Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites.

Abstract

Recently, CuI - and AgI -based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only AgI -based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of CuI -based analogues. Here we show that, owing to the much higher energy level for the Cu 3d10 orbitals than for the Ag 4d10 orbitals, CuI atoms energetically favor 4-fold coordination, forming [CuX4 ] tetrahedra (X=halogen), but not 6-fold coordination as required for [CuX6 ] octahedra. In contrast, AgI atoms can have both 6- and 4-fold coordinations. Our density functional theory calculations reveal that the synthesis of CuI halide double perovskites may instead lead to non-perovskites containing [CuX4 ] tetrahedra, as confirmed by our material synthesis efforts.