Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping

Solution‐processed copper(I) thiocyanate (CuSCN) typically exhibits low crystallinity with short‐range order; the defects result in a high density of trap states that limit the device's performance. Despite the extensive electronic applications of CuSCN, its defect properties are not understood in detail. Through X‐ray absorption spectroscopy, pristine CuSCN prepared from the standard diethyl sulfide‐based recipe is found to contain under‐coordinated Cu atoms, pointing to the presence of SCN − vacancies. A defect passivation strategy is introduced by adding solid I 2 to the processing solution. At small concentrations, the iodine is found to exist as I − which can substitute for the missing SCN − ligand, effectively healing the defective sites and restoring the coordination around Cu. Computational study results also verify this point. Applying I 2 ‐doped CuSCN as a p‐channel in thin‐film transistors shows that the hole mobility increases by more than five times at the optimal doping concentration of 0.5 mol.%. Importantly, the on/off current ratio and the subthreshold characteristics also improve as the I 2 doping method leads to the defect‐healing effect while avoiding the creation of detrimental impurity states. An analysis of the capacitance‐voltage characteristics corroborates that the trap state density is reduced upon I 2 addition.