A Heteronuclear W/Cu/S Clusters‐Based Donor–Acceptor Polymer for Perovskite Solar Cells

Abstract Designing the donor–acceptor polymers‐based modifiers with good charge mobility and abundant surface functional groups to bind on perovskite material is highly demanded to boost interfacial charge extraction and transport while yet realized. Here, two [WS ₄ Cu ₄ Br] ⁺ and [WS ₄ Cu ₅ Br ₂ ] ⁺ cluster units are bridged by triphenylamine ligands to yield an unprecedented a heteronuclear W/Cu/S clusters‐based donor–acceptor polymer. Due to the effect of Rydberg orbital components in different clusters mainly contributed by Cu ions, Cu‐rich units have negative potential, whereas Cu‐deficient groups display positive potential. This facilitates the formation of a circuit network with ligands acting as “wires” to realize efficient charge transport. Mobility tests reveal that the hole mobility of polymer film is 3.81 × 10 ⁻⁵ cm ² V ⁻¹ s ⁻¹ . Such a polymer can efficiently extract and transport the holes from perovskite film, and thus improving the cell performance and stability. This work opens the opportunities for designing donor–acceptor polymers based on heteronuclear W/Cu/S clusters.