Three novel dopant-free hole-transporting materials (HTMs) based on phthalocyanine core containing (4-methyl formate) phenoxy or (4-butyl formate) phenoxy as the peripheral groups with cupper or zinc as the core metals (CuPcNO₂-OMFPh, CuPcNO₂-OBFPh, ZnPcNO₂-OBFPh) were designed and synthesized. All of the phthalocyanine complexes show excellent thermal stabilities, appropriate energy levels and suitable hole mobilities. The potential of three HTMs were tested in perovskite solar cells (PSCs) and ZnPcNO₂-OBFPh based PSC obtained power conversion efficiency (PCE) of 15.74% under 100 mA cm⁻² standard AM 1.5G solar illumination. Most important of all, PSC based on ZnPcNO₂-OBFPh shows better stability than that of the other two phthalocyanines and Spiro-OMeTAD under continuous light irradiation at 60 °C and maximum power point tracking in ambient air without encapsulation after 500 h. The results show that the introduction of appropriate peripheral groups and core metals can improve the performance and stability of PSCs dramatically, which provides an alternative way to develop HTMs for efficient and stable PSCs.

三种新型的基于酞菁核芯的无掺杂空穴传输材料（HTM），其中以（4-甲酸甲酯）苯氧基或（4-甲酸甲酸丁酯）苯氧基为外围基团，以铜或锌为核心金属（CuPcNO ₂ -OMFPh，设计并合成了CuPcNO ₂ -OBFPh，ZnPcNO ₂ -OBFPh）。所有的酞菁配合物均表现出优异的热稳定性，合适的能级和合适的空穴迁移率。在钙钛矿太阳能电池（PSC）中测试了三种HTM的电势，基于ZnPcNO ₂ -OBFPh的PSC在100 mA cm ^-2标准AM 1.5G太阳光照下获得了15.74％的功率转换效率（PCE）。最重要的是，基于ZnPcNO _2的PSC-OBFPh在60°C的连续光照射下以及在500 h后无需封装的环境空气中的最大功率点跟踪下，显示出比其他两种酞菁和Spiro-OMeTAD更好的稳定性。结果表明，引入合适的外围基团和核心金属可以显着提高PSC的性能和稳定性，这为开发高效，稳定的PSC的HTM提供了另一种方法。