有机太阳能电池中的光物理过程研究
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摘要
有机太阳能电池以其清洁、可弯曲和易于大面积制作等优点成为新能源研究中的热点,而有机太阳能电池要真正成为一种低成本、有市场竞争力的可替代绿色能源,首先必须在光电转换效率方面取得突破。在有机太阳能电池中,激子复合是影响光电转换效率的重要因素,为了洞悉有机太阳能电池中的光致电子转移机理,本文以马库斯(Marcus)电子转移理论为基础,通过荧光猝灭重点研究低聚噻吩与富勒烯间的光致电子转移规律。主要研究工作及取得的创新性成果如下:
(1)由于低聚噻吩与富勒烯的吸收谱存在交迭,研究中将不可避免地遇到内滤效应影响的问题。荧光内滤效应的作用将会对光谱测量产生不可忽视的干扰,使得实验数据不能真实反映荧光猝灭的程度,从而也就无法正确地分析材料间的电子转移效率。针对这一难题,本文首先就内滤效应中的竞争吸收和再吸收过程对荧光猝灭率的影响机理分别进行了研究,通过建立二元系统混合吸收的物理模型,提出了去除内滤效应影响的校正方法,为获取正确可靠的荧光猝灭率提供了保障,也为解决内滤效应影响这一光谱分析中的共性问题提供了一条新的途径。
(2)施主、受主间的电子转移过程宏观地体现为荧光的猝灭,通过荧光分析就能研究低聚噻吩与富勒烯间的电子转移效率。借助本文所发明的校正方法,首次对低聚噻吩(3T～7T)与富勒烯(C_(60)、C_(70)、C_(84))间的荧光猝灭进行了系统性研究,发现了光致电子转移效率随低聚噻吩分子链长及富勒烯电子亲和力变化的规律;同时,根据Marcus的电子转移理论,对描述电子转移可能性的自由能变化进行了研究,利用Weller方程对所发现的电子转移规律进行了印证。
(3)为了了解取代基对电子转移效率的影响,本文首次对引入取代基的三联噻吩(3P)与富勒烯(C_(60)、C_(70)、C_(84))间的荧光猝灭进行研究,并与参照材料(5T)进行了对比分析,结果表明其与富勒烯间的电子转移效率同样依赖于富勒烯的电子亲和力,且荧光猝灭率有所上升,但引入取代基后,光吸收及本征荧光强度有所下降。研究结果对于有机光敏材料的合成具有指导意义。
(4)有机太阳能电池的制备技术是实现太阳能转化为电能的关键。本文对基于低聚噻吩(6T、7T)和富勒烯(C_(60)、C_(70))的有机太阳能电池的制备进行探索性研究,取得了阶段性进展和实践经验,为今后研究工作的深入开展奠定了基础。
本文的研究工作得到国家自然科学基金的资助(项目编号:20573030)。
Because of the advantages of its clear, flexible and easy to be produced in large-scale, Organic solar cells become the focus in new energy area. But to make it to be a low cost, competitive, alternative green energy, a breakthrough in photoelectric conversion efficiency should be made first. In organic solar cells, the recombination of exciton is an important influence factor of photoelectric conversion efficiency. For insight into the photo-induced electron transfer mechanism in organic solar cells, in this work, based on Marcus theory on electron transfer, we investigate the photo-induced electron transfer from oligothiophenes to fullerenes via fluorescence quenching. The major research and innovative results obtained are as follows:
(1) In our study, since the absorption spectra of oligothiophenes and fullerenes are overlapping, the inner-filter effect leads to an unrealistically high ratio of fluorescence quenching. Therefor, the experimental data can not be a true reflection of the degree of fluorescence quenching, and thus the efficiency of electron transfer in donor-acceptor system will cannot be properly analyzed. In order to obtain the quenching ratio which can reflect the efficiency of electron transfer realistically, an original correction method is developed via setting up a physical model of absoption of binary system, to remove the affects of the inner-filter effect. This study also provides a new way for solving the general problem of the inner-filter effect.
(2) Fluorescence quenching is a macro phenomenon of electron transfer in donor-acceptor system, so, the efficiency of electron transfer from oligothiophenes to fullerenes can be studied by fluorescence analyzing. With our correction method, the fluorescence quenching of oligothiophenes(3T～7T) /fullerenes(C_(60)、C_(70)、C_(84)) mixtures in solution is studied systemly, and the results show that the electron transfer in oligothiophenes / fullerenes mixtures is clearly dependent on the chain length of oligothiophene and the electron affinity of the fullerenes. Meanwhile, according to Marcus theory on electron transfer, the change in Gibbs free energy for charge separation is also studied, and the results based on Weller equation are in full agreement with above conclusions.
(3) To understand the influence of substituents on electron transfer, terthiophene with substituents (3P) is analyzed via fluorescence quenching, the results show that the efficiency of electron transfer from 3P to fullerenes also depends on the electron affinity of fullerenes. Compared with the reference material (5T), the fluorescence quenching ratios have risen, but the absorption and intrinsic fluorescence intensity decreased. This study has some significance to synthesis of organic photosensitive materials.
