PET基柔性太阳能电池薄膜电极的制备及其光电转换性能的研究
发布时间：2018-08-03 14:32
【摘要】：柔性有机太阳能电池由于其重量轻、成本低、容易加工、适于大面积生产等特点已经引起人们的广泛关注。但是传统的机械脆性较高的透明导电电极,比如ITO薄膜等,其制备过程需要较高的热处理温度,难以满足在热敏感性的柔性聚合物基底上制备有机太阳能电池的薄膜电极的需要。另一方面,有机太阳能电池的稳定性和能量转换效率与传统的无机太阳能电池相比也还是有一定的差距。因此众多的研究者致力于研究光电性能好,柔韧性高,更适合于制备在热敏感性的聚合物基底上的透明导电薄膜电极；同时,结合改善电极的结构与形貌特点来进一步提高电极性能,从而提高有机太阳能电池等光电器件的重要工作参数,如能量转化率,工作稳定性等,为柔性光电器件的发展,奠定重要的实验与技术基础。本文通过室温磁控溅射的方式,通过表面改性,微量掺杂,溅射参数控制等手段,实现了OMO表面结构、形貌、性能的优化控制,结合透明导电薄膜电极的微观结构特性,光电性能,机械性能,以及光电转换特性的研究,探索了透明电极光电性能与薄膜微观结构,表面形貌的相关性,揭示了其内在联系,并确立了几种OMO结构薄膜的最佳性能,为柔性太阳能电池等柔性光电器件的发展奠定技术基础。主要的研究内容包括： 第一,通过制备OMO(oxide-metal-oxide)三明治结构的ITO-AgQxITO(IAOI)电极,有效地降低了薄膜电极的厚度,从而极大地改善了电极的柔韧性。本研究在OMO结构的基础上,对于中间层M (metal)进行了改进,即通过对纯Ag纳米中间金属层掺杂微量的O,使金属Ag薄膜发生极微小的氧化成为AgOx薄膜,在极大地改善了中间层金属Ag薄膜的透光性的同时,保持了金属Ag的良好导电性能。相比于传统的OMO电极和单层ITO电极,透光性能得到了大幅度提高,保持了相当的导电性,从而采取此种电极作为有机太阳能电池的透明导电电极,将有机太阳能电池的能量转换效率从由ITO为电极的4.72%提高到以IAOI为电极的5.88%,将效率提高了25%。通过弯曲实验证实了这种IAOI薄膜电极具有和ITO-Ag-ITO(IAI)电极相似的柔韧性,适于柔性太阳能电池的电极制备。 第二,在ITO作为外层氧化物的OMO电极研究的基础上,用ZnO代替ITO,从而制备出了不含In、透明导电性优于传统OMO结构的2ZnO-Ag-ZnO(ZAZ)电极的ZnO-AgOx-ZnO(ZAOZ)电极。并且弯曲实验表明,其柔韧性远远好于传统单层ITO电极。由于ZnO与光活性聚合物层的能级匹配性,采用ZAOZ电极作为倒置结构太阳能电池不仅光电转换效率(6.34%)高于传统ITO电极的太阳能电池(5.76%)和用ZnO-Ag-ZnO(ZAZ)作电极制备的太阳能电池(5.65%),而且由于采用了倒置结构,相比于传统结构的柔性有机太阳能电池的5天有效期,其稳定性也得到了提高,在30天之后能量转换效率依然高于初始效率的85%。 第三,在ITO-AgOx-ITO电极的基础上,采用了纳米颗粒阵列的三维结构,制备了三维ITO-AgOx-ITO纳米颗粒阵列(IAOI-NPA)电极。由于采取了三维结构,这样不仅由于降低了颗粒间连续薄膜层的厚度而使电极的柔韧性得到了很大的提高,而且通过调节纳米颗粒间的距离,从而改进了薄膜的减反射性,极大地降低了薄膜电极对于入射光的反射率,直接提高了透光性能。将此三维结构的薄膜用于有机太阳能电池,相比于二维的ITO电极和ITO-Ag-ITO电极,不仅具有更优异的光电性能,而且增大了电极和光活性聚合物的接触面积,从而有效解决了尽量减小光活性层厚度以减小激子传输距离和增大光活性层厚度以增大光吸收的矛盾,同时垂直于基底方向的ITO纳米颗粒阵列也为电荷的传输和收集提供了直接的路径,从而大大地提高了电荷的传输和收集效率,从而提高了能量转换效率,将传统的平面ITO电极的太阳能电池转换效率提高了22%。 通过以上内容的研究,不仅解决了传统OMO结构中间金属层厚度与光电性能之间的矛盾,加深了人们对于纳米光电薄膜光学特性调控机理,电荷传递机制的理论认识,而且有效地改善了ITO结构电极的机械脆性,为实现柔性有机太阳能电池提供了技术支撑。而且通过对PET柔性基底简单有效的表面改性,实现了三维透明薄膜电极的制备,为提高柔性有机太阳能电池的光电转换效率提供了新思路。
[Abstract]:Flexible organic solar cells have attracted wide attention because of their light weight, low cost, easy processing and suitable for large area production. However, the traditional transparent and conductive electrodes with high mechanical brittleness, such as ITO films, need higher thermal temperature to meet the thermal sensitivity of flexible polymers. On the other hand, the stability and energy conversion efficiency of organic solar cells, on the other hand, still have a certain gap compared with the traditional inorganic solar cells. Therefore, many researchers are devoted to the study of good photoelectric properties, high flexibility, and more suitable for the preparation of thermal