We report an organic luminescent small molecule, Bis(1-phenylisoquinoline) (acetylacetonate) iridium(III) or Ir(piq)2(acac), that can function as a stable and efficient hole selective contact (HSC) for crystalline silicon (c-Si) solar cells. The devices with the Ir(piq)2(acac) HSC exhibit superior charge transport properties and high stability for up to 30 days in the air without packaging. The photovoltaic characteristics with the solution-processed Ir(piq)2(acac) HSC exhibit little dependence on the blade coating speed and film thickness, demonstrating tolerance to coating and thickness variations. Moreover, the series resistance of the solar cells and the surface work function of the Ir(piq)2(acac) HSCs exhibit analogous correlations to the annealing temperature, suggesting that the fill factor (FF) enhancement originates from an upward energy band bending and a reduced barrier height which facilitates hole transport and collection. The conventional c-Si solar cell incorporating an Ir(piq)2(acac) HSC achieves a 17.8% power conversion efficiency (PCE) with a 78.9% FF, both exceeding the reference counterpart with a 16.9% PCE and 76.8% FF. This work opens up possibilities for exploring a variety of organic luminescent small molecules as efficient hole selective contacts in high-efficiency and low-cost silicon photovoltaics. Graphic Abstract

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