HighlightsThe (011) facet has excellent charge transport properties achieving closer alignment of energy levels.By exploiting the (011) facet a device (0.06 cm2) and a module (29 cm2) achieved power conversion efficiencies of 25.24% and 21.12%, respectively.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01103-8.