铜铟铝硒（CIAS）与CdS、ZnS薄膜光伏材料的研究
摘要
目前环境保护、节能减排已经成为世界各国的基本国策。本论文选题为研究铜铟硒类太阳能电池吸收层和缓冲层材料等新型光伏材料对发展新材料、新能源,贯彻可持续发展战略有重要意义。论文工作中用物理气相沉积和化学水浴法分别制备了太阳能电池吸收层CIAS薄膜,缓冲层CdS和ZnS薄膜,运用微观分析和表面分析手段(XRD、TEM、 SEM、EDS及XPS等)对薄膜的形貌、结构、成分以及光电性能进行检测分析。
采用真空蒸发多层膜(VEMF)法将Cu、In、Al三种金属分别蒸镀到玻璃基底上形成CIA预制层。中频孪生非平衡磁控溅射(FTUMS)技术用Cu靶和自行研制的In-Al复合靶制备CIA预制层。再采用固态源硒化法形成CIAS薄膜。研究了不同硒化工艺对CIAS薄膜的表面形貌、结构、成分和光电性能的影响,以及Al相对含量对CIAS薄膜性能的影响。结果表明：常温下制备的CIA预制层薄膜,结构为非晶态；硒化后形成CIAS化合物薄膜,主相为黄铜矿结构,也存在非晶或微晶结构,说明用A1代替In是可行的。检测了其电阻率在半导体材料范围内,Al含量可调节CIAS薄膜的禁带宽度(1.60-1.95eV)。从成膜一般规律与制备过程探讨了VEMF与IFTUMS两种方法制备薄膜的成膜过程与机理。
采用化学水浴法(CBD)制备了CdS和ZnS薄膜。研究不同工艺条件对薄膜性能的影响,运用场发射TEM和XPS等检测手段研究了退火前后厚度为100nm的CdS和ZnS薄膜的性能。结果表明：CdS和ZnS薄膜均为非晶或微晶且出现立方相晶粒；当波长大于550nm时,其光透射率超过70%,带隙接近理论值。TEM暗场像分别观察到CdS薄膜AA和ZnS薄膜BB晶面取向的晶粒(尺寸20-100nm)。退火前CdS和ZnS薄膜的原子比约为1：1,退火后的CdS和ZnS薄膜都有S元素缺失。获得制备CdS和ZnS薄膜的最佳工艺参数。进而从CBD法的成膜原理讨论了CdS和ZnS薄膜的成膜过程。
Environmental protection, Energy-saving, and Reduce emissions of pollutants has become the world's basic policy. The topic of the paper to study on new photovoltaic materials Copper indium selenium(CIS) and like Solar cells'photovoltaic materials of absorber and buffer layers has the important significance in the development of new materials, new energy, and implement the strategy of sustainable development. Solar cell absorption layer (CIAS film) and buffer layer (CdS and ZnS films) were prepared by physical vapor deposition (PVD) and chemical bath deposition (CBD) in this work, respectively. Morphology, structure, composition, and photoelectric performances of the films were detected and analyzed by microscopic and surface analysis(XRD、TEM、SEM、EDS and XPS etc.).
Using a vacuum evaporated multilayer film (VEMF) method, three metals(Cu, In, Al) were deposited onto the glass substrate to form the CIA precursor. By IF twin unbalanced magnetron sputtering (FTUMS) technology, with Cu and self-developed In-Al composite target CIA precursor was prepared. CIAS film was formed by the solid source selenide method. It was studied that different selenide process to affect the surface morphology, structure, composition, and photoelectric properties. Also, the relative content of Al impacted CIAS films'performances. As the results, that CIA films prepared at room temperature were amorphous. CIAS compound film's main phase was a chalcopyrite structure. The films also involved the amorphous or microcrystalline structure. So using Al instead of In is feasible. Its resistivity was within semiconductor material limits. Al content could be adjusted to change the band gap Eg for the CIAS films (1.60-1.95eV). It was investigated the preparation process and mechanism according to the general principle of fabrication films for VEMF and IFTUMS techniques.
CdS and ZnS films prepared by CBD. It was studied that different process conditions to impact of a variety of performance of thin films for CdS and ZnS films of100nm thickness before and after annealed by the field emission TEM and XPS. As the results, that CdS and ZnS films are amorphous or microcrystalline, and the cubic phase grain. As the wavelength was greater than550nm, the transmittance was more than70%. Band gap was close to the theoretical value. TEM dark field image of grains (100-200nm) of CdS and ZnS films with he operation of AA and BB lattice face orientation were observed, respectively. Before nnealed, the content ratios were Cd:S=I:1, and Zn:S=1:1. After annealed, S amount was (?)st more. Then, the optimum process Parameters of preparation of CBD were obtained. ilm-forming process was discussed by film-forming principle of CBD.
