The analogues of cesium lead bromide promise outstanding optical and electrical properties, significantly more stable than organic-inorganic hybrid perovskite in ambient atmosphere. Pure CsPbBr3 and Cs4PbBr6 single crystals were separately grown by AVC (anti-solvent vapor-assisted crystallization process) with dimensions of millimeters. We found the correlation between photocurrent generation and PL (photoluminescence) in perovskite crystals. The CsPbBr3 crystals, which have 3D perovskite structure, showed a sensitive steady-state photoresponse and a poor PL signal. Contrastively, the Cs4PbBr6 crystals, which have 0D perovskite structure, exhibited more than 1 order magnitude higher PL intensity than CsPbBr3, which generated an ultralow photocurrent under illumination. We attribute their contrasting opto-electrical characteristics to a difference of exciton binding energy, induced by coordination geometry of [PbBr6]4- octahedron sublattice. Our works help to wide the understanding of the relation of chemical structure with PL and photocurrent generation of perovskite compounds. |