Recently discovered alongside its sister compounds KV3Sb5 and RbV3Sb5, CsV3Sb5 crystallizes with an ideal kagome network of vanadium and antimonene layers separated by alkali metal ions. This work presents the electronic properties of CsV3Sb5, demonstrating bulk superconductivity in single crystals with a Tc = 2.5 K. The normal state electronic structure is studied via angleresolved photoemission spectroscopy (ARPES) and density functional theory (DFT), which categorize CsV3Sb5 as a Z2 topological metal. Multiple protected Dirac crossings are predicted in close proximity to the Fermi level (EF ), and signatures of normal state correlation effects are also suggested by a high temperature charge density wave-like instability. The implications for the formation of unconventional superconductivity in this material are discussed.

The newly introduced class of 3D halide perovskites, termed "hollow" perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX perovskites ( A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations ( en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, H NMR, TGA, SEM/EDX), we have assigned the general formula (A)( en) (M)(X) to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [ MX] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI and FASnI. The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.

The temperature-dependent structure evolution of the hybrid halide perovskite compounds, formamidinium tin iodide (FASnI, FA = CH[NH]) and formamidinium lead bromide (FAPbBr), has been monitored using high-resolution synchrotron X-ray powder diffraction between 300 and 100 K. The data are consistent with a transition from cubic Pm3m (No. 221) to tetragonal P4/mbm (No. 127) for both materials upon cooling; this occurs for FAPbBr between 275 and 250 K, and for FASnI between 250 and 225 K. Upon further cooling, between 150 and 125 K, both materials undergo a transition to an orthorhombic Pnma (No. 62) structure. The transitions are confirmed by calorimetry and dielectric measurements. In the tetragonal regime, the coefficients of volumetric thermal expansion of FASnI and FAPbBr are among the highest recorded for any extended inorganic crystalline solid, reaching 219 ppm K for FASnI at 225 K. Atomic displacement parameters of all atoms for both materials suggest dynamic motion is occurring in the inorganic sublattice due to the flexibility of the inorganic network and dynamic lone pair stereochemical activity on the B-site. Unusual pseudocubic behavior is displayed in the tetragonal phase of the FAPbBr, similar to that previously observed in FAPbI.

A thiol-amine solvent mixture is used to dissolve ten inexpensive bulk oxides (Cu2O, ZnO, GeO2, As2O3, Ag2O, CdO, SnO, Sb2O3, PbO, and Bi2O3) under ambient conditions. Dissolved oxides can be converted to the corresponding sulfides using the thiol as the sulfur source, while selenides and tellurides can be accessed upon mixing with a stoichiometric amount of dissolved selenium or tellurium. The practicality of this method is illustrated by solution depositing Sb2Se3 thin films from compound inks of dissolved Sb2O3 and selenium that give high photoelectrochemical current response. The direct band gap of the resulting material can be tuned from 1.2-1.6 eV by modulating the ink formulation to give compositionally controlled Sb2Se(3-x)S(x) alloys.