sensitivity. The transparent conductive film electrode on the polymer substrate, and the improvement of the electrode performance by improving the structure and morphology of the electrode, thus improving the important working parameters of the optoelectronic devices such as the organic solar cells, such as the energy conversion rate and the working stability, is an important experiment and technology for the development of the flexible optoelectronic devices. In this paper, by means of surface modification, micro doping and sputtering parameter control, the surface structure, morphology and properties of OMO are controlled by room temperature magnetron sputtering, and the microstructure characteristics of transparent conductive film electrode, photoelectric property, mechanical energy and photoelectric conversion characteristics are studied, and the transparent electric aurora is explored. The correlation between the electrical properties and the microstructure of the thin films and the surface morphology reveals the internal relations, and establishes the best properties of several OMO structural films, which lays a technical foundation for the development of flexible photovoltaic devices such as flexible solar cells. The main research contents include:
First, by preparing the ITO-AgQxITO (IAOI) electrode of the OMO (oxide-metal-oxide) sandwich structure, the thickness of the film electrode was effectively reduced and the flexibility of the electrode was greatly improved. On the basis of the OMO structure, this study improved the intermediate layer M (metal), that is, by doping a trace O in the pure Ag nanometer intermediate metal layer. The thin oxidation of metal Ag film becomes AgOx thin film, which greatly improves the transmittance of the metal Ag film in the middle layer, while maintaining the good conductivity of the metal Ag. Compared with the traditional OMO electrode and the single layer ITO electrode, the light transmittance has been greatly improved and the electrical conductivity is guaranteed, thus the electrode is taken as the electrode. For the transparent conducting electrode of the organic solar cell, the energy conversion efficiency of the organic solar cell is increased from 4.72% of the ITO electrode to 5.88% of the IAOI as the electrode. The efficiency is improved by the efficiency of 25%. through the bending test. It is proved that the IAOI thin film electrode has the flexibility similar to the ITO-Ag-ITO (IAI) electrode and is suitable for the flexible solar cell. Preparation of the electrode.
