Dynamic Symmetry Breaking and Spin Splitting in Metal Halide Perovskites

Abstract

Metal halide perovskites exhibit a materials physics that is distinct from traditional inorganic and organic semiconductors. While materials such as CH3NH3PbI3 are non-magnetic, the presence of heavy elements (Pb and I) in a non-centrosymmetric crystal environment result in a significant spin-splitting of the frontier electronic bands through the Rashba-Dresselhaus effect. We show, from a combination of \textit{ab initio} molecular dynamics, density-functional theory, and relativistic quasi-particle \textit{GW} theory, that the nature (magnitude and orientation) of the band splitting depends on the local asymmetry around the Pb and I sites in the perovskite structure. The potential fluctuations vary in time as a result of thermal disorder and a dynamic lone pair instability of the Pb(II) 6s${}^2$6p${}^0$ ion. We show that the same physics emerges both for the organic-inorganic CH3NH3PbI3 and the inorganic CsPbI3 compound. The results are relevant to the photophysics of these compounds and are expected to be general to other lead iodide containing perovskites.

6 pages, 4 figures. (Supplemental information: 10 pages, 11 figures)

References in corpus (9)

• Local polar fluctuations in lead halide perovskite crystals
• Revealing the role of organic cations in hybrid halide perovskites CH3NH3PbI3
• Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites
• Indirect to direct bandgap transition in methylammonium lead halide perovskite
• Giant Rashba Splitting in CH3NH3PbBr3 Organic-Inorganic Perovskite
• Spontaneous Octahedral Tilting in the Cubic Inorganic Caesium Halide Perovskites CsSnX${}_3$ and CsPbX${}_3$ (X = F, Cl, Br, I)
• Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells
• GW quasiparticle band gap of the hybrid organic-inorganic perovskite CH${}_3$NH${}_3$PbI${}_3$: Effect of spin-orbit interaction, semicore electrons, and self-consistency
• Spin-orbit enhanced carrier lifetimes in noncentrosymmetric semiconductors

Cited by in corpus (11)

• Evidence of large polarons in photoemission band mapping of the perovskite semiconductor CsPbBr${}_3$
• Quantifying Charge Carrier Mobilities and Recombination Rates in Metal Halide Perovskites from Time-Resolved Microwave Photo-conductivity Measurements
• The effects of intrinsic local distortions vs. dynamic thermal motions on the stability and band gaps of cubic oxide and halide perovskites
• Towards predictive band gaps for halide perovskites: Lessons from one-shot and eigenvalue self-consistent GW
• Accurate and efficient band-gap predictions for metal halide perovskites at finite temperature
• Rashba and Dresselhaus effects in 2D Pb-I-based perovskites
• Structural dynamics in hybrid halide perovskites: Bulk Rashba splitting, spin texture, and carrier localization
• Lone Pair Rotational Dynamics in Solids
• Lattice fluctuations, not excitonic correlations, mediated electronic localization in TiSe${}_2$
• Stress effects on vibrational spectra of a cubic hybrid perovskite: A probe of local strain
• Pressure and Inversion Symmetry Breaking Field Driven First Order Phase Transition and Formation of Dirac Circle in Perovskites