三苯胺衍生物的光物理行为及光电转换聚合物的性能研究
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摘要
本文首先以二苯胺、苯胺、对硝基苯胺为原料，加入对氟硝基苯在一定条件下缩合生成了4-硝基-三苯胺、4，4′-二硝基-三苯胺及4，4′，4″-三硝基-三苯胺。然后用Pd-C催化，将硝基取代三苯胺加氢还原得到4-氨基-三苯胺、4，4′-二胺基-三苯胺及4，4′，4″-三氨基-三苯胺。测试了各种三苯胺衍生物在不同极性溶剂、温度、浓度和猝灭剂时的荧光光谱和吸收光谱，研究了其光物理性能。
从分子设计入手，在苝四酸二酐和萘四酸二酐分子上引入三苯胺基团，即用苝(萘)四羧酸二酐分别与4-氨基-三苯胺、4，4′-二胺基-三苯胺及4，4′，4″-三氨基-三苯胺反应，合成了一系列新型染料敏化剂。通过元素分析和傅立叶变换红外(FTIR)等方法表征了酰亚胺衍生物的分子结构；热重分析(TGA)、差热分析(DSC)研究表明其具有良好的热稳定性；紫外-可见吸收光谱(UV-Vis)和循环伏安法(CV)研究了三苯胺结构基团的引入对酰亚胺衍生物的分子能级结构的影响规律，发现三苯胺基团的引入改变了整个染料体系的能级结构，染料的最低未占有轨道(LUMO)能级下降，激发态能级与二氧化钛导带能级相近，轨道发生相互偶合，更利于电子的传递；用UV-Vis、荧光光谱仪(PL)和分子构象模拟等手段研究了引入三苯胺基团对酰亚胺衍生物分子聚集方式的影响规律，证明各苝(萘)酰亚胺衍生物形成了非共面结构。
制备了TiO_2纳米晶多孔膜电极，以合成的各种酰亚胺衍生物为染料对其进行光敏化，组装了电池器件。观察到敏化后的太阳能电池在可见光区域有很强的光电流响应，在90mW／cm~2的白光照射下，器件的短路光电流为0.23mA／cm~2，开路光电压为300mV，填充因子48％，400nm波长处的光电转换效率(IPCE)达到45％，总效率为0.033％。
First of all, 4-nitrotriphenylamine, 4,4′-dinitrotriphenylamine and 4,4′,4″-trinitrotriphenylamine were synthesized from condensation of diphenylamine, aniline,4-nitrophenylamine with 4-fluoronitrobenzene. Redution of nitrophenylamines to thecorresponding amino substituted triphenylamine using the C-Pd catalysts.Fluorescence spectrum and the absorption spectrum of each kind of triphenylaminederivative were tested under different solvent, temperature, concentration, and itsphotophysics performance was studied.
A series of novel triphenylamine-containing aromatic diamine were synthesizedfrom the amination reaction between 4-aminotriphenylamine, 4, 4′-diaminotriphenylamine, 4, 4′, 4″-triaminotriphenylamine and perylene or naphthalenetetracarboxylic dianhydride. Their molecular structures were characterized byelementary analyses and FTIR measurements. The thermostability was investigatedby thermogravimetric analysis (TGA) and the differential Scanning Calorimetry(DSC). UV-Vis and the cyclic voltammetry (CV) was used to investigate the change ofthe energy level structure. Introduction of triphenylamine structure groups changed theentire dye system energy level, and the dye excited state energy level match to thetitanium dioxide conduction band energy level which favors electronic transmission.The change of aggregation way of aromatic diamine was studied by UV-Vis,photoluminescence spectroscopy (PL) and the molecular conformation simulation, andnon-coplane structure of each aromatic diamine derivatives were proven.
