Giant and Tunable Excitonic Optical Anisotropy in Single-Crystal Halide Perovskites.

During the last years, giant optical anisotropy has demonstrated its paramount importance for light manipulation. In spite of recent advances in the field, the achievement of continuous tunability of optical anisotropy remains an outstanding challenge. Here, we present a solution to the problem through the chemical alteration of halogen atoms in single-crystal halide perovskites. As a result, we manage to continually modify the optical anisotropy by 0.14. We also discover that the halide perovskite can demonstrate optical anisotropy up to 0.6 in the visible range─the largest value among non-van der Waals materials. Moreover, our results reveal that this anisotropy could be in-plane and out-of-plane depending on perovskite shape─rectangular and square. As a practical demonstration, we have created perovskite anisotropic nanowaveguides and shown a significant impact of anisotropy on high-order guiding modes. These findings pave the way for halide perovskites as a next-generation platform for tunable anisotropic photonics.

Changes in the hydrogen nuclear kinetic energy across the several phases of methylammonium lead tribromide.

We present an experimental investigation of methylammonium lead tribromide single crystals in the orthorhombic, tetragonal, and cubic phases based on inelastic and deep inelastic neutron scattering experiments. We show how the average hydrogen nuclear kinetic energy, mainly affected by zero-point vibrational energies, shows differences larger compared to the changes simply related to temperature effects when moving from one phase to another. In particular, the Gaussian contribution to the average nuclear kinetic energy is larger in the tetragonal phase compared to the cubic and orthorhombic ones. Moreover, we find that the vibrational densities of states of MAPbBr3 single crystals in the orthorhombic phase are compatible with previously reported results on powder samples, and that the only vibrational modes that show slightly different frequencies compared to MAPbI3 are those in the energy range between 100 and 300 cm-1, related to librational/rotational modes. As these shifts are of about 10 cm-1 and do not affect any higher-energy vibrational mode, we conclude that the zero-point energies and average nuclear kinetic energies in the two-hybrid organic/inorganic perovskites are expected to be approximately the same within a harmonic framework.