Methoxy‐substituted triphenylamines served as a core to design innovative, cost‐effective hole transport materials essential for the development of efficient perovskite solar cells

Abstract Developing effective perovskite solar cells requires hole transport materials (HTMs) with affordable manufacturing, strong charge mobility, and high efficiency. The four novel HTMs (Qx1‐TPA–Qx6‐TPA) generated by different acceptor engineering of OMeTPA donor were analyzed in this study to establish their structural and photophysical characteristics. Our results demonstrated the effective coherence of the newly proposed HTMs regarding charge excitation and transmission qualities that are ideal for ultrafast hole mobility. A time‐dependent density functional theory was also employed to assess the optical characteristics, such as the emission and absorption spectra. The findings demonstrate that the functionalized HTMs with acceptor groups exhibit proper alignment of the HTM/Perovskite bands, with smaller Stokes shifts (10–24 nm), less absorption in the visible region (≤434) with minimal overlap against the perovskite layer, and deeper HOMO levels (−4.42 to −4.55 eV). These attributes suggest appropriate photophysical properties for effective solar cells. The investigated HTMs show reduced reorganization energy of the hole (0.113–0.146 eV), which indicates robust hole mobility. Additionally, improved solubility and surface‐wetting qualities are implied by greater negative solvation‐free energy values (−21.68 to −40.81 kcal/mol). This study expands our knowledge of push–pull molecular engineering for diverse HTMs, which hold great potential for effective and useful application in PSCs.