We prepared the TiO_2 nanocrystalline electrode which sensitized by synthesizeddyes and assembled the solar cells. We find that the cells have very strongphotoelectric current response in the 400nm-600nm visible light region after TiO_2nanocrystalline electrode was sensitized. The highest cell effiency was 0.033％, short-circuit current(J_(sc)) was 0.23mA/cm~2, Open Circuit Voltage(V_(oc)) was300mV, fill factor was 0.48, IPCE(400nm) was 45％under 90mW/cm~2 light intensity.
从分子设计入手，在苝四酸二酐和萘四酸二酐分子上引入三苯胺基团，即用苝(萘)四羧酸二酐分别与4-氨基-三苯胺、4，4′-二胺基-三苯胺及4，4′，4″-三氨基-三苯胺反应，合成了一系列新型染料敏化剂。通过元素分析和傅立叶变换红外(FTIR)等方法表征了酰亚胺衍生物的分子结构；热重分析(TGA)、差热分析(DSC)研究表明其具有良好的热稳定性；紫外-可见吸收光谱(UV-Vis)和循环伏安法(CV)研究了三苯胺结构基团的引入对酰亚胺衍生物的分子能级结构的影响规律，发现三苯胺基团的引入改变了整个染料体系的能级结构，染料的最低未占有轨道(LUMO)能级下降，激发态能级与二氧化钛导带能级相近，轨道发生相互偶合，更利于电子的传递；用UV-Vis、荧光光谱仪(PL)和分子构象模拟等手段研究了引入三苯胺基团对酰亚胺衍生物分子聚集方式的影响规律，证明各苝(萘)酰亚胺衍生物形成了非共面结构。
制备了TiO_2纳米晶多孔膜电极，以合成的各种酰亚胺衍生物为染料对其进行光敏化，组装了电池器件。观察到敏化后的太阳能电池在可见光区域有很强的光电流响应，在90mW／cm~2的白光照射下，器件的短路光电流为0.23mA／cm~2，开路光电压为300mV，填充因子48％，400nm波长处的光电转换效率(IPCE)达到45％，总效率为0.033％。
First of all, 4-nitrotriphenylamine, 4,4′-dinitrotriphenylamine and 4,4′,4″-trinitrotriphenylamine were synthesized from condensation of diphenylamine, aniline,4-nitrophenylamine with 4-fluoronitrobenzene. Redution of nitrophenylamines to thecorresponding amino substituted triphenylamine using the C-Pd catalysts.Fluorescence spectrum and the absorption spectrum of each kind of triphenylaminederivative were tested under different solvent, temperature, concentration, and itsphotophysics performance was studied.
A series of novel triphenylamine-containing aromatic diamine were synthesizedfrom the amination reaction between 4-aminotriphenylamine, 4, 4′-diaminotriphenylamine, 4, 4′, 4″-triaminotriphenylamine and perylene or naphthalenetetracarboxylic dianhydride. Their molecular structures were characterized byelementary analyses and FTIR measurements. The thermostability was investigatedby thermogravimetric analysis (TGA) and the differential Scanning Calorimetry(DSC). UV-Vis and the cyclic voltammetry (CV) was used to investigate the change ofthe energy level structure. Introduction of triphenylamine structure groups changed theentire dye system energy level, and the dye excited state energy level match to thetitanium dioxide conduction band energy level which favors electronic transmission.The change of aggregation way of aromatic diamine was studied by UV-Vis,photoluminescence spectroscopy (PL) and the molecular conformation simulation, andnon-coplane structure of each aromatic diamine derivatives were proven.
We prepared the TiO_2 nanocrystalline electrode which sensitized by synthesizeddyes and assembled the solar cells. We find that the cells have very strongphotoelectric current response in the 400nm-600nm visible light region after TiO_2nanocrystalline electrode was sensitized. The highest cell effiency was 0.033％, short-circuit current(J_(sc)) was 0.23mA/cm~2, Open Circuit Voltage(V_(oc)) was300mV, fill factor was 0.48, IPCE(400nm) was 45％under 90mW/cm~2 light intensity.
引文
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