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Title: A pencil-and-paper method for elucidating halide double perovskite band structures

Abstract

Halide double perovskites are an important emerging alternative to lead-halide perovskites in a variety of optoelectronic applications. Compared to ABX 3 single perovskites (A = monovalent cation, X = halide), A 2BB'X 6 double perovskites exhibit a wider array of compositions and electronic structures, promising finer control over physical and electronic properties through synthetic design. Yet, a clear understanding of how chemical composition dictates the electronic structures of this large family of materials is still lacking. In this work, we develop a qualitative Linear Combination of Atomic Orbitals (LCAO) model that describes the full range of band structures for double perovskites. Our simple model allows for a direct connection between the inherently local bonding between atoms in the double perovskite and the resulting delocalized bands of the solid. In particular, we show how bands in halide double perovskites originate from the molecular orbitals of metal–hexahalide coordination complexes and describe how these molecular orbitals vary within a band. Our findings provide both an enhanced understanding of known perovskite compositions and predictive power for identifying new compositions with targeted properties. We present a table, which permits the position of the conduction band minimum and valence band maximum in most double perovskites tomore » be immediately determined from the frontier atomic orbitals of the B-site metals. Using purely qualitative arguments based on orbital symmetries and their relative energies, the direct/indirect nature of the bandgap of almost all halide double perovskites can thus be correctly predicted. We hope that this theory provides an intuitive understanding of halide double perovskite band structures and enables lessons from molecular chemistry to be applied to these extended solids.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Stanford Univ., CA (United States)
  2. Univ. of Bayreuth (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1571834
Alternate Identifier(s):
OSTI ID: 1582224
Grant/Contract Number:  
AC02-76SF00515; DGE-114747
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 48; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Slavney, Adam H., Connor, Bridget A., Leppert, Linn, and Karunadasa, Hemamala I. A pencil-and-paper method for elucidating halide double perovskite band structures. United States: N. p., 2019. Web. doi:10.1039/C9SC03219C.
Slavney, Adam H., Connor, Bridget A., Leppert, Linn, & Karunadasa, Hemamala I. A pencil-and-paper method for elucidating halide double perovskite band structures. United States. doi:10.1039/C9SC03219C.
Slavney, Adam H., Connor, Bridget A., Leppert, Linn, and Karunadasa, Hemamala I. Mon . "A pencil-and-paper method for elucidating halide double perovskite band structures". United States. doi:10.1039/C9SC03219C.
@article{osti_1571834,
title = {A pencil-and-paper method for elucidating halide double perovskite band structures},
author = {Slavney, Adam H. and Connor, Bridget A. and Leppert, Linn and Karunadasa, Hemamala I.},
abstractNote = {Halide double perovskites are an important emerging alternative to lead-halide perovskites in a variety of optoelectronic applications. Compared to ABX3 single perovskites (A = monovalent cation, X = halide), A2BB'X6 double perovskites exhibit a wider array of compositions and electronic structures, promising finer control over physical and electronic properties through synthetic design. Yet, a clear understanding of how chemical composition dictates the electronic structures of this large family of materials is still lacking. In this work, we develop a qualitative Linear Combination of Atomