The hole-transporting material (HTM) is an important component of perovskite solar cells (PSCs) because it plays a crucial role in achieving high performance. The most frequently used HTM is 2,2′,7,7′-tetrakis­(N,N-di-p-methoxyphenylamino)-9,9′-spirobifluorene (Spiro-OMeTAD). Spiro-OMeTAD requires dopants such as Li­(TFSI) to realize high power conversion efficiencies (PCEs). However, these dopants cause severe instability issues in PSCs. The Spiro-OMeTAD layer also tends to undergo severe morphological deformation at high temperature, which produces large voids and further reduces the cell performance. These drawbacks must be overcome for the commercialization of PSCs. Therefore, it is strongly desirable to develop high-performance dopant-free HTMs to replace Spiro-OMeTAD. Here, we synthesize two cyano-substituted spirobifluorene-based HTMs, SF27 and SF48, for this purpose. These compounds are derived from Spiro-N, which is a Spiro-OMeTAD analogue obtained via the replacement of the p-methoxy substituents with strong electron-donating p-N,N-dimethylamino groups. The influence of cyano substituents on the optoelectronic properties, PCEs, and charge transport behavior in PSCs are investigated. These compounds have a highest occupied molecular orbital energy level that is well-matched to the valence band of perovskite layers. The hole mobility of SF48 (o-cyano-substituted) was determined to be higher than that of SF27 (m-cyano-substituted), although it is lower than those of Spiro-OMeTAD and the reference compound Spiro-N. Mesoporous PSCs were fabricated using these new HTMs without dopants under relatively low HTM concentration conditions, and the cell performance was compared to that of devices with Spiro-OMeTAD and Spiro-N. The PSC with non-doped SF48 exhibited a high PCE of 18.7%, which is comparable to that of the reference PSCs with doped Spiro-OMeTAD (18.6%). In addition, the thermal stability of SF48 at 85 °C in air was superior to that of Spiro-OMeTAD, both with and without dopants. Therefore, the SF48 spirobifluorene-based compound is determined to be quite effective as a high-performance dopant-free HTM for PSCs.

Halogenated solvents (e.g., chlorobenzene and chloroform) are typically used for hole-transporting materials (HTMs) in perovskite solar cells (PSCs); however, their use should be avoided as they are known to be hazardous to the environment. Herein, we synthesized a nonhalogenated-solvent-soluble, dopant-free HTM, SF62. When depositing HTMs for PSCs, SF62 could be dissolved with a nonhalogenated and green solvent, ethyl acetate. It is one of the most common organic solvents and is known to have a low environmental impact. Non-doped-SF62-based PSCs exhibited higher power-conversion efficiency (18.6%) than doped 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamino)-9,9'-spirobifluorene (Spiro-OMeTAD)-based ones (18.3%), with enhanced stability.