A series of α-Fe2O3 thin films with distinct morphologies are prepared via a facile polystyrene-block-polyethylene oxide templated sol–gel method. By tailoring the poor solvent contents and FeCl3-to-polymer weight ratio in the sol–gel solutions, quasi-isoporous α-Fe2O3 thin films with different substructures and thicknesses are obtained. Via a thermal annealing post-treatment, double layered structures are induced by a synergistic dewetting and Oswald ripening effect. Special focus is set on the α-Fe2O3 thin films prepared with no annealing/annealing-medium FeCl3 concentration, as they possess uniform periodic structures, which is suitable to be used as hole blocking modification layer of perovskite solar cells (PSCs). An improved power conversion efficiency (PCE) is obtained when the double layered α-Fe2O3 thin film is applied as the hole blocking modification layer for PSCs. The improved PCE primarily originates from the increased VOC, which probably benefits from the synergistic effect of the suppressed charge carrier recombination at the interfaces, the enhanced light transmittance as well as the superior electron extraction capacity.
