【作者】 张鑫狄；

【导师】 江国顺；

【作者基本信息】 中国科学技术大学 ， 材料学， 2011， 硕士

【摘要】 自从1976年[1]被发现以来,混合物半导体CIS(CuInSe₂、CuIn(S_xSe_1-x)₂、CuInS₂)就作为当今热门的太阳能材料而广受关注。作为黄铜矿相的半导体,CuInSe₂、CuIn(S_xSe_1-x)₂、CuInS₂分别具有从1.04eV到1.55eV的带隙宽度区间,而最适合吸收太阳光的带隙宽度是1.45eV,所以CIS很适合做高效率太阳能电池的材料。另外,CIS还具有长期稳定、无毒等优点。本论文研究的是溶剂热法制备的CIS。溶剂热法制备的CIS纳米颗粒可以制备成电池器件,目前已经可以做到6.7%的效率[2]。不同于传统的制备CIS电池的真空法,诸如真空蒸镀法[3-5]和溅射法[6-11],溶剂热法具有相对简单的制备过程和低廉的成本,适合做薄膜太阳电池的大规模工业化生产。溶剂热法制备CuInSe₂、CuIn(S_xSe_1-x)₂、CuInS₂薄膜的具体工艺稍有不同。CuInSe₂和CuInS₂都可以用溶剂热法直接产生,然后分别经硒化和硫化后制成CuInSe₂和CuInS₂薄膜。CuIn(S_xSe_1-x)₂有两条工艺路径,一条是先用溶剂热法制成CuInSe₂粉体,涂膜后硫化制成CuIn(S_xSe_1-x)₂薄膜。另一条是用溶剂热法制备CuIn(S_xSe_1-x)₂粉体,然后硒化或硫化制成薄膜。本论文只研究了溶剂热制备CuIn(S_xSe_1-x)₂粉体,没有研究后期成膜的过程。影响溶剂热法产物的主要因素有前驱溶剂的元素比例,高温反应的温度,以及反应的时间。通过调节这三个要素,不但可以控制反应产物的质量,还可以控制CuIn(S_xSe_1-x)₂中S和Se的元素比例,制备相应的CuIn(S_xSe_1-x)₂粉体。在粉体成膜方面,主要影响因素为硒化或硫化的时间,以及硒化或硫化的温度。实验发现,薄膜结晶度,致密度,均匀度,以及CuIn(S_xSe_1-x)₂薄膜的S/Se比例,都受到硒化或硫化温度和时间的控制。通过扫描电子显微镜（SEM）、电子能谱（EDS）、XRD以及Raman等测试仪器,对薄膜的性质进行了表征。更多还原

【Abstract】 The compound semiconductor CIS(CuInSe₂、CuIn(S_xSe_1-x)₂、CuInS₂) has been attracted interest for use in photovoltaic solar cells since 1976 [1]. As a chalcopyrite semiconductor, CuInSe₂, CuIn(S_xSe_1-x)₂ and CuInS₂ had band gaps range from 1.04eV to 1.55eV. The theoretical optimum value for photovoltaic’s applications is 1.45eV, so CIS is suitable for preparing high conversion efficiency solar cell. What’more, CIS thin film solar cells have other advantages, such as long-term stability and nontoxic.In this paper, we studied CIS prepared by solvothermal method. CuInSe₂ nanoparticles which were synthesized by solvothermal method can be made as solar cells. Using this method, solar cells with efficiency of 6.7% have been fabricated [2]. Be differ from vacuum-based methods, such as evaporation [5-7] and sputtering [8-13], solvothermal method was used here due to its relatively simple procedures and low cost. These two advantages made solvothermal method suited for large-scale industrialization of solar cells.There were differences in specific process routes of preparing CuInSe₂, CuIn(S_xSe_1-x)₂ and CuInS₂ by solvothermal method. CuInSe₂ and CuInS₂ thin films can be prepared by reacting CuInSe₂/CuInS₂ nanoparticles in Se/H2S, and CuInSe₂ and CuInS₂ nanoparticles can be synthesized by solvothermal method directly. Two routes to CuIn(S_xSe_1-x)₂ thin films had been reported. First route was the reaction of CuInSe₂ which were synthesized by solvothermal method with H2S. The other route was selenization or sulphurization of CuIn(S_xSe_1-x)₂ prepared by solvothermal method. In this paper, only the process of synthesizing CuIn(S_xSe_1-x)₂ nanoparticles was studied in the second route.There were three main factors which affected the product prepared by solvothermal method: ratio of elements in precursor, temperature of the reaction and time of the reaction. By controlling these three factors, we can synthesize nanoparticles with high quality, and the ratio of Se and S of CuIn(S_xSe_1-x)₂ nanoparticles can also be controlled. On the other hand, temperature and time of the selenization or sulphurization were main factors on making thin films. It was found that the compositions, degree of crystallinity, homogeneity and ratio of Se and S of the final CuIn(S_xSe_1-x)₂ thin films were controlled by temperature and time of the selenization or sulphurization.XRD, SEM, EDS, Raman are used to characterized the property of the CIS thin film.更多还原