Second, on the basis of the study of ITO as the OMO electrode of outer oxide, using ZnO instead of ITO, the ZnO-AgOx-ZnO (ZAOZ) electrode of 2ZnO-Ag-ZnO (ZAZ) electrode without In and transparent conductivity is better than that of the traditional OMO structure. And the flexural experiment shows that its flexibility is far better than that of the traditional monolayer ITO electrode. The energy level matching of the layer, using the ZAOZ electrode as the inverted structure solar cell not only the photoelectric conversion efficiency (6.34%) higher than the traditional ITO electrode solar cell (5.76%) and the ZnO-Ag-ZnO (ZAZ) as the electrode of the solar cell (5.65%), and because of the inverted structure, compared to the traditional structure of the flexible organic solar cell of 5. The stability was also improved during the day of validity. After 30 days, the energy conversion efficiency is still higher than the initial efficiency of 85%..
Third, on the basis of the ITO-AgOx-ITO electrode, three dimensional ITO-AgOx-ITO nano particle array (IAOI-NPA) electrode was prepared by using the three-dimensional structure of the nanoparticle array. The distance between nanoscale particles improves the antireflection property of the film, greatly reduces the reflectivity of the film electrode to the incident light, and improves the light transmittance directly. The application of this three-dimensional structure film to the organic solar cell is not only superior to the two-dimensional ITO electrode and the ITO-Ag-ITO electrode, but also has more excellent photoelectric properties. The contact area of the electrode and the photoactive polymer is larger, which effectively solves the contradiction between reducing the thickness of the light active layer as much as possible to reduce the exciton transmission distance and increasing the thickness of the photoactive layer to increase the optical absorption. At the same time, the ITO nanoparticle array perpendicular to the direction of the substrate provides a direct path for the transmission and collection of charge. The earth improves the efficiency of charge transmission and collection, thus improving the efficiency of energy conversion. The efficiency of solar cells with traditional planar ITO electrodes is increased by 22%.
Through the study of the above contents, the contradiction between the thickness of the middle metal layer and the photoelectric properties of the traditional OMO structure is not only solved, but the theoretical understanding of the mechanism of the optical properties and charge transfer mechanism of the nanometer optoelectronic film is deepened, and the mechanical brittleness of the ITO structure electrode is improved effectively, so as to realize the flexible organic solar cell. It provides a technical support. And through the simple and effective surface modification of the PET flexible substrate, the preparation of the three-dimensional transparent thin film electrode has been realized, which provides a new idea for improving the photoelectric conversion efficiency of the flexible organic solar cells.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.42
本文编号：2162049
[Abstract]:Flexible organic solar cells have attracted wide attention because of their light weight, low cost, easy processing and suitable for large area production. However, the traditional transparent and conductive electrodes with high mechanical brittleness, such as ITO films, need higher thermal temperature to meet the thermal sensitivity of flexible polymers. On the other hand, the stability and energy conversion efficiency of organic solar cells, on the other hand, still have a certain gap compared with the traditional inorganic solar cells. Therefore, many researchers are devoted to the study of good photoelectric properties, high flexibility, and more suitable for the preparation of thermal sensitivity. The transparent conductive film electrode on the polymer substrate, and the improvement of the electrode performance by improving the structure and morphology of the electrode, thus improving the important working parameters of the optoelectronic devices such as the organic solar cells, such as the energy conversion rate and the working stability, is an important experiment and technology for the development of the flexible optoelectronic devices. In this paper, by means of surface modification, micro doping and sputtering parameter control, the surface structure, morphology and properties of OMO are controlled by room temperature magnetron sputtering, and the microstructure characteristics of transparent conductive film electrode, photoelectric property, mechanical energy and photoelectric conversion characteristics are studied, and the transparent electric aurora is explored. The correlation between the electrical properties and the microstructure of the thin films and the surface morphology reveals the internal relations, and establishes the best properties of several OMO structural films, which lays a technical foundation for the development of flexible photovoltaic devices such as flexible solar cells. The main research contents include:
First, by preparing the ITO-AgQxITO (IAOI) electrode of the OMO (oxide-metal-oxide) sandwich structure, the thickness of the film electrode was effectively reduced and the flexibility of the electrode was greatly improved. On the basis of the OMO structure, this study improved the intermediate layer M (metal), that is, by doping a trace O in the pure Ag nanometer intermediate metal layer. The thin oxidation of metal Ag film becomes AgOx thin film, which greatly improves the transmittance of the metal Ag film in the middle layer, while maintaining the good conductivity of the metal Ag. Compared with the traditional OMO electrode and the single layer ITO electrode, the light transmittance has been greatly improved and the electrical conductivity is guaranteed, thus the electrode is taken as the electrode. For the transparent conducting electrode of the organic solar cell, the energy conversion efficiency of the organic solar cell is increased from 4.72% of the ITO electrode to 5.88% of the IAOI as the electrode. The efficiency is improved by the efficiency of 25%. through the bending test. It is proved that the IAOI thin film electrode has the flexibility similar to the ITO-Ag-ITO (IAI) electrode and is suitable for the flexible solar cell. Preparation of the electrode.
