Positional Effect of the Triphenylamine Group on the Optical and Charge‐Transfer Properties of Thiophene‐Based Hole‐Transporting Materials

Hybrid organic-inorganic perovskite solar cells (PSCs) have shown significant potential for use in the energy field. Typically, hole-transporting materials (HTMs) play an important role in affecting the power conversion efficiency (PCE) of PSCs. A deep understanding of the structure-property relationship plays a vital role in developing efficient HTMs. Herein, the relationship between the structure and properties of two small organic HTMs H2,5 and H3,4 were systematically investigated in terms of the electronic and optical properties, the hole-transporting behavior by using density functional theory (DFT) and Marcus electron transfer theory. The results demonstrated that the high power conversion efficiency of the H2,5-based PSC was caused by strong interactions with the perovskite material on the interface and an enhanced hole mobility in H2,5 compared with H3,4. The strong interaction derives from the short bond length of O atom of HTM and Pb atom of perovskite material, and the highly hole mobility derives from the quasi-planar conjugated conformation and tight packing model of neighboring molecules in H2,5. In addition, we found that the planar structure enhances the intermolecular interaction between HTM and perovskite materials compared with the 'V'-shaped molecule. Importantly, we also note that the HOMO level of the isolated molecule is not always proportional to the open-circuit voltages of PSCs since the HOMO level might move toward a higher level when the interaction between HTM and interface of perovskite was included. The work gives essential information for rational designing efficient HTMs.