苯并唑类聚合物光伏材料的设计合成与性能研究
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摘要
本文以拓宽聚合物的吸收光谱、改善其溶解性能和提高载流子迁移率为目的,设计与合成了三个系列的新型苯并唑类共轭聚合物。再分别以它们为活性层材料,制备了本体异质结光伏器件,讨论了光活性材料、形貌等与光伏器件性能的关系。具体内容包括：
(1)在苯并噻二唑的5,6位引入辛氧基,在其4,7位引入不同个数的噻吩单元(0,1,2),得到相应的单体M1,M2,M3。再将它们与苯并二噻吩二锡通过Stille偶联得到三种新型窄带隙共轭聚合物(P1,P2,P3)。鉴于这三种聚合物材料较宽的吸收光谱(300-820 nm),我们制备了基于P1,P2,P3为给体材料和PCBM为受体材料的本体异质结太阳能电池。初步的器件结果显示P3的能量转换效率高达4.02%,是一种很有商业前景的光伏材料。
(2)以5,6-辛氧基-二噻吩苯并噻二唑(DODTBT)为受体单元,芴或2,7-咔唑为给体单元,通过Suzuki偶联反应得到两种新的聚合物—P4和P5,再加上前一章的P3,考察不同给体单元对此类聚合物材料光伏性能的影响。
(3)首次将含烷氧链的苯并噁二唑单元引入聚合物光伏材料中,合成了四种新型窄带隙聚合物(PBDT-BX, PBDT-DTBX, PC-DTBX和PF-DTBX),并对其进行了详细表征。研究发现,它们具有良好的溶解性能、较好的热稳定性和较窄的带隙,且它们的光电性能由于其给体单元不同而各有差异。在AM 1.5 G,80mW/cm2光照下,器件结构ITO/PEDOT:PSS/polymer:PC61BM(1:2)/Ca/Al,基于PBDT-DTBX和PC-DTBX光伏器件的能量转换效率分别为2.90%和1.31%。结果表明苯并嗯二唑(BX)基共轭聚合物是一类很有前景的光伏材料。
In order to broaden the absorption spectrum of conjugated polymer donor materials, improve their solubility and hole mobility, three new series of new benzoxazolyl conjugated polymers were designed and synthesized in this dissertation. Bulk heterojunction(BHJ) polymer solar cells were fabricated using these conjugated polymers blended with PCBM as active layers. Furthermore the relationship between active layers, morphology and photovoltaic performance were also discussed. The main results are as follows:
(1) Three alternating conjugated copolymers, comprised of benzodithiophene(BDT) and 5,6-dioctyloxy-benzothiadiazole(DOBT) derivatives with (0,1,2) thiophene unit, were synthesized via Stille cross-coupling reaction. These copolymers seemed promising for the application in BHJ solar cells due to their good solubility and high hole mobility as well as their low bandgap. The photovoltaic properties of the copolymers were investigated based on the blend of different the polymer/PC71BM weight ratio under AM1.5G illumination at 100 mW/cm2. The device with ITO/PEDOT:PSS/P3:PC71BM(1:2, w/w)/Ca/Al gave the best performance, with a power conversion efficiency of 4.02%.
(2) Using 5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)benzothiadiazole (DODTBT) as an electron-deficient moiety and fluorene or 2,7-carbazole as an electron-rich moiety, we synthesized two new low bandgap copolymers with good solubility, P4 and P5, respectively. Combined with P3 from the previous chapter, we investigated different donor moiety effect on photovoltaic properties of such kind of conjugated polymer materials.
(3) Four D-A alternating low bandgap copolymers, using 5, 6-bisalkoxylbenzooxadiazole (BX) as an electron-deficient moiety and benzodithiophene or 2,7-carbazole or fluorene as an electron-rich unit, were synthesized and well characterized. The copolymers possess good solubility, high thermal stability, broad absorption as well as low bandgap ranging from 1.52 eV to 1.73 eV. Their electronic and photovoltaic properties can be easily tuned by incorporating different donor moieties into the polymer backbone. The preliminary photovoltaic device based on PBDT-DTBX:PC61BM gave a PCE value of 2.90%, which showed that BX probably is a promising electron accepting building block in organic electronics.