Second, on the basis of the study of ITO as the OMO electrode of outer oxide, using ZnO instead of ITO, the ZnO-AgOx-ZnO (ZAOZ) electrode of 2ZnO-Ag-ZnO (ZAZ) electrode without In and transparent conductivity is better than that of the traditional OMO structure. And the flexural experiment shows that its flexibility is far better than that of the traditional monolayer ITO electrode. The energy level matching of the layer, using the ZAOZ electrode as the inverted structure solar cell not only the photoelectric conversion efficiency (6.34%) higher than the traditional ITO electrode solar cell (5.76%) and the ZnO-Ag-ZnO (ZAZ) as the electrode of the solar cell (5.65%), and because of the inverted structure, compared to the traditional structure of the flexible organic solar cell of 5. The stability was also improved during the day of validity. After 30 days, the energy conversion efficiency is still higher than the initial efficiency of 85%..
Third, on the basis of the ITO-AgOx-ITO electrode, three dimensional ITO-AgOx-ITO nano particle array (IAOI-NPA) electrode was prepared by using the three-dimensional structure of the nanoparticle array. The distance between nanoscale particles improves the antireflection property of the film, greatly reduces the reflectivity of the film electrode to the incident light, and improves the light transmittance directly. The application of this three-dimensional structure film to the organic solar cell is not only superior to the two-dimensional ITO electrode and the ITO-Ag-ITO electrode, but also has more excellent photoelectric properties. The contact area of the electrode and the photoactive polymer is larger, which effectively solves the contradiction between reducing the thickness of the light active layer as much as possible to reduce the exciton transmission distance and increasing the thickness of the photoactive layer to increase the optical absorption. At the same time, the ITO nanoparticle array perpendicular to the direction of the substrate provides a direct path for the transmission and collection of charge. The earth improves the efficiency of charge transmission and collection, thus improving the efficiency of energy conversion. The efficiency of solar cells with traditional planar ITO electrodes is increased by 22%.
Through the study of the above contents, the contradiction between the thickness of the middle metal layer and the photoelectric properties of the traditional OMO structure is not only solved, but the theoretical understanding of the mechanism of the optical properties and charge transfer mechanism of the nanometer optoelectronic film is deepened, and the mechanical brittleness of the ITO structure electrode is improved effectively, so as to realize the flexible organic solar cell. It provides a technical support. And through the simple and effective surface modification of the PET flexible substrate, the preparation of the three-dimensional transparent thin film electrode has been realized, which provides a new idea for improving the photoelectric conversion efficiency of the flexible organic solar cells.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.42
【参考文献】
相关期刊论文 前1条
1 ;Flexible organic light-emitting diodes with ITO/Ag/ITO multi-layers as anodes[J];Chinese Science Bulletin;2004年13期
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