单基板全固态介观太阳能电池研究

发布时间：2018-02-27 18:17

本文关键词： 全固态染料敏化碳对电极 P型掺杂钙钛矿介观太阳能电池　出处：《华中科技大学》2014年博士论文　论文类型：学位论文

【摘要】：随着社会科技的发展,能源对人类生存的意义逐步扩大,以至于直接决定着我们未来的生活质量。在传统化石能源开始出现枯竭迹象的二十一世纪,太阳能以其来源广泛巨大,环境友好且可持续利用等特点越来越受到各界的关注。在这其中有一种将太阳能直接转换成电能的光伏器件正以惊人的速度发展起来,与传统的PN结太阳能电池不同的是,这种器件依靠三维网状多孔结构来进行光子的捕获且电子和空穴分离之后分别在不同的相中传递,这些特点有利于获得更高的光子收集效率同时减小电子空穴复合几率,从而获得更高的光电转换效率。而这种用来收集光子的三维多孔材料的孔径一般在2-50nm之间,属于介孔范围,因此这种光伏器件被称为介观太阳能电池。采用介观结构进行光子捕获的概念最早是在1991年被瑞士洛桑联邦理工学院(EPFL)的Gratzel和O'Regan在染料敏化太阳能电池(DSSC)中使用。凭借其低廉的成本与简易的工艺,与传统PN结电池相比具有相当强竞争力。然而,在全固态介观太阳能电池的研究中,大部分器件都是采用贵金属(如金、银等)作为对电极,这一点已成为其商业化道路上的最大障碍。本论文中的研究从全固态DSSC电池起,发展了一套以廉价的碳电极代替贵金属电极的太阳能电池器件的制作方法,并对这种结构中的碳对电极层、二氧化锆间隔层进行了分析与优化,通过路易斯酸P型掺杂使得空穴传输材料/碳对电极界面的电荷传输与注入得到提升；之后将类似的结构应用到新兴的二氧化钛/钙钛矿结构的异质结介观太阳能电池上,并采用有序介孔碳取代了之前的炭黑,也获得了显著的效果。本论文具体的内容为：对基于碳对电极的全固态DSSC的结构及制作进行了分析,并比较了这种多孔接触的对电极与基于普通平面接触对电极对光伏器件,证明了大的接触面积对器件的性能影响,然后研究了不同的碳膜厚度对太阳能电池中的材料填充、电荷注入、电子空穴复合以及光电性能参数的影响,最后采用不同配比的炭黑石墨制作了碳电极,并研究了其不同的电学性能及孔隙特征,分析了它们对太阳能电池光电性能的影响。对基于碳对电极的全固态DSSC中的间隔层的用途和意义做出了研究,观察了其对spiro-OMeTAD填充的影响,从二氧化锆层的膜厚、颗粒大小的角度对全固态DSSC进行优化,并分析它们对太阳能电池内部电荷传输复合的影响,使得二氧化锆间隔层既能作为间隔层阻挡电子空穴的复合又能作为反射层反射更多的光子提高光的利用率。在实现了空穴传输材料和对电极的大面积接触的基础上,采用了路易斯酸四氯化锡添加到空穴传输材料spiro-OMeTAD中作为P型掺杂剂,使得spiro-OMeTAD薄膜的电导率明显上升,而且XPS测试表明spiro-OMeTAD分子的HOMO能级向费米能级发生了移动,从而可以获得更好的电荷传输效果；另外,紫外可见吸收光谱和时间分辨的荧光光谱说明了四氯化锡与spiro-OMeTAD可形成电荷转移复合物,且比之前使用的LiTFSI具有更高的掺杂效率；而采用四氯化锡掺杂之后的全固态DSSC的填充因子和光电转换效率也都得到了明显提升。将具有独特形貌的有序介孔碳材料应用到基于钙钛矿材料的异质结介观太阳能电池,将介孔和介观的概念从光阳极扩展到了对电极之中。所采用的有序介孔碳材料是通过溶剂挥发诱导自组装过程合成,相比于其他方法要简单易行且成本低廉无毒害物质产生,可形成有大量均一有序的介孔和内部联通的框架结构。相比于无序的炭黑颗粒,含有这种有序介孔碳材料的二氧化钛／钙钛矿结构的异质结电池获得了更低的电荷传输电阻和更高光电转换效率。
[Abstract]:With the development of social science and technology , the significance of energy to human existence is gradually expanded so as to directly determine the quality of life in our future . In the twenty - first century , the solar energy is widely used in the 21st century , which is characterized by its extensive source , environment friendship and sustainable utilization . In this paper , we have developed a method for manufacturing solar cell devices with low cost carbon electrodes instead of noble metal electrodes from all solid - state DSSC cells , and the carbon counter electrode layer and the zirconium dioxide spacer layer in this structure are analyzed and optimized , and the similar structures are applied to the heterojunction mesoscopic solar cells of the new titanium dioxide / perovskite structure , and the prior carbon black is replaced by ordered mesoporous carbon , and remarkable effect is obtained . The structure and fabrication of all solid - state DSSC based on carbon dual electrodes were analyzed . The effect of large contact area on the performance of photovoltaic devices was compared . The effect of different carbon film thickness on the properties of solar cells was studied . The purpose and significance of spacer layers in full solid DSSC based on carbon - to - electrode were studied . The influence of the spacer layer on the charge transport of solar cells was observed . The effect of these layers on the charge transport recombination in solar cells was analyzed . On the basis of realizing large - area contact of hole transport material and counter electrode , using tin tetrachloride as P - type dopant in hole transport material , the conductivity of ZnO - OMeTA film is obviously increased , and the XPS test shows that the homo - OMeTA has higher doping efficiency than previously used LiTFSI , and the filling factor and photoelectric conversion efficiency of all solid DSSC after tin tetrachloride doping are obviously improved . Compared with the disordered carbon black particles , the heterojunction cell containing the titanium dioxide / perovskite structure with the ordered mesoporous carbon material obtains lower charge transfer resistance and higher photoelectric conversion efficiency .

【学位授予单位】：华中科技大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.4

【共引文献】