化学与沉积CIS太阳能电池功能层薄膜及其光电性能研究
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摘要
CuInS2是一种性能优越的太阳能电池材料,其具有光吸收率高,禁带宽度接近太阳能电池最佳禁带宽度,直接带隙半导体,即可制成p型薄膜也可做成n型薄膜,理论转化效率高,成本低等特点,被人们称为最有希望的光伏器件材料之一。本文旨在探求应用低能耗、环境友好的化学浴沉积方法,设计合理的实验路线,优化实验参数,制备出高结晶度的硫化铜与氧化锌薄膜,并研究其光学及电学特性。本论文的主要研究内容可分为以下两大部分:
1.设计反应路线,运用传统化学浴沉积与微波辅助方法成功制备出CuS薄膜,并比较了两种方法制备薄膜的热力学和动力学过程。研究反应时间、溶液pH值以及添加剂等反应参数对制备过程的影响。通过调节这些反应参数有效控制了制备过程,最终制备出结晶良好、符合化学计量比、表面具有特殊形貌的CuS薄膜,并对其带隙与电导率进行了计算。通过改造场发射测试方法对薄膜的场发射性能进行了评价,同时研究了反应时间与络合剂/分散剂的改变对其场发射性能的影响,通过计算薄膜的功函数、几何场增强因子以及有效发射面积,得到影响场发射性能的主导因素。
2.设计反应路线,运用传统化学浴沉积方法成功制备出ZnO薄膜。研究溅射参数、络合剂与反应溶液环境等反应参数对制备过程的影响。通过调节这些反应参数有效控制了制备过程,最终制备出结晶良好、具有纤锌矿结构的、具有高度(0002)取向的ZnO薄膜,并对其带隙与电导率进行了计算。选取波长为630nm的红光激光器作为光源,对ZnO一维纳米阵列是否存在光陷效应进行了证明。将ZnO进行Al元素的n型掺杂,并利用紫外-可见漫反射光谱对ZnO:Al一维纳米阵列进行了雾度的测试,研究了随着反应时间以及掺杂量的增加雾度的变化规律;对未掺杂ZnO与Al掺杂ZnO一维纳米阵列进行了电阻率和Hall效应的测试,研究了Al掺杂量的增加对薄膜载流子浓度以及迁移率的影响。
CuInS2 is a solar cell materials with superior performance. It has the following advantages, such as: high light absorption rate, its band gap being close to the optimum band gap solar cells, direct band gap semiconductor, being doped to both p-type and n-type semiconductor membranes, the highest theoretical conversion efficiency, and low cost. So, it is known as the most promising material for photovoltaic devices. This article aims to synthesize copper sulfide and zinc oxide thin films with high crystallinity and to study their optical and electrical properties by using low energy, environmentally friendly chemical bath deposition method, designing the experimental program, and optimize the experimental parameters. The main contents of this paper can be divided into two parts:
1. CuS thin film was successfully prepared using traditional and microwave assisted chemical bath deposition method by designing reaction route, and also thermodynamics and kinetics processes of thin films preparaed by these two methods are compared. The reaction parameters such as: reaction time, pH value, and additive are investigated carefully to see how these parameters influence on the whole preparation process. By adjusting the parameters of these reactions, the preparation processes are under controlled. Therefore, CuS thin films are synthesized with a good crystalline, strict stoichiometric ratio, and a special surface morphology. The correlative optical and electrical properties are tested. Especially, the transmittance and reflection of the thin films are measured and the corresponding band gaps are calculated. Meanwhile, the electric resistivity is measured. The field emission properties of the as-prepared thin films are evaluated through alterating the testing method. The factors affecting on the field emission properties such as reaction time and chelations/additives are researched. Then the dominant factors which affect the field emission properties are derived by calculating the work function, geometric enhancement factor and effective emission area of the thin films.
2. ZnO 1D nanorod arrays are prepared by designing reaction route, using chemical bath deposition. The reaction parameters such as the parameters of RF-sputtering, the category of the chelation and the environment of the solution are investigated. By adjusting these parameters, the growth of the nanorods are under controlled. A ZnO nanorod arrays with good crystalline, wurtzite structure and high c-axis orientation are obtained. Then, we select a red laser with the wavelength of 630 nm as a light source to prove whether these kind of one-dimensional ZnO arrays have light trapping effect or not. As we all know, the pure ZnO has a low electric resistivity. So, the Al doped ZnO n-type semiconductor is prepared. The haze of ZnO:Al 1D nanorod arrays are investigated by using UV-Vis spectroscopy, and the change of haze with the variation of the reaction time and Al dopant composition are tested. A set of comparative experiments including electrical resistivity test and Hall effect test are carried on both doped ZnO and undoped ZnO. Finally, we study the change of mobility and carrier concentration with the increasement of Al doping on the films.
