【作者】 李慧；

【导师】 李战峰；

【作者基本信息】 太原理工大学 ， 凝聚态物理， 2017， 硕士

【摘要】 钙钛矿太阳能电池已经迅速成为大规模太阳能商业化的有力候选者,因为它们成本较低,易于加工并且目前已经能达到22.1%的光电转化效率（PCE）。通常使用2,2’,7,7’-四（N,N’-二对甲氧基苯胺）-9,9’-螺二芴（Spiro-OMeTAD）作为空穴传输材料,可以有效提高其光电转化效率。然而,其复杂的合成和多步骤纯化使其成本昂贵并且限制了该材料在制造规模生产中的潜力。因此,开发具有高效率和长稳定性的成本有效的空穴传输材料尤为重要。在本文中,做了以下工作:（1）论文第三章,我们以咔唑为中心核,通过Suzuki偶联反应、Stille偶联反应、C-N交叉偶联反应分别得到三取代和四取代的三甲氧基苯咔唑、噻吩咔唑以及甲氧基二苯胺咔唑（HTM1,HTM2,HTM3,HTM4,HTM5和HTM6）,均具有合适的HOMO能级。另外该类材料具有良好的稳定性,热失重5%时对应的温度分别为390.1℃、367.3℃、423.0℃、389.6℃、332.0℃以及392.5℃。基于HTM1、HTM2、HTM3、HTM4、HTM5五种小分子材料作为空穴传输材料,制备具有典型的平面构型的FTO/SnO₂/CH3NH3PbI3/HTM/Au的器件,在AM 1.5G,功率为100mW/cm2的太阳光照射下,测得的能量转化效率分别为0.03%、0.04%、17.56%、0.02%、2.68%。（2）论文第四章,我们提出了PSCs的新型空穴传输材料4,4’-二甲氧基二苯胺取代的螺[3.3]庚烷-2,6-二芴（SDF-OMeTAD）。SDF-OMeTAD的合成途径仅需要从廉价的原料开始的两个步骤。使用市售的2,7-二溴芴和季戊四醇四溴化物作为原料,通过一步反应合成SDF-4Br,并且不需要柱色谱来纯化即可得到中心核。然后使用钯催化的Buchwald-Hartwig C-N交叉偶联反应获得目标化合物SDF-OMeTAD。SDF-OMeTAD在常见的有机溶剂如二氯甲烷,氯仿,氯苯和甲苯中具有良好的溶解性,有利于溶液加工。制备FTO/SnO₂/CH3NH3PbI3/SDF-OMeTAD/Au的典型平面结构器件,在100mW/cm2 AM 1.5G光照条件下的可以达到的最优PCE为13.0%,开路电压为1.10V。（3）论文第五章,我们合成了三种新的合成简便的空穴传输材料,中心核分别为一氟苯、二氟苯、二甲氧基苯,分别通过C-N交叉偶联反应获得两个对甲氧基二芳基胺基团取代分子,分别得到1FPhDPA、2FPhDPA、2OMePh DPA。分别从分子结构、光学、热学和电化学对其进行测试分析,我们得到该类空穴传输材料具有合适的HOMO能级,分别为-5.28 eV、-5.20eV、-5.21 eV。这三种新的小分子材料通过一步法即可合成,原料可直接购得,其降低的成本和较少的环境影响对于大规模生产是非常有希望的,这为钙钛矿太阳能电池的发展提供了参考。更多还原

【Abstract】 Perovskite solar cells have quickly become a powerful candidate for large-scale solar commercialization because they are less costly,easy to process and have now achieved 22.1% photoelectric conversion efficiency（PCE）.（N,N’-di-p-methoxyaniline）-9,9’-spirobifluorene（Spiro-OMeTAD）is usually used as a hole transporting material,and it is possible to effectively improve the Photoelectric conversion efficiency.However,its complex synthesis and multi-step purification make it costly and limit the potential of the material in manufacturing scale production.Therefore,it is particularly important to develop cost-effective hole transport materials with high efficiency and long stability.In this article,the following work is done:（1）In the third chapter,we use the carbazole as the central nucleus,through the Suzuki coupling reaction,Stille coupling reaction,C-N cross-coupling reaction were trisubstituted and tetra-substituted trimethoxy phenyl carbazole,thienyl carbazole and Methyldiphenylcarbazole（HTM1,HTM2,HTM3,HTM4,HTM5 and HTM6）have the appropriate HOMO level.In addition,the material has good stability,and the corresponding temperatures are 390.1 ℃,367.3 ℃,423.0 ℃,389.6 ℃,332.0 ℃ and 392.5 ℃ respectively when the weight loss is5%.Based on the above five kinds of small molecular materials（HTM1,HTM2,HTM3,HTM4,HTM5）as the hole transport material,the device of FTO / Sn O₂/ CH3NH3PbI3 / HTM / Au with typical planar configuration was prepared.Under the irradiation of AM 1.5G and power of 100 mW / cm2,The energy conversion efficiencies were 0.03%,0.04%,17.56%,0.02%,2.68%,respectively.（2）In the fourth chapter,we propose a new type of hole transporting material for PSCs 4,4’-dimethoxydiphenylamine-substituted spiro [3.3]heptane-2,6-difluorene（SDF-OMeTAD）.The synthetic pathway of SDF-OMeTAD requires only two steps from the start of the inexpensive starting material（Scheme 1）.Using the commercially available 2,7-dibromofluorene and pentaerythritol tetrabromide as starting materials,SDF-4Br was synthesized by one-step reaction and the center nuclei were obtained without purification by column chromatography.The target compound SDF-OMeTAD was then obtained using the palladium-catalyzed Buchwald-Hartwig C-N cross-coupling reaction.SDF-OMeTAD has good solubility in common organic solvents such as dichloromethane,chloroform,chlorobenzene and toluene,which is beneficial to solution processing.A typical planar structure device for FTO / SnO₂ /CH3NH3PbI3 / SDF-OMeTAD / Au was prepared with an optimum PCE of13.0% and an open circuit voltage of 1.10 V at 100 mW / cm2 AM 1.5 G lighting conditions.（3）In the fifth chapter,we synthesized three new synthetic hole transport materials,the central core were monofluorobenzene,difluorobenzene,dimethoxybenzene,respectively,by CN cross-coupling reaction to obtain two1-methoxy-diarylamine group,1FPh DPA,2FPhDPA,2OMePhDPA,respectively.The results show that the HOMO energy level is-5.28 eV,-5.20 eV and-5.21 eV,respectively,from the molecular structure,optical,thermal and electrochemical tests.These three new small molecular materials can be synthesized by one step,and the raw materials can be purchased directly.The reduced cost and less environmental impact are very promising for mass production.This is the development of perovskite solar cells Provided a reference.更多还原