Cargando…

The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics

A-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 A(2)BB′X(6) halide double perovskite semiconducting materials for application in energy and device technologies. To this end, we have investigated an intrigu...

Descripción completa

Detalles Bibliográficos
Autores principales: Varadwaj, Pradeep R., Marques, Helder M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7655969/
https://www.ncbi.nlm.nih.gov/pubmed/33195026
http://dx.doi.org/10.3389/fchem.2020.00796
_version_ 1783608278777856000
author Varadwaj, Pradeep R.
Marques, Helder M.
author_facet Varadwaj, Pradeep R.
Marques, Helder M.
author_sort Varadwaj, Pradeep R.
collection PubMed
description A-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 A(2)BB′X(6) 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, A(2)AgRhCl(6) (A = Li, Na, K, Rb, and Cs), using density functional theory at the SCAN-rVV10 level. The lattice stability and bonding properties emanating from this study of A(2)AgRhCl(6) matched well with those that have already been synthesized, characterized and discussed [viz. Cs(2)AgBiX(6) (X = Cl, Br)]. Exploration of traditional and recently proposed tolerance factors has enabled us to identify A(2)AgRhCl(6) (A = 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-rVV10, 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 A(2)AgRhCl(6) (A = 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(2)AgRhCl(6) 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.
format Online
Article
Text
id pubmed-7655969
institution National Center for Biotechnology Information
language English
publishDate 2020
publisher Frontiers Media S.A.
record_format MEDLINE/PubMed
spelling pubmed-76559692020-11-13 The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics Varadwaj, Pradeep R. Marques, Helder M. Front Chem Chemistry A-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 A(2)BB′X(6) 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, A(2)AgRhCl(6) (A = Li, Na, K, Rb, and Cs), using density functional theory at the SCAN-rVV10 level. The lattice stability and bonding properties emanating from this study of A(2)AgRhCl(6) matched well with those that have already been synthesized, characterized and discussed [viz. Cs(2)AgBiX(6) (X = Cl, Br)]. Exploration of traditional and recently proposed tolerance factors has enabled us to identify A(2)AgRhCl(6) (A = 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-rVV10, 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 A(2)AgRhCl(6) (A = 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(2)AgRhCl(6) 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. Frontiers Media S.A. 2020-10-28 /pmc/articles/PMC7655969/ /pubmed/33195026 http://dx.doi.org/10.3389/fchem.2020.00796 Text en Copyright © 2020 Varadwaj and Marques. http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Varadwaj, Pradeep R.
Marques, Helder M.
The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics
title The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics
title_full The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics
title_fullStr The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics
title_full_unstemmed The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics
title_short The Cs(2)AgRhCl(6) Halide Double Perovskite: A Dynamically Stable Lead-Free Transition-Metal Driven Semiconducting Material for Optoelectronics
title_sort cs(2)agrhcl(6) halide double perovskite: a dynamically stable lead-free transition-metal driven semiconducting material for optoelectronics
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7655969/
https://www.ncbi.nlm.nih.gov/pubmed/33195026
http://dx.doi.org/10.3389/fchem.2020.00796
work_keys_str_mv AT varadwajpradeepr thecs2agrhcl6halidedoubleperovskiteadynamicallystableleadfreetransitionmetaldrivensemiconductingmaterialforoptoelectronics
AT marqueshelderm thecs2agrhcl6halidedoubleperovskiteadynamicallystableleadfreetransitionmetaldrivensemiconductingmaterialforoptoelectronics
AT varadwajpradeepr cs2agrhcl6halidedoubleperovskiteadynamicallystableleadfreetransitionmetaldrivensemiconductingmaterialforoptoelectronics
AT marqueshelderm cs2agrhcl6halidedoubleperovskiteadynamicallystableleadfreetransitionmetaldrivensemiconductingmaterialforoptoelectronics