(4) Manufacture technique of organic solar cells is the key to realizing the conversion from solar energy into electrical energy. In this paper, the preparation of organic solar cells based on oligothiophenes(6T、7T) and fullerenes(C_(60)、C_(70)) is explored, some interim progresses are obtained, and the practical experiences accumulated lay a foundation for further research..
This research has been supported by the National Natural Science Fundation (No. 20573030).
(1)由于低聚噻吩与富勒烯的吸收谱存在交迭,研究中将不可避免地遇到内滤效应影响的问题。荧光内滤效应的作用将会对光谱测量产生不可忽视的干扰,使得实验数据不能真实反映荧光猝灭的程度,从而也就无法正确地分析材料间的电子转移效率。针对这一难题,本文首先就内滤效应中的竞争吸收和再吸收过程对荧光猝灭率的影响机理分别进行了研究,通过建立二元系统混合吸收的物理模型,提出了去除内滤效应影响的校正方法,为获取正确可靠的荧光猝灭率提供了保障,也为解决内滤效应影响这一光谱分析中的共性问题提供了一条新的途径。
(2)施主、受主间的电子转移过程宏观地体现为荧光的猝灭,通过荧光分析就能研究低聚噻吩与富勒烯间的电子转移效率。借助本文所发明的校正方法,首次对低聚噻吩(3T～7T)与富勒烯(C_(60)、C_(70)、C_(84))间的荧光猝灭进行了系统性研究,发现了光致电子转移效率随低聚噻吩分子链长及富勒烯电子亲和力变化的规律;同时,根据Marcus的电子转移理论,对描述电子转移可能性的自由能变化进行了研究,利用Weller方程对所发现的电子转移规律进行了印证。
(3)为了了解取代基对电子转移效率的影响,本文首次对引入取代基的三联噻吩(3P)与富勒烯(C_(60)、C_(70)、C_(84))间的荧光猝灭进行研究,并与参照材料(5T)进行了对比分析,结果表明其与富勒烯间的电子转移效率同样依赖于富勒烯的电子亲和力,且荧光猝灭率有所上升,但引入取代基后,光吸收及本征荧光强度有所下降。研究结果对于有机光敏材料的合成具有指导意义。
(4)有机太阳能电池的制备技术是实现太阳能转化为电能的关键。本文对基于低聚噻吩(6T、7T)和富勒烯(C_(60)、C_(70))的有机太阳能电池的制备进行探索性研究,取得了阶段性进展和实践经验,为今后研究工作的深入开展奠定了基础。
本文的研究工作得到国家自然科学基金的资助(项目编号:20573030)。
Because of the advantages of its clear, flexible and easy to be produced in large-scale, Organic solar cells become the focus in new energy area. But to make it to be a low cost, competitive, alternative green energy, a breakthrough in photoelectric conversion efficiency should be made first. In organic solar cells, the recombination of exciton is an important influence factor of photoelectric conversion efficiency. For insight into the photo-induced electron transfer mechanism in organic solar cells, in this work, based on Marcus theory on electron transfer, we investigate the photo-induced electron transfer from oligothiophenes to fullerenes via fluorescence quenching. The major research and innovative results obtained are as follows:
(1) In our study, since the absorption spectra of oligothiophenes and fullerenes are overlapping, the inner-filter effect leads to an unrealistically high ratio of fluorescence quenching. Therefor, the experimental data can not be a true reflection of the degree of fluorescence quenching, and thus the efficiency of electron transfer in donor-acceptor system will cannot be properly analyzed. In order to obtain the quenching ratio which can reflect the efficiency of electron transfer realistically, an original correction method is developed via setting up a physical model of absoption of binary system, to remove the affects of the inner-filter effect. This study also provides a new way for solving the general problem of the inner-filter effect.
(2) Fluorescence quenching is a macro phenomenon of electron transfer in donor-acceptor system, so, the efficiency of electron transfer from oligothiophenes to fullerenes can be studied by fluorescence analyzing. With our correction method, the fluorescence quenching of oligothiophenes(3T～7T) /fullerenes(C_(60)、C_(70)、C_(84)) mixtures in solution is studied systemly, and the results show that the electron transfer in oligothiophenes / fullerenes mixtures is clearly dependent on the chain length of oligothiophene and the electron affinity of the fullerenes. Meanwhile, according to Marcus theory on electron transfer, the change in Gibbs free energy for charge separation is also studied, and the results based on Weller equation are in full agreement with above conclusions.
(3) To understand the influence of substituents on electron transfer, terthiophene with substituents (3P) is analyzed via fluorescence quenching, the results show that the efficiency of electron transfer from 3P to fullerenes also depends on the electron affinity of fullerenes. Compared with the reference material (5T), the fluorescence quenching ratios have risen, but the absorption and intrinsic fluorescence intensity decreased. This study has some significance to synthesis of organic photosensitive materials.
(4) Manufacture technique of organic solar cells is the key to realizing the conversion from solar energy into electrical energy. In this paper, the preparation of organic solar cells based on oligothiophenes(6T、7T) and fullerenes(C_(60)、C_(70)) is explored, some interim progresses are obtained, and the practical experiences accumulated lay a foundation for further research..
This research has been supported by the National Natural Science Fundation (No. 20573030).
引文
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