Donor-acceptor conjugated polymers are considered advanced semiconductor materials for the development of thin-film electronics. One of the most attractive families of polymeric semiconductors in terms of photovoltaic applications are benzodithiophene-based polymers owing to their highly tunable electronic and physicochemical properties, and readily scalable production. In this work, we report the synthesis of three novel push–pull benzodithiophene-based polymers with different side chains and their investigation as hole transport materials (HTM) in perovskite solar cells (PSCs). It is shown that polymer P3 that contains triisopropylsilyl side groups exhibits better film-forming ability that, along with high hole mobilities, results in increased characteristics of PSCs. Encouraging a power conversion efficiency (PCE) of 17.4% was achieved for P3-based PSCs that outperformed the efficiency of devices based on P1, P2, and benchmark PTAA polymer. These findings feature the great potential of benzodithiophene-based conjugated polymers as dopant-free HTMs for the fabrication of efficient perovskite solar cells.

In the last decade, perovskite photovoltaics gained popularity as a potential rival for crystalline silicon solar cells, which provide comparable efficiency for lower fabrication costs. However, insufficient stability is still a bottleneck for technology commercialization. One of the key aspects for improving the stability of perovskite solar cells (PSCs) is encapsulating the photoactive material with the hole-transport layer (HTL) with low gas permeability. Recently, it was shown that the double HTL comprising organic and inorganic parts can perform the protective function. Herein, a systematic investigation and comparison of four double HTLs incorporating polytriarylamine and thermally evaporated transition metal oxides in the highest oxidation state are presented. In particular, it was shown that MoO_x, WO_x, and VO_x-based double HTLs provided stable performance of PSCs for 1250 h, while devices with NbO_x lost 30% of their initial efficiency after 1000 h. Additionally, the encapsulating properties of all four double HTLs were studied in trilayer stacks with HTL covering perovskite, and insignificant changes in the absorber composition were registered after 1000 h under illumination. Finally, it was demonstrated using ToF-SIMS that the double HTL prevented the migration of perovskite volatile components within the structure. Our findings pave the way towards improved PSC design that ensures their long-term operational stability.

Evaporated pyrene-based hole transport materials deliver 17.9% efficiency in dopant free perovskite solar cells.