基于芳香稠环共轭聚合物的制备及其光伏性能研究
发布时间：2019-04-09 06:48
【摘要】：利用光电器件将太阳能转化为电能是解决当今能源危机的重要举措。有机太阳电池材料因其自身特有的优势如质量轻易携带、产品成本低廉、柔性良好应用价值高,成为研究热点。目前最新报道的聚合物太阳电池的光电转换效率(PCE)已超过13%。在此良好的发展趋势下,设计合成具有较宽吸收光谱、高空穴迁移率及合适能级的聚合物材料是我们努力实现的目标。本文的工作重点是合成三种含芳香稠环单元的聚合物,通过研究材料的光学、电化学和光伏性能,揭示材料的分子结构与器件性能之间的关系,为今后研究工作提供新的思路。本文系统阐述了聚合物太阳电池器件的发展、工作原理及材料的表征手段,并通过Stille聚合反应制备了七种给体-受体(D-A)型共轭聚合物,主要内容如下:(1)设计合成了以噻吩并苯并二噻吩(BDTT)为给体,噻吩并吡咯二酮(TPD)为受体材料的两种具有大平面结构的聚合物PBDTT-EH和PBDTT-EO。在分子骨架相同情况下,PBDTT-EO的烷基侧链更长,表现出更佳的溶解性;由于聚合物的平面性较大,在紫外-可见吸收光谱中展现良好的π-π堆积效应,根据C-V曲线图得出的聚合物的HOMO能级有差异,归因于烷基链的不同。在器件的光伏性能表征中,基于PBDTT-EH和PBDTT-EO的器件效率分别为1.92%和2.86%,结果表明烷基侧链的选择可改变共轭程度,影响器件效率。(2)利用喹喔啉(Qx)单元分别与噻吩取代的苯并噻二唑(DTBT)及氟化的噻吩取代的苯并噻二唑(DFBT)聚合,合成两种聚合物PDTBT-Qx以及PDFBT-Qx。将DTBT以不同氟原子取代后,促进分子内氢键的形成,加强分子间的相互作用;通过较长的2-癸基十四烷基取代喹喔啉单元,改善聚合物的溶解性,并提高聚合物分子的平面性。PDTBT-Qx器件效率比氟取代的聚合物的器件效率相对较低,主要是因为吸收光谱蓝移所致。(3)合成以氟代的联噻吩(PT)衍生物为给体,喹喔啉(Qx)的衍生物为受体的含不同氟原子数目的三种聚合物PQx-PT、PFQx-PT以及PFFQx-PT。利用氟代联噻吩中“F—S分子锁”效应,增强聚合物骨架的平面性以及结晶性。光学性能显示随着取代基氟原子个数增多,光谱发生蓝移,三个聚合物的光学带隙分别为1.48eV、1.57 eV和1.66 eV。可以发现随着F原子的增加,光学带隙随之增大。
[Abstract]:Using photoelectric devices to convert solar energy into electric energy is an important measure to solve the current energy crisis. Organic solar cell material has become a research hotspot because of its unique advantages such as easy carrying of quality, low cost of products and high application value of flexible solar cells. The recently reported photoelectric conversion efficiency of polymer solar cells (PCE) has exceeded 13%. Under this good development trend, the design and synthesis of polymer materials with wide absorption spectrum, high hole mobility and appropriate energy levels are the goals we have made great efforts to achieve. In this paper, three kinds of polymers containing aromatic dense ring units are synthesized. By studying the optical, electrochemical and photovoltaic properties of the materials, the relationship between the molecular structure of the materials and the properties of the devices is revealed, which provides a new idea for the future research work. In this paper, the development, working principle and characterization methods of polymer solar cell devices are described systematically. Seven donor-receptor (D _ (A) conjugated polymers are prepared by Stille polymerization. The main contents are as follows: (1) two polymers with large planar structure, PBDTT-EH and PBDTT-EO., were designed and synthesized using thiophene benzodithiophene (BDTT) as donor and thiophene pyrrolidone (TPD) as acceptor material. When the molecular skeleton is the same, the alkyl side chain of PBDTT-EO is longer and the solubility is better. Due to the large planarity of the polymers and the good 蟺-蟺 stacking effect in the UV-vis absorption spectra, the HOMO energy levels of the polymers are different according to the C _ (?) V curve, which is attributed to the difference of the alkyl chains. In the photovoltaic performance characterization of the device, the device efficiency based on PBDTT-EH and PBDTT-EO is 1.92% and 2.86%, respectively. The results show that the degree of conjugation can be changed by the choice of alkyl side chain. Influence the device efficiency. (2) using quinoxaline (Qx) unit and thiophene substituted benzothiadiazole (DTBT) and fluorinated thiophene substituted benzothiadiazole (DFBT) respectively to synthesize two kinds of polymers PDTBT-Qx and PDFBT-Qx.. DTBT was replaced by different fluorine atoms to promote the formation of intramolecular hydrogen bonds and enhance the interaction between molecules. Through longer 2-decyl tetradecylquinoxaline units, the solubility of polymers is improved and the planarity of polymer molecules is improved. The efficiency of PDTBT-Qx devices is lower than that of fluoro-substituted polymers. The main reason is the blue shift of absorption spectrum. (3) Synthesis of three kinds of polymers PQx-PT,PFQx-PT and PFFQx-PT. containing different number of fluorine atoms using fluorinated bithiophene (PT) derivative as donor and quinoxaline (Qx) derivative as acceptor. The planarity and crystallinity of the polymer skeleton were enhanced by using the "FES molecular locking" effect in fluoro-bithiophene. The optical properties showed that with the increase of the number of substituted fluorine atoms, the spectra shifted blue, and the optical band gaps of the three polymers were 1.48eV, 1.57 eV and 1.66 eV., respectively. It can be found that the optical band gap increases with the increase of F atom.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.2;TM914.4
