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•Transition metal complexes as p-type dopants in perovskite solar cells is reviewed.•TMC-based hole-transporting materials in PSCs are discussed in detail.•Metal phthalocyanines and porphyrins are promising HTMs to be further explored.
In the past few years, the photovoltaic community has witnessed a fast growth of inorganic-organic hybrid perovskite solar cells (PSCs) due to their exceptional power conversion efficiencies with a certified record value exceeding 25%, which rivals the established commercial solar cell technologies. In the state-of-the-art PSCs, a hole-transporting layer (HTL) typically consisting of an active hole-transporting material (HTM) and some additives or dopants, takes the responsibility of transporting the photo-generated holes from the perovskite to the selective contact electrode, and is a key component for achieving high-performance and stable PSCs. In this review article, recent advances in the development of transition metal complexes in HTLs for PSCs including HTMs and p-type dopants are presented.