Structural fluctuations cause spin-split states in tetragonal (CH3NH3)PbI3 as evidenced by the circular photogalvanic effect

Abstract

Lead halide perovskites are used in thin-film solar cells, which owe their high efficiency to the long lifetimes of photocarriers. Various calculations find that a dynamical Rashba effect could significantly contribute to these long lifetimes. This effect is predicted to cause a spin splitting of the electronic bands of inversion-symmetric crystalline materials at finite temperatures, resulting in a slightly indirect band gap. Direct experimental evidence of the existence or the strength of the spin splitting is lacking. Here, we resonantly excite photocurrents in single crystalline ([Formula: see text])[Formula: see text] with circularly polarized light to clarify the existence of spin splittings in the band structure. We observe a circular photogalvanic effect, i.e., the photocurrent depends on the light helicity, in both orthorhombic and tetragonal ([Formula: see text])[Formula: see text] At room temperature, the effect peaks for excitation photon energies [Formula: see text] meV below the direct optical band gap. Temperature-dependent measurements reveal a sign change of the effect at the orthorhombic-tetragonal phase transition, indicating different microscopic origins in the two phases. Within the tetragonal phase, both [Formula: see text] and the amplitude of the circular photogalvanic effect increase with temperature. Our findings support a dynamical Rashba effect in this phase, i.e., a spin splitting caused by thermally induced structural fluctuations which break inversion symmetry.