AUTHOR=Varadwaj Pradeep R. , Marques Helder M. 

TITLE=The Cs2AgRhCl6 Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics

JOURNAL=Frontiers in Chemistry

VOLUME=8

YEAR=2020

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2020.00796

DOI=10.3389/fchem.2020.00796

ISSN=2296-2646

ABSTRACT=<p><italic>A</italic>-Site doping with alkali ions, and/or metal substitution at the B and B′-sites, are among the key strategies in the innovative development of <italic>A</italic><sub>2</sub>BB′X<sub>6</sub> halide double perovskite semiconducting materials for application in energy and device technologies. To this end, we have investigated an intriguing series of five halide-based non-toxic systems, <italic>A</italic><sub>2</sub>AgRhCl<sub>6</sub> (<italic>A</italic> = Li, Na, K, Rb, and Cs), using density functional theory at the SCAN-<italic>rVV</italic>10 level. The lattice stability and bonding properties emanating from this study of <italic>A</italic><sub>2</sub>AgRhCl<sub>6</sub> matched well with those that have already been synthesized, characterized and discussed [viz. Cs<sub>2</sub>AgBiX<sub>6</sub> (X = Cl, Br)]. Exploration of traditional and recently proposed tolerance factors has enabled us to identify <italic>A</italic><sub>2</sub>AgRhCl<sub>6</sub> (<italic>A</italic> = K, Rb and Cs) as stable double perovskites. The band structure and density of states calculations suggested that the electronic transition from the top of the valence band [Cl(3p)+Rh(4d)] to the bottom of the conduction band [(Cl(3p)+Rh(4d)] is inherently direct at the X-point of the first Brillouin zone. The (non-spin polarized) bandgap of these materials was found in the range 0.57–0.65 eV with SCAN-<italic>rVV</italic>10, which were substantially smaller than those computed with hybrid HSE06 and PBE0, and quasi-particle GW methods. This, together with the appreciable refractive index and high absorption coefficient in the region covering the range 1.0–4.5 eV, enabled us to demonstrate that <italic>A</italic><sub>2</sub>AgRhCl<sub>6</sub> (<italic>A</italic> = K, Rb, and Cs) are likely candidate materials for photoelectric applications. The results of our phonon calculations at the harmonic level suggested that the Cs<sub>2</sub>AgRhCl<sub>6</sub> is the only system that is dynamically stable (no imaginary frequencies found around the high symmetry lines of the reciprocal lattice), although the elastic moduli properties suggested all five systems examined are mechanically stable.</p>