The molecular self-organization of organic semiconductors, which is mainly determined by the structural design, film processing, and device configuration, is one of the crucial factors for achieving high-performance organic photovoltaics (OPVs) and perovskite solar cells (PvSCs). In this study, we newly synthesized and developed strongly self-organized small molecules via alkyl side-chain engineering. Replacing “H” to “C₆H₁₃” on the thienyl group, SM2 showed a well-ordered face-on orientation. Due to favorable self-organization leading to effective charge carrier dynamics, including enhanced charge transfer/transport and suppressed recombination, SM2-based OPVs and PvSCs exhibited improved device performance compared to the devices based on SM1 without an additional hexyl side-chain. The best fullerene-based OPV and planar PvSC with SM2 as a small-molecule donor and as a hole transport layer (HTL) achieved an unprecedentedly high efficiency of 9.38% and 20.56%, in contrast with SM1-based devices showing lower efficiency of 8.70% and 15.37%. Furthermore, the planar PvSCs based on undoped-SM2 HTL exhibited comparable efficiency but provided excellent heat and humidity stability compared with doped spiro-OMeTAD-based devices. These results clearly indicated that SM2 with highly-ordered and favorable self-organization is a promising organic semiconductor for future applications of high-performance organic and inorganic-organic hybrid electronics.

有机半导体的分子自组织主要由结构设计，薄膜加工和器件配置决定，是实现高性能有机光伏（OPV）和钙钛矿太阳能电池（PvSC）的关键因素之一。在这项研究中，我们通过烷基侧链工程新合成并开发了强自组织的小分子。将“ H”替换为“ C ₆ H _13”在噻吩基上，SM2显示出整齐的面朝上取向。由于良好的自组织导致有效的电荷载流子动态，包括增强的电荷转移/传输和抑制的重组，与基于SM1的器件相比，基于SM2的OPV和PvSC的器件性能有所提高，而没有附加的己基侧链。最佳的基于富勒烯的OPV和平面PvSC以及SM2作为小分子供体和空穴传输层（HTL），实现了前所未有的高效率，分别为9.38％和20.56％，而基于SM1的器件的效率更低，为8.70 ％和15.37％。此外，与基于掺杂螺旋-OMeTAD的器件相比，基于非掺杂SM2 HTL的平面PvSC表现出可比的效率，但具有出色的热稳定性和湿度稳定性。