Spontaneous anion-exchange synthesis of optically active mixed-valence Cs2Au2I6 perovskites from layered CsAuCl4 perovskites.

Cs2Au2I6, a lead-free photovoltaic material, has been synthesized via controlled and systematic addition of hydroiodic acid (HI) to CsAuCl4. X-ray diffraction studies suggest the formation of Cs2Au2I6 when a threshold concentration of HI is added to CsAuCl4. The final compound shows good stability against light, oxygen and moisture and at temperatures up to 140 °C without any phase degradation. The stability of Cs2Au2I6 is also confirmed by its high negative formation energy and the convex hull diagram constructed using Density Functional Theory (DFT). Absorption studies suggest an abrupt band shift from 2.31 eV to 1.06 eV when HI concentration reaches the threshold limit (∼100 µl). A sharp absorption edge was found for Cs2Au2I6 with an Urbach energy of 59 meV, indicating lower structural disorder and higher crystallinity.

Structural transformations and physical properties of (1 - x) Na0.5Bi0.5TiO3 - x BaTiO3 solid solutions near a morphotropic phase boundary.

Piezoelectric and other physical properties are significantly enhanced at (or near) a morphotropic phase boundary (MPB) in ferroelectrics. MPB materials have attracted significant attention owing to both fundamental physics as well as the possibility of well-regulated energy and information storage devices which are dominated by lead (Pb)-based materials. Here, we report the crystal structure, Raman spectra, dielectric constant and polarization near the MPB of lead free (1 - x) Na0.5Bi0.5TiO3 - x BaTiO3 (0.00 ⩽ x ⩽ 0.10) solid-solution, prepared by sol-gel auto combustion technique and sintered by microwave sintering technique. With the addition of BaTiO3 into Na0.5Bi0.5TiO3, it induces a structural phase transition from R3c (a single phase) to R3c + P4mm (a dual phase) close to x = 0.06 and 0.07 and transform to a high symmetry tetragonal phase P4mm at higher compositions (x = 0.08 to 0.10) as evident from our x-ray Rietveld refinement and Raman spectroscopic results. We perform first-principles calculations based on density functional theory that confirm a structural transition from a rhombohedral to a tetragonal phase under increasing x. In the prepared solid solution, an anomalous enhancement of remnant polarization ([Formula: see text]) was observed for x = 0.06 and 0.07, which has been explained based on the existence of the MPB. On the other hand, the value of coercive field [Formula: see text] was found to be decreased linearly from x = 0.00 to 0.06; it is constant for higher compositions. Further details of the ferroelectric properties on the electric field poled samples have been studied and compared with the as-grown (unpoled) samples.

Novel optically active lead-free relaxor ferroelectric (Ba0.6Bi0.2Li0.2)TiO3.

We discovered a near-room-temperature lead-free relaxor-ferroelectric (Ba0.6Bi0.2Li0.2)TiO3 (BBLT) having A-site compositionally disordered ABO3 perovskite structure. Microstructure-property relations revealed that the chemical inhomogeneities and development of local polar nano-regions (PNRs) are responsible for dielectric dispersion as a function of probe frequencies and temperatures. Rietveld analysis indicates mixed crystal structure with 80% tetragonal structure (space group P4mm) and 20% orthorhombic structure (space group Amm2), which is confirmed by the high resolution transmission electron diffraction (HRTEM). Dielectric constant and tangent loss dispersion with and without illumination of light obey nonlinear Vogel-Fulcher (VF) relations. The material shows slim polarization-hysteresis (P-E) loops and excellent displacement coefficients (d 33 ~ 233 pm V(-1)) near room temperature, which gradually diminish near the maximum dielectric dispersion temperature (T m ). The underlying physics for light-sensitive dielectric dispersion was probed by x-ray photon spectroscopy (XPS), which strongly suggests that mixed valence of bismuth ions, especially Bi(5+) ions, comprise most of the optically active centers. Ultraviolet photoemission measurements showed most of the Ti ions are in 4 + states and sit at the centers of the TiO6 octahedra; along with asymmetric hybridization between O 2p and Bi 6s orbitals, this appears to be the main driving force for net polarization. This BBLT material may open a new path for environmental friendly lead-free relaxor-ferroelectric research.