Emergence of topological electronic phases in elemental lithium under pressure.

Lithium, a prototypical simple metal under ambient conditions, has a surprisingly rich phase diagram under pressure, taking up several structures with reduced symmetry, low coordination numbers, and even semiconducting character with increasing density. Using first-principles calculations, we demonstrate that some predicted high-pressure phases of elemental Li also host topological electronic structures. Beginning at 80 GPa and coincident with a transition to the previously predicted Pbca phase, we find Li to be a Dirac nodal line semimetal. We further calculate that Li retains linearly dispersing energy bands near the Fermi energy in subsequent predicted higher-pressure phases and that it exhibits a Lifshitz transition between two Cmca phases at 220 GPa. The Fd[Formula: see text]m phase at 500 GPa forms buckled honeycomb layers that give rise to a Dirac crossing 1 eV below the Fermi energy. The well-isolated topological nodes near the Fermi level in these phases result from increasing p-orbital character with density at the Fermi level, itself a consequence of rising 1s core wavefunction overlap, and a preference for nonsymmorphic symmetries in the crystal structures favored at these pressures. Our results provide evidence that under pressure, bulk 3D materials with light elements, or even pure elemental systems, can undergo phase transitions hosting nontrivial topological phase transitions hosting nontrivial topological properties near the Fermi level with measurable consequences and that, through pressure, we can access these phases in elemental lithium.

Gold-Cage Perovskites: A Three-Dimensional AuIII-X Framework Encasing Isolated MX63- Octahedra (MIII = In, Sb, Bi; X = Cl-, Br-, I-).

The Cs8AuIII4MIIIX23 (M = In3+, Sb3+, Bi3+; X = Cl-, Br-, I-) perovskites are composed of corner-sharing Au-X octahedra that trace the edges of a cube containing an isolated M-X octahedron at its body center. This structure, unique within the halide perovskite family, may be derived from the doubled cubic perovskite unit cell by removing the metals at the cube faces. To our knowledge, these are the only halide perovskites where the octahedral sites do not bear an average 2+ charge. Charge compensation in these materials requires a stoichiometric halide vacancy, which is disordered around the Au atom at the unit-cell corner and orders when the crystallization is slowed. Using X-ray crystallography, X-ray absorption spectroscopy, and pair distribution function analysis, we elucidate the structure of this unusual perovskite. Metal-site alloying produces further intricacies in this structure, which our model explains. Compared to other halide perovskites, this class of materials shows unusually low absorption onset energies ranging between ca. 1.0 and 2.4 eV. Partial reduction of Au3+ to Au+ affords an intervalence charge-transfer band, which redshifts the absorption onset of Cs8Au4InCl23 from 2.4 to 1.5 eV. With connected Au-X octahedra and isolated M-X octahedra, this structure type combines zero- and three-dimensional metal-halide sublattices in a single material and stands out among halide perovskites for its ordering of homovalent metals, ordering of halide vacancies, and incorporation of purely trivalent metals at the octahedral sites.

High Compression-Induced Conductivity in a Layered Cu-Br Perovskite.

We show that the onset pressure for appreciable conductivity in layered copper-halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu-Cl perovskites require pressures >50 GPa to show a conductivity of 10-4  S cm-1 , whereas here a Cu-Br congener, (EA)2 CuBr4 (EA=ethylammonium), exhibits conductivity as high as 2×10-3  S cm-1 at only 2.6 GPa, and 0.17 S cm-1 at 59 GPa. Substitution of higher-energy Br 4p for Cl 3p orbitals lowers the charge-transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High-pressure X-ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression-induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression-induced conductivity of Cu-halide perovskites to more technologically accessible pressures.

An automatically curated first-principles database of ferroelectrics.

Ferroelectric materials have technological applications in information storage and electronic devices. The ferroelectric polar phase can be controlled with external fields, chemical substitution and size-effects in bulk and ultrathin film form, providing a platform for future technologies and for exploratory research. In this work, we integrate spin-polarized density functional theory (DFT) calculations, crystal structure databases, symmetry tools, workflow software, and a custom analysis toolkit to build a library of known, previously-proposed, and newly-proposed ferroelectric materials. With our automated workflow, we screen over 67,000 candidate materials from the Materials Project database to generate a dataset of 255 ferroelectric candidates, and propose 126 new ferroelectric materials. We benchmark our results against experimental data and previous first-principles results. The data provided includes atomic structures, output files, and DFT values of band gaps, energies, and the spontaneous polarization for each ferroelectric candidate. We contribute our workflow and analysis code to the open-source python packages atomate and pymatgen so others can conduct analogous symmetry driven searches for ferroelectrics and related phenomena.

Tuning the bandgap of Cs2AgBiBr6 through dilute tin alloying.

The promise of lead halide hybrid perovskites for optoelectronic applications makes finding less-toxic alternatives a priority. The double perovskite Cs2AgBiBr6 (1) represents one such alternative, offering long carrier lifetimes and greater stability under ambient conditions. However, the large and indirect 1.95 eV bandgap hinders its potential as a solar absorber. Here we report that alloying crystals of 1 with up to 1 atom% Sn results in a bandgap reduction of up to ca. 0.5 eV while maintaining low toxicity. Crystals can be alloyed with up to 1 atom% Sn and the predominant substitution pathway appears to be a ∼2 : 1 substitution of Sn2+ and Sn4+ for Ag+ and Bi3+, respectively, with Ag+ vacancies providing charge compensation. Spincoated films of 1 accommodate a higher Sn loading, up to 4 atom% Sn, where we see mostly Sn2+ substitution for both Ag+ and Bi3+. Density functional theory (DFT) calculations ascribe the bandgap redshift to the introduction of Sn impurity bands below the conduction band minimum of the host lattice. Using optical absorption spectroscopy, photothermal deflection spectroscopy, X-ray absorption spectroscopy, 119Sn NMR, redox titration, single-crystal and powder X-ray diffraction, multiple elemental analysis and imaging techniques, and DFT calculations, we provide a detailed analysis of the Sn content and oxidation state, dominant substitution sites, and charge-compensating defects in Sn-alloyed Cs2AgBiBr6 (1:Sn) crystals and films. An understanding of heterovalent alloying in halide double perovskites opens the door to a wider breadth of potential alloying agents for manipulating their band structures in a predictable manner.