1.设计反应路线,运用传统化学浴沉积与微波辅助方法成功制备出CuS薄膜,并比较了两种方法制备薄膜的热力学和动力学过程。研究反应时间、溶液pH值以及添加剂等反应参数对制备过程的影响。通过调节这些反应参数有效控制了制备过程,最终制备出结晶良好、符合化学计量比、表面具有特殊形貌的CuS薄膜,并对其带隙与电导率进行了计算。通过改造场发射测试方法对薄膜的场发射性能进行了评价,同时研究了反应时间与络合剂/分散剂的改变对其场发射性能的影响,通过计算薄膜的功函数、几何场增强因子以及有效发射面积,得到影响场发射性能的主导因素。
2.设计反应路线,运用传统化学浴沉积方法成功制备出ZnO薄膜。研究溅射参数、络合剂与反应溶液环境等反应参数对制备过程的影响。通过调节这些反应参数有效控制了制备过程,最终制备出结晶良好、具有纤锌矿结构的、具有高度(0002)取向的ZnO薄膜,并对其带隙与电导率进行了计算。选取波长为630nm的红光激光器作为光源,对ZnO一维纳米阵列是否存在光陷效应进行了证明。将ZnO进行Al元素的n型掺杂,并利用紫外-可见漫反射光谱对ZnO:Al一维纳米阵列进行了雾度的测试,研究了随着反应时间以及掺杂量的增加雾度的变化规律;对未掺杂ZnO与Al掺杂ZnO一维纳米阵列进行了电阻率和Hall效应的测试,研究了Al掺杂量的增加对薄膜载流子浓度以及迁移率的影响。
CuInS2 is a solar cell materials with superior performance. It has the following advantages, such as: high light absorption rate, its band gap being close to the optimum band gap solar cells, direct band gap semiconductor, being doped to both p-type and n-type semiconductor membranes, the highest theoretical conversion efficiency, and low cost. So, it is known as the most promising material for photovoltaic devices. This article aims to synthesize copper sulfide and zinc oxide thin films with high crystallinity and to study their optical and electrical properties by using low energy, environmentally friendly chemical bath deposition method, designing the experimental program, and optimize the experimental parameters. The main contents of this paper can be divided into two parts:
1. CuS thin film was successfully prepared using traditional and microwave assisted chemical bath deposition method by designing reaction route, and also thermodynamics and kinetics processes of thin films preparaed by these two methods are compared. The reaction parameters such as: reaction time, pH value, and additive are investigated carefully to see how these parameters influence on the whole preparation process. By adjusting the parameters of these reactions, the preparation processes are under controlled. Therefore, CuS thin films are synthesized with a good crystalline, strict stoichiometric ratio, and a special surface morphology. The correlative optical and electrical properties are tested. Especially, the transmittance and reflection of the thin films are measured and the corresponding band gaps are calculated. Meanwhile, the electric resistivity is measured. The field emission properties of the as-prepared thin films are evaluated through alterating the testing method. The factors affecting on the field emission properties such as reaction time and chelations/additives are researched. Then the dominant factors which affect the field emission properties are derived by calculating the work function, geometric enhancement factor and effective emission area of the thin films.
2. ZnO 1D nanorod arrays are prepared by designing reaction route, using chemical bath deposition. The reaction parameters such as the parameters of RF-sputtering, the category of the chelation and the environment of the solution are investigated. By adjusting these parameters, the growth of the nanorods are under controlled. A ZnO nanorod arrays with good crystalline, wurtzite structure and high c-axis orientation are obtained. Then, we select a red laser with the wavelength of 630 nm as a light source to prove whether these kind of one-dimensional ZnO arrays have light trapping effect or not. As we all know, the pure ZnO has a low electric resistivity. So, the Al doped ZnO n-type semiconductor is prepared. The haze of ZnO:Al 1D nanorod arrays are investigated by using UV-Vis spectroscopy, and the change of haze with the variation of the reaction time and Al dopant composition are tested. A set of comparative experiments including electrical resistivity test and Hall effect test are carried on both doped ZnO and undoped ZnO. Finally, we study the change of mobility and carrier concentration with the increasement of Al doping on the films.
引文
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