采用真空蒸发多层膜(VEMF)法将Cu、In、Al三种金属分别蒸镀到玻璃基底上形成CIA预制层。中频孪生非平衡磁控溅射(FTUMS)技术用Cu靶和自行研制的In-Al复合靶制备CIA预制层。再采用固态源硒化法形成CIAS薄膜。研究了不同硒化工艺对CIAS薄膜的表面形貌、结构、成分和光电性能的影响,以及Al相对含量对CIAS薄膜性能的影响。结果表明：常温下制备的CIA预制层薄膜,结构为非晶态；硒化后形成CIAS化合物薄膜,主相为黄铜矿结构,也存在非晶或微晶结构,说明用A1代替In是可行的。检测了其电阻率在半导体材料范围内,Al含量可调节CIAS薄膜的禁带宽度(1.60-1.95eV)。从成膜一般规律与制备过程探讨了VEMF与IFTUMS两种方法制备薄膜的成膜过程与机理。
采用化学水浴法(CBD)制备了CdS和ZnS薄膜。研究不同工艺条件对薄膜性能的影响,运用场发射TEM和XPS等检测手段研究了退火前后厚度为100nm的CdS和ZnS薄膜的性能。结果表明：CdS和ZnS薄膜均为非晶或微晶且出现立方相晶粒；当波长大于550nm时,其光透射率超过70%,带隙接近理论值。TEM暗场像分别观察到CdS薄膜AA和ZnS薄膜BB晶面取向的晶粒(尺寸20-100nm)。退火前CdS和ZnS薄膜的原子比约为1：1,退火后的CdS和ZnS薄膜都有S元素缺失。获得制备CdS和ZnS薄膜的最佳工艺参数。进而从CBD法的成膜原理讨论了CdS和ZnS薄膜的成膜过程。
Environmental protection, Energy-saving, and Reduce emissions of pollutants has become the world's basic policy. The topic of the paper to study on new photovoltaic materials Copper indium selenium(CIS) and like Solar cells'photovoltaic materials of absorber and buffer layers has the important significance in the development of new materials, new energy, and implement the strategy of sustainable development. Solar cell absorption layer (CIAS film) and buffer layer (CdS and ZnS films) were prepared by physical vapor deposition (PVD) and chemical bath deposition (CBD) in this work, respectively. Morphology, structure, composition, and photoelectric performances of the films were detected and analyzed by microscopic and surface analysis(XRD、TEM、SEM、EDS and XPS etc.).
Using a vacuum evaporated multilayer film (VEMF) method, three metals(Cu, In, Al) were deposited onto the glass substrate to form the CIA precursor. By IF twin unbalanced magnetron sputtering (FTUMS) technology, with Cu and self-developed In-Al composite target CIA precursor was prepared. CIAS film was formed by the solid source selenide method. It was studied that different selenide process to affect the surface morphology, structure, composition, and photoelectric properties. Also, the relative content of Al impacted CIAS films'performances. As the results, that CIA films prepared at room temperature were amorphous. CIAS compound film's main phase was a chalcopyrite structure. The films also involved the amorphous or microcrystalline structure. So using Al instead of In is feasible. Its resistivity was within semiconductor material limits. Al content could be adjusted to change the band gap Eg for the CIAS films (1.60-1.95eV). It was investigated the preparation process and mechanism according to the general principle of fabrication films for VEMF and IFTUMS techniques.
CdS and ZnS films prepared by CBD. It was studied that different process conditions to impact of a variety of performance of thin films for CdS and ZnS films of100nm thickness before and after annealed by the field emission TEM and XPS. As the results, that CdS and ZnS films are amorphous or microcrystalline, and the cubic phase grain. As the wavelength was greater than550nm, the transmittance was more than70%. Band gap was close to the theoretical value. TEM dark field image of grains (100-200nm) of CdS and ZnS films with he operation of AA and BB lattice face orientation were observed, respectively. Before nnealed, the content ratios were Cd:S=I:1, and Zn:S=1:1. After annealed, S amount was (?)st more. Then, the optimum process Parameters of preparation of CBD were obtained. ilm-forming process was discussed by film-forming principle of CBD.
引文
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