(1)在苯并噻二唑的5,6位引入辛氧基,在其4,7位引入不同个数的噻吩单元(0,1,2),得到相应的单体M1,M2,M3。再将它们与苯并二噻吩二锡通过Stille偶联得到三种新型窄带隙共轭聚合物(P1,P2,P3)。鉴于这三种聚合物材料较宽的吸收光谱(300-820 nm),我们制备了基于P1,P2,P3为给体材料和PCBM为受体材料的本体异质结太阳能电池。初步的器件结果显示P3的能量转换效率高达4.02%,是一种很有商业前景的光伏材料。
(2)以5,6-辛氧基-二噻吩苯并噻二唑(DODTBT)为受体单元,芴或2,7-咔唑为给体单元,通过Suzuki偶联反应得到两种新的聚合物—P4和P5,再加上前一章的P3,考察不同给体单元对此类聚合物材料光伏性能的影响。
(3)首次将含烷氧链的苯并噁二唑单元引入聚合物光伏材料中,合成了四种新型窄带隙聚合物(PBDT-BX, PBDT-DTBX, PC-DTBX和PF-DTBX),并对其进行了详细表征。研究发现,它们具有良好的溶解性能、较好的热稳定性和较窄的带隙,且它们的光电性能由于其给体单元不同而各有差异。在AM 1.5 G,80mW/cm2光照下,器件结构ITO/PEDOT:PSS/polymer:PC61BM(1:2)/Ca/Al,基于PBDT-DTBX和PC-DTBX光伏器件的能量转换效率分别为2.90%和1.31%。结果表明苯并嗯二唑(BX)基共轭聚合物是一类很有前景的光伏材料。
In order to broaden the absorption spectrum of conjugated polymer donor materials, improve their solubility and hole mobility, three new series of new benzoxazolyl conjugated polymers were designed and synthesized in this dissertation. Bulk heterojunction(BHJ) polymer solar cells were fabricated using these conjugated polymers blended with PCBM as active layers. Furthermore the relationship between active layers, morphology and photovoltaic performance were also discussed. The main results are as follows:
(1) Three alternating conjugated copolymers, comprised of benzodithiophene(BDT) and 5,6-dioctyloxy-benzothiadiazole(DOBT) derivatives with (0,1,2) thiophene unit, were synthesized via Stille cross-coupling reaction. These copolymers seemed promising for the application in BHJ solar cells due to their good solubility and high hole mobility as well as their low bandgap. The photovoltaic properties of the copolymers were investigated based on the blend of different the polymer/PC71BM weight ratio under AM1.5G illumination at 100 mW/cm2. The device with ITO/PEDOT:PSS/P3:PC71BM(1:2, w/w)/Ca/Al gave the best performance, with a power conversion efficiency of 4.02%.
(2) Using 5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)benzothiadiazole (DODTBT) as an electron-deficient moiety and fluorene or 2,7-carbazole as an electron-rich moiety, we synthesized two new low bandgap copolymers with good solubility, P4 and P5, respectively. Combined with P3 from the previous chapter, we investigated different donor moiety effect on photovoltaic properties of such kind of conjugated polymer materials.
(3) Four D-A alternating low bandgap copolymers, using 5, 6-bisalkoxylbenzooxadiazole (BX) as an electron-deficient moiety and benzodithiophene or 2,7-carbazole or fluorene as an electron-rich unit, were synthesized and well characterized. The copolymers possess good solubility, high thermal stability, broad absorption as well as low bandgap ranging from 1.52 eV to 1.73 eV. Their electronic and photovoltaic properties can be easily tuned by incorporating different donor moieties into the polymer backbone. The preliminary photovoltaic device based on PBDT-DTBX:PC61BM gave a PCE value of 2.90%, which showed that BX probably is a promising electron accepting building block in organic electronics.
引文
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