei C C, Zhao Y, Zhang X D 2012 Acta Phys. Sin. 61 137801 (in Chinese) [王延峰, 黄茜, 宋庆功, 刘阳, 魏长春, 赵颖, 张晓丹 2012 61 137801]
[22]	Wang F G, Lv M S, Pang Z Y, Yang T L, Dai Y, Han S H 2008 Appl. Surf. Sci. 254 6983
[23]	Li H L, Zhang Z, L Y B, Huang J Z, Zhang Y, Liu R X 2013 Acta Phys. Sin. 62 047101 (in Chinese) [李泓霖, 张仲, 吕英波, 黄金昭, 张英, 刘如喜 2013 62 047101]
[24]	Zhang F C, Zhang Z Y, Zhang W H, Yan J F, Yun J N 2009 Acta Opt. Sin. 29 1025 (in Chinese) [张富春, 张志勇, 张威虎, 阎军峰, 贠江妮 2009 光学学报 29 1025]

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