多元硫属化合物一维纳米阵列太阳电池的构筑与性能研究

Multinary chalcogenides are considered to be the most promising candidates for photovoltaic applications due to their unique structure and prominent properties. Presently, the solar cells based on 1D nanostructure arrays are mainly focused on some simple-structure compounds. The goal of this project is to explore and develop the facile and universal synthesis methods to prepare 1D nanoarrays of I-M-VI compounds. In this project, combined with the traditional template and substrate techniques, a novel solvothermal detached system has been proposed to synthesize 1D nanoarrays of multinary chalcogenides. With the subsequent deposition of II-VI compounds as the buffer layer, the low-cost inorganic solar cells will be constructed. Due to their large surface area and high length-to-diameter ratio, the PV devices based on 1D nanoarrays will exhibit high efficiency in light-harvesting, optical absorption and carrier collection, which can avoid the obstacle of electron transport in nanocrystalline solar cells and the conflict between optical absorption depth and carrier collection length in planar bilayer cells. Based on the quantum confinement effect, a better spectral response and full-spectrum absorption should be achieved. The precise control of the 1D nanostructure arrays would be essential for enhancing the short-circuit current and open-circuit voltage. Then, the thermodynamic and kinetic principles governing the growth process of the 1D nanoarrays could be deduced. To improve the conversion efficiency of the solar cells, the preparation conditions, material structures, photovoltaic properties of the products and the inherent laws of correlations in them should be studied.

多元硫属化合物由于其独特的组成结构和优越的光电性质，在光伏领域具有广阔的应用前景。本申请旨在突破一维纳米阵列太阳电池集中于简单化合物的局限，结合传统模板及衬底生长技术，设计溶剂热分离体系，发展I-M-VI族多元硫属化合物一维纳米阵列简单、普适的制备方法。通过沉积II-VI族化合物缓冲层，构筑低成本无机太阳电池。利用其较大的表面积和长径比，提高光捕获、光吸收及载流子收集效率，有效解决纳米晶太阳电池中电子迁移的障碍以及传统平面太阳电池中光吸收深度与载流子收集距离之间的矛盾；基于一维纳米结构的量子限域效应，增强器件的光谱响应，实现对太阳光的广谱吸收；通过对一维纳米结构阵列的精细控制，提高光伏器件的短路电流和开路电压；研究热力学和动力学对多元硫属化合物一维纳米阵列生长的控制原理，分析制备条件对产物结构、器件性能的影响及其相互关系和内在规律，优化实验参数，提高多元硫属化合物太阳电池的光电转换效率。

功能纳米材料由于其优越的物理化学性质及广泛的应用前景而备受关注。其中，多元硫属化合物作为重要的多功能材料体系，由于其结构、组成的多样性和灵活性，在诸多领域均展现了巨大的应用潜力。本项目以制备多元硫属化合物一维纳米阵列为基本目标，以发展新型功能纳米材料与器件为总体任务，着重以能源与环境为功能导向，通过设计简单、普适的化学合成方法，制备出不同种类的功能纳米结构材料，研究材料的制备与结构、性能之间的联系，探索材料的器件化与潜在应用价值。本项目成功发展了多种新型功能纳米材料体系的制备，主要包括以下四个方面：首先，在多元硫化物一维阵列的构筑方面，在金属基底上生长了BiSI, Bi19S27I3及CuSbS2-Cu2S等一维纳米结构阵列，并构筑了相应的光电器件；其次，在多元硫化物功能纳米材料的制备方面，不仅首次制备了Ag3Pb2Sb3S8, CuNi2InS4以及MInSnS4等系列四元硫化物纳米晶，还利用置换法成功合成了MCr2S4和M2SnS4系列三元硫化物磁性半导体；再次，在新型光/电催化功能材料的发展方面，首次利用低温液相合成方法制备了Aurivillius型Bi2MO5F (M = Nb, Ta)纯相，并成功得到了Bi2TiO4F2分级多孔状空心结构及BiF3-Bi2NbO5F核-壳结构，均表现出了优秀的光催化性质。利用甲酸镍的原位热处理合成了Ni重掺杂g-C3N4以及MoS2/Ni3S2/Ni与rGO/NiO/Ni复合物等催化材料；最后，在新型超级电容器电极材料的探索方面，在泡沫镍基底上利用水热法原位生长了过渡金属对苯二甲酸盐以及没食子酸镍等一系列金属有机配合物用于赝电容器，首次以商用涤纶布为基底生长Cu(OH)2一维纳米阵列应用于可穿戴超级电容器，还首次利用蚕砂及狗尾草籽等天然生物质制备先进碳纳米材料用于双电层电容器。这些合成技术的发展对探索功能纳米材料与器件的制备及应用具有重要意义，为纳米材料科学的发展提供了实验依据。