基于芳香稠環(huán)共軛聚合物的制備及其光伏性能研究
發(fā)布時間：2019-04-09 06:48
【摘要】：利用光電器件將太陽能轉(zhuǎn)化為電能是解決當(dāng)今能源危機(jī)的重要舉措。有機(jī)太陽電池材料因其自身特有的優(yōu)勢如質(zhì)量輕易攜帶、產(chǎn)品成本低廉、柔性良好應(yīng)用價值高,成為研究熱點(diǎn)。目前最新報道的聚合物太陽電池的光電轉(zhuǎn)換效率(PCE)已超過13%。在此良好的發(fā)展趨勢下,設(shè)計合成具有較寬吸收光譜、高空穴遷移率及合適能級的聚合物材料是我們努力實(shí)現(xiàn)的目標(biāo)。本文的工作重點(diǎn)是合成三種含芳香稠環(huán)單元的聚合物,通過研究材料的光學(xué)、電化學(xué)和光伏性能,揭示材料的分子結(jié)構(gòu)與器件性能之間的關(guān)系,為今后研究工作提供新的思路。本文系統(tǒng)闡述了聚合物太陽電池器件的發(fā)展、工作原理及材料的表征手段,并通過Stille聚合反應(yīng)制備了七種給體-受體(D-A)型共軛聚合物,主要內(nèi)容如下:(1)設(shè)計合成了以噻吩并苯并二噻吩(BDTT)為給體,噻吩并吡咯二酮(TPD)為受體材料的兩種具有大平面結(jié)構(gòu)的聚合物PBDTT-EH和PBDTT-EO。在分子骨架相同情況下,PBDTT-EO的烷基側(cè)鏈更長,表現(xiàn)出更佳的溶解性;由于聚合物的平面性較大,在紫外-可見吸收光譜中展現(xiàn)良好的π-π堆積效應(yīng),根據(jù)C-V曲線圖得出的聚合物的HOMO能級有差異,歸因于烷基鏈的不同。在器件的光伏性能表征中,基于PBDTT-EH和PBDTT-EO的器件效率分別為1.92%和2.86%,結(jié)果表明烷基側(cè)鏈的選擇可改變共軛程度,影響器件效率。(2)利用喹喔啉(Qx)單元分別與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,合成兩種聚合物PDTBT-Qx以及PDFBT-Qx。將DTBT以不同氟原子取代后,促進(jìn)分子內(nèi)氫鍵的形成,加強(qiáng)分子間的相互作用;通過較長的2-癸基十四烷基取代喹喔啉單元,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對較低,主要是因?yàn)槲展庾V藍(lán)移所致。(3)合成以氟代的聯(lián)噻吩(PT)衍生物為給體,喹喔啉(Qx)的衍生物為受體的含不同氟原子數(shù)目的三種聚合物PQx-PT、PFQx-PT以及PFFQx-PT。利用氟代聯(lián)噻吩中“F—S分子鎖”效應(yīng),增強(qiáng)聚合物骨架的平面性以及結(jié)晶性。光學(xué)性能顯示隨著取代基氟原子個數(shù)增多,光譜發(fā)生藍(lán)移,三個聚合物的光學(xué)帶隙分別為1.48eV、1.57 eV和1.66 eV。可以發(fā)現(xiàn)隨著F原子的增加,光學(xué)帶隙隨之增大。
[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.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O631.2;TM914.4
本文編號：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.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O631.2;TM914.4
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