双受主共掺杂CuMO2（M=Al，Ga，In，Sc）的改性机理研究与薄膜制备

Transparent conductive oxide CuMO2(M=Al,Ga,In,Sc) have been the focus of the research in the worldwide because of their p-type intrinsic semiconductor characteristics. However, the low conductivity and light transmittance is the most important problem to the development of CuMO2, and doping is an effective way to solve this problem. Unfortunately, the single element doping still cannot meet the demand of application, and the double acceptor co-doping is considered as an effective means to further improve its photoelectric characteristics. Therefore, in this project, the dual-acceptor co-doped CuMO2 is achieved by introducing different doping elements only in M site, and in M and O site at same time. The crystal structure models of two types of dual-acceptor co-doped CuMO2 with different elements at different doping concentrations are established and optimized and their properties are calculated by the method of first principles calculation. The effects of doping type, doping element and doping concentration on the crystal structure, defects properties, electrical properties and optical properties of dual-acceptor co-doped CuMO2 are revealed on the atomic scale based on the analysis of calculation results, and the dual-acceptor co-doping modification mechanism of CuMO2 are illuminated systematically. Then, the dual-acceptor co-doped CuMO2 films with high quality are prepared by magnetron sputtering method according to the doping conditions determined by doping modification mechanism, and their photoelectric properties were further improved by annealing. The project is expected to establish the systematic and solid theoretical and experimental basis for the successful preparation and application of high performance p-type transparent conducting materials in the future.

透明导电氧化物CuMO2(M=Al,Ga,In,Sc)具有本征p型半导体特性，是当今世界的研究热点和重点，然而低的电导率和透光率是制约其发展的难题，掺杂是解决这一问题的有效途径。单元素的掺杂依然不能满足使用需求，而双受主共掺杂被认为是进一步提高其光电性质的有效手段。为此，本项目将通过仅在M位，以及同时在M和O位引入不同掺杂元素实现CuMO2的双受主共掺杂, 采用第一性原理的方法建立和优化不同浓度的不同元素以两种类型双受主共掺杂CuMO2的晶体结构模型并计算其各项性质，分析结果并从原子尺度揭示掺杂类型、元素种类和浓度对CuMO2晶体结构、缺陷性质、电子特性和光学性质的影响规律，系统阐明CuMO2的双受主共掺杂改性机理。然后依据掺杂改性机理确定的掺杂条件，采用磁控溅射法制备出较高质量的双受主共掺杂CuMO2薄膜，并通过退火进一步提高其光电性质，为高性能p型透明导电材料的制备奠定理论和实验基础。

透明导电氧化物CuMO2(M=Al, Ga, In, Sc)具有本征p型半导体特性，是当今世界的研究热点和重点，然而低的电导率和透光率是制约其发展的难题，掺杂是解决这一问题的有效途径。为此，本项目采用基于密度泛函理论的第一性原理计算方法，首先系统研究了不同浓度的四种掺杂元素Ca、Mg、N、S对2H-和3R-CuMO2（M=Al，Ga，In，Sc）的晶体结构、电子特性和光学性质的影响规律，阐明了掺杂CuMO2的改性机理。然后，通过引入Ca-Mg、S-Ca和S-Mg双元素组开展了2H-CuAlO2的M-O位和M-M位双受主共掺杂研究并得出了相关结论。结果表明：随着掺杂浓度增加，Ca、Mg、N、S掺杂都使CuMO2的晶格参数和晶胞体积发生变化，针对不同材料，Mg、N掺杂后的变化规律有所不同，而Ca、S掺杂后的规律基本一致。Ca、Mg掺杂CuAlO2、CuGaO2、CuScO2的带隙都逐渐增加，而S掺杂则呈现减小趋势。Ca、Mg、S掺杂对3R-CuInO2的带隙影响不大，N则会使其在高掺杂浓度下变为金属。Ca、Mg掺杂对CuMO2费米能级附近的价带顶和导带底的影响很小，N元素对CuMO2的价带顶和导带底都有一定影响，尤其是对价带顶的作用较强，而S元素主要影响了价带顶。四种掺杂元素对CuGaO2和CuScO2光学性质的影响不大，而Ca、Mg元素对于CuAlO2和CuInO2的影响较大。共掺杂对2H-CuAlO2结构和性质的影响与单元素掺杂基本一致，电子特性以S元素的作用为主，而晶体结构和光学性质以Ca、Mg的作用为主，交互作用并不明显。N元素参与的共掺杂会导致多种CuMO2由半导体变为金属。目前开展了CuAlO2薄膜的一些实验研究，后续将继续进行研究并最终制备出高质量的共掺杂CuMO2薄膜。该研究可为高性能CuMO2的制备提供理论依据和实验指导，为实现具有良好性能的全透明p-n结的生产奠定基础。