Molecule-Adsorbed Topological Insulator and Metal Surfaces: A Comparative First-Principles Study

We compare electronic structure characteristics of three different kinds of benzene-adsorbed (111) surfaces: that of Bi₂Te₃, a prototypical topological insulator, that of Au, a prototypical inert metal, and that of Pt, a prototypical catalytic metal. Using first-principles calculations based on dispersion-corrected density functional theory, we show that benzene is chemisorbed on Pt, but physisorbed on Au and Bi₂Te₃. The adsorption on Bi₂Te₃ is particularly weak, consistent with a minimal perturbation of the electronic structure at the surface of the topological insulator, revealed by a detailed analysis of the interaction of the molecular orbitals with the topological surface states

Rashba Effect in a Single Colloidal CsPbBr₃ Perovskite Nanocrystal Detected by Magneto-Optical Measurements

This study depicts the influence of the Rashba effect on the band-edge exciton processes in all-inorganic CsPbBr₃ perovskite single colloidal nanocrystal (NC). The study is based on magneto-optical measurements carried out at cryogenic temperatures under various magnetic field strengths in which discrete excitonic transitions were detected by linearly and circularly polarized measurements. Interestingly, the experiments show a nonlinear energy splitting between polarized transitions versus magnetic field strength, indicating a crossover between a Rashba effect (at the lowest fields) to a Zeeman effect at fields above 4 T. We postulate that the Rashba effect emanates from a lattice distortion induced by the Cs⁺ motion degree of freedom or due to a surface effect in nanoscale NCs. The unusual magneto-optical properties shown here underscore the importance of the Rashba effect in the implementation of such perovskite materials in various optical and spin-based devices

High Chloride Doping Levels Stabilize the Perovskite Phase of Cesium Lead Iodide

Cesium lead iodide possesses an excellent combination of band gap and absorption coefficient for photovoltaic applications in its perovskite phase. However, this is not its equilibrium structure under ambient conditions. In air, at ambient temperature it rapidly transforms to a nonfunctional, so-called yellow phase. Here we show that chloride doping, particularly at levels near the solubility limit for chloride in a cesium lead iodide host, provides a new approach to stabilizing the functional perovskite phase. In order to achieve high doping levels, we first co-deposit colloidal nanocrystals of pure cesium lead chloride and cesium lead iodide, thereby ensuring nanometer-scale mixing even at compositions that potentially exceed the bulk miscibility of the two phases. The resulting nanocrystal solid is subsequently fused into a polycrystalline thin film by chemically induced, room-temperature sintering. Spectroscopy and X-ray diffraction indicate that the chloride is further dispersed during sintering and a polycrystalline mixed phase is formed. Using density functional theory (DFT) methods in conjunction with nudged elastic band techniques, low-energy pathways for interstitial chlorine diffusion into a majority-iodide lattice were identified, consistent with the facile diffusion and fast halide exchange reactions observed. By comparison to DFT-calculated values (with the PBE exchange-correlation functional), the relative change in band gap and the lattice contraction are shown to be consistent with a Cl/I ratio of a few percent in the mixed phase. At these incorporation levels, the half-life of the functional perovskite phase in a humid atmosphere increases by more than an order of magnitude