Graphical Abstract
![](https://wqketang.oss-cn-beijing.aliyuncs.com/zip-unzip/zip-de1e96e9-6a67-4f7d-89b1-93896181a8e2/nr-9-6-1600/files/nr-9-6-1600-FE1.jpg?Expires=1739912818&OSSAccessKeyId=STS.NTvWNG6BrfAXAFVm85YS6dMhj&Signature=Yf2RojBuEGYOoV06k5n7FET1m34%3D&security-token=CAISywJ1q6Ft5B2yfSjIr5fDHPTz251T0YOzQ2DniThgVdwai4jDiDz2IHtKenhsBOsbtfk1mG5W5%2FgZlqJ9SptIAEfJa9d99MyEKKUj2tCT1fau5Jko1beHewHKeTOZsebWZ%2BLmNqC%2FHt6md1HDkAJq3LL%2Bbk%2FMdle5MJqP%2B%2FUFB5ZtKWveVzddA8pMLQZPsdITMWCrVcygKRn3mGHdfiEK00he8TouufTinpHMskGA1Aell7Mvyt6vcsT%2BXa5FJ4xiVtq55utye5fa3TRYgxowr%2Fwo0v0YpGya5YzHXwcPskvdKZbo78UqLQlla6w%2BGqFJqvPxr%2Fp8t%2Fx5fWJKAezhVgs8cVM8JOjIqKOscIsihsPk7ATWcD1LXoQ6vH1ZZ5%2FAzVZaVWUEMpNqcRxTMldXaQqhSZT8m3upKXzOJeX7ls9%2Fv%2FV7p2s06gHUTzDnGoABahy5BlbrBXr6Ybboln3HKkGMI8p5rY4gnAiIMkq1%2FFkDMbnUGwENWKvQ05sT%2BH4IV5s147ilZIubT3EimEEK7FVolwN0Chpd5FMh0iJPLAMSrbe2knHRNhZimDskS3xbxrPuo8PyMGsJyeQZ2uLTpevxvPhQ%2BU3CqQnKuxl%2FgwUgAA%3D%3D)
A series of conductive polymers, i.e., poly(3-methylthiophene) (PMT), poly(thiophene) (PT), poly(3-bromothiophene) (PBT) and poly(3-chlorothiophene) (PCT), were prepared via the electrochemical polymerization process. Subsequently, their application as hole-transporting materials (HTMs) in CH3NH3PbI3 perovskite solar cells was explored. It was found that rationally increasing the work function of HTMs proves beneficial in improving the open circuit voltage (Voc) of the devices with an ITO/conductive-polymer/CH3NH3PbI3/C60/BCP/Ag structure. In addition, the higher-Voc devices with a higher-work-function HTM exhibited higher recombination resistances. The highest open circuit voltage of 1.04 V was obtained from devices with PCT, with a work function of–5.4 eV, as the hole-transporting layer. Its power conversion efficiency attained a value of approximately 16.5%, with a high fill factor of 0.764, an appreciable open voltage of 1.01 V and a short circuit current density of 21.4 mA·cm–2. This simple, controllable and low-cost manner of preparing HTMs will be beneficial to the production of large-area perovskite solar cells with a hole-transporting layer.
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