本文编号：2454940
[Abstract]:Using photoelectric devices to convert solar energy into electric energy is an important measure to solve the current energy crisis. Organic solar cell material has become a research hotspot because of its unique advantages such as easy carrying of quality, low cost of products and high application value of flexible solar cells. The recently reported photoelectric conversion efficiency of polymer solar cells (PCE) has exceeded 13%. Under this good development trend, the design and synthesis of polymer materials with wide absorption spectrum, high hole mobility and appropriate energy levels are the goals we have made great efforts to achieve. In this paper, three kinds of polymers containing aromatic dense ring units are synthesized. By studying the optical, electrochemical and photovoltaic properties of the materials, the relationship between the molecular structure of the materials and the properties of the devices is revealed, which provides a new idea for the future research work. In this paper, the development, working principle and characterization methods of polymer solar cell devices are described systematically. Seven donor-receptor (D _ (A) conjugated polymers are prepared by Stille polymerization. The main contents are as follows: (1) two polymers with large planar structure, PBDTT-EH and PBDTT-EO., were designed and synthesized using thiophene benzodithiophene (BDTT) as donor and thiophene pyrrolidone (TPD) as acceptor material. When the molecular skeleton is the same, the alkyl side chain of PBDTT-EO is longer and the solubility is better. Due to the large planarity of the polymers and the good 蟺-蟺 stacking effect in the UV-vis absorption spectra, the HOMO energy levels of the polymers are different according to the C _ (?) V curve, which is attributed to the difference of the alkyl chains. In the photovoltaic performance characterization of the device, the device efficiency based on PBDTT-EH and PBDTT-EO is 1.92% and 2.86%, respectively. The results show that the degree of conjugation can be changed by the choice of alkyl side chain. Influence the device efficiency. (2) using quinoxaline (Qx) unit and thiophene substituted benzothiadiazole (DTBT) and fluorinated thiophene substituted benzothiadiazole (DFBT) respectively to synthesize two kinds of polymers PDTBT-Qx and PDFBT-Qx.. DTBT was replaced by different fluorine atoms to promote the formation of intramolecular hydrogen bonds and enhance the interaction between molecules. Through longer 2-decyl tetradecylquinoxaline units, the solubility of polymers is improved and the planarity of polymer molecules is improved. The efficiency of PDTBT-Qx devices is lower than that of fluoro-substituted polymers. The main reason is the blue shift of absorption spectrum. (3) Synthesis of three kinds of polymers PQx-PT,PFQx-PT and PFFQx-PT. containing different number of fluorine atoms using fluorinated bithiophene (PT) derivative as donor and quinoxaline (Qx) derivative as acceptor. The planarity and crystallinity of the polymer skeleton were enhanced by using the "FES molecular locking" effect in fluoro-bithiophene. The optical properties showed that with the increase of the number of substituted fluorine atoms, the spectra shifted blue, and the optical band gaps of the three polymers were 1.48eV, 1.57 eV and 1.66 eV., respectively. It can be found that the optical band gap increases with the increase of F atom.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.2;TM914.4
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