【作者】 李莉；

【导师】 袁忠义；

【作者基本信息】 南昌大学 ， 化学， 2021， 硕士

【摘要】 萘酞菁（Nc）具有较大的共轭体系、较高的摩尔消光系数、良好的化学稳定性,是一类性能优良的有机空穴传输材料。未修饰的萘酞菁溶解性差,最低未占有轨道（LUMO）能级过高（-3.61 e V）,无法作为n-型有机半导体材料应用于太阳能电池。本研究将具有长烷基的吸电子的酰亚胺基团引入到萘酞菁中,增加了分子的溶解性,降低了分子的LUMO能级,成功地合成了一系列新型的电子传输材料,并将其用于体相异质结有机太阳能电池,包括以下两方面内容:1)镓萘酞菁酰亚胺作为活性层受体材料的设计、合成及光伏应用研究。以邻二甲苯为原料,通过十一步反应,包括溴化、光催化溴化、Diels-Alder反应、水解、脱水羧合、酰亚胺烷基化、取代反应等,合成了五个具有6-十一烷基酰亚胺基团和轴向取代基团的镓萘酞菁酰亚胺化合物9-13。这类化合物有较好的溶解性（氯仿中溶解度大于30 mg/m L）、LUMO能级（-3.89～-3.95 e V）、很宽的薄膜吸收范围（600 nm-1200 nm）、特别高的摩尔消光系数(3.75～6.18×10⁵M^-1 cm^-1)、良好的热稳定性（T_d>325 ℃）。可将其作为活性层受体材料用于体相异质结太阳能电池。其中化合物12获得了1.28%的光电转化效率（PCE）。2)硅萘酞菁酰亚胺化合物作为阴极界面层材料的设计、合成及光伏应用研究。以6,7-二溴萘酸酐为原料,通过六步反应,包括酰亚胺半全氟烷基化、氰基取代、缩合和配位反应等,合成了两个具有半全氟烷基酰亚胺基团和离子化轴向基团的硅萘酞菁酰亚胺化合物18和化合物19。这类化合物有较宽的薄膜吸收范围（600-1100 nm）、特别高的摩尔消光系数(6.08～6.12×10⁵ M^-1 cm^-1)、良好的热稳定性（T_d>185 ℃）、较低的LUMO能级（-3.92～-3.93 e V）、在极性溶剂中具有一定的溶解性（甲醇中溶解度大于1 mg/m L）。以PM6/Y6作为活性层材料,将化合物19作为阴极界面层材料应用于体相异质结太阳能电池,与未修饰阴极界面层材料的体相异质结太阳能电池相比,其PCE分别从12.00%提升到15.27%。这是首次将萘酞菁酰亚胺作为阴极界面层材料应用于太阳能电池中。更多还原

【Abstract】 Naphthalocyanine（Nc）derivatives with large-conjugated cores are excellent organic hole transporting materials,which have high molar extinction coefficients and good stability.However,they have poor solubility,and their lowest unoccupied molecular orbital（LUMO）energy levels are too high to be electron transporting materials.In this work,the electron-withdrawing imide groups with long alkyl chains were introduced into the phthalocyanines to increase the solubility and reduce LUMO energy levels.A series of novel naphthalocyanine tetraimides were designed,synthesized,and applied to bulk-heterojunction organic solar cells（BHJOSCs）as electron-transporting materials.It contains the following two sections.1)Design,sysnthesis and photovoltaic application study of gallium naphthalocyanine tetraimides（compounds 9-13）as active layer acceptors.In this study,five gallium naphthalocyanine tetraimides with 6-undecyl alkyl chain and different axial substituent groups were synthesized from o-xylene through eleven-step reaction,including bromination,photocatalytic bromination,Diels-Alder,hydrolysis,dehydration,imide alkylation,and substitution.These compounds have good solubility（solubility in chloroform>30 mg/m L）,low LUMO energy levels（-3.89～-3.95 e V）,wide film absorption range（600-1200 nm）,high molar extinction coefficient(3.75～6.18×10⁵ M^-1 cm^-1),and good thermal stability（T_d>325 ℃）.They could be used as acceptors in bulk-heterojunction solar cells（BHJOSCs）.The power conversion efficiency of compound 12 was 1.28%.2)Design,synthesis and photovoltaic applications study of silicon naphthalocyanine tetraimides as cathode interface layer materials.In this study,two silicon naphthalocyanine tetraimides with semi-perfluoroalkyl chains and two different dimethylamines were synthesized from 6,7-dibromonaphthalic anhydride through six-step reaction,including semi-perfluorinated alkylation of imides,cyanide substitution,condensation,and coordination.Both of them have wide film absorption range（600-1100 nm）,high molar extinction coefficients(6.08～6.12×10⁵M^-1 cm^-1),good thermal stability（T_d>185 ℃）,low LUMO energy level（-3.92～-3.93 e V）,and moderate solubility（solubility in methanol>1 mg/m L）.compound 19 was used as cathode interface layer materials in PM6/Y6-based BHJOSCs.Comparing with the BHJOSCs without cathode interface layers,the power conversion efficiency was increased from12.00%to 15.27%.This is the first time for naphthalocyanine tetraimides to be used as cathode interface layer materials in solar cells.更多还原