Hole transporting materials (HTMs), owing to their unique bottom position in inverted perovskite solar cells (PSCs), exert a considerable influence on the hole-transporting process and the morphology/performance of the perovskite layers. Considering the well-known interfacial problems associated with commonly-used NiO_x and poly(triarylamine) HTMs in traditional inverted PSCs, there is an urgent need for exploring efficient HTMs exhibiting good film formability/processability and interfacial contact to meet the specific requirements of high-performance and stable inverted PSCs. Herein, we fabricated inverted PSCs involving two star-like, dopant-free, corannulene-cored HTMs with O-terminals (sym-penta(N, N-bis(4-methoxyphenyl)aniline)corannulene, namely Cor-OMePTPA) and S-terminals (sym-penta(N, N-bis(4-(methylthio)phenyl)aniline)corannulene, namely Cor-SMePTPA) for the first time. The Cor-SMePTPA HTM exhibited a stronger hole-transporting ability and a better interfacial chemical linkage when compared to the Cor-OMePTPA HTM. The device containing Cor-SMePTPA HTM delivered a power conversion efficiency of 21.70%, which was the highest among inverted PSCs based on methylthio (SMe)-terminated HTMs. Furthermore, comprehensive experimental and theoretical characterizations clearly showed that the core and outer terminals (O or S) affected the optoelectric and chemical properties of the HTMs as well as the photovoltaic performance and stability of the corresponding PSCs, highlighting the superiority of the design involving a corannulene core and SMe groups in HTMs for inverted PSCs. We believe that such dopant-free corannulene-cored HTMs can have considerable potential for realizing highly efficient and stable PSCs in the future.

空穴传输材料（HTM）由于其在倒置钙钛矿太阳能电池（PSC）中独特的底部位置，对钙钛矿层的空穴传输过程和形态/性能产生相当大的影响。考虑到与传统倒置 PSC 中常用的 NiO _x和聚（三芳胺）HTM 相关的众所周知的界面问题，迫切需要探索具有良好成膜性/加工性和界面接触性的高效 HTM，以满足高要求的特定要求。 -性能稳定的倒置PSC。在此，我们制造了倒置 PSC，涉及两个带有 O 端的星状、无掺杂剂、corannulene 核 HTM（sym -penta( N, N-双(4-甲氧基苯基)苯胺)corannulene，即Cor-OMePTPA)和S-末端( sym -penta( N, N首次发现-双(4-(甲硫基)苯基)苯胺)corannulene，即Cor-SMePTPA)。与Cor-OMePTPA HTM相比，Cor-SMePTPA HTM表现出更强的空穴传输能力和更好的界面化学键合。含有Cor-SMePTPA HTM的器件的功率转换效率为21.70%，这是基于甲硫基（SMe）封端的HTM的倒置PSC中最高的。此外，综合实验和理论表征清楚地表明，核心和外部端子（O或S）影响HTM的光电和化学性质以及相应PSC的光伏性能和稳定性，凸显了涉及设计的优越性。倒置 PSC 的 HTM 中的 Corannulene 核心和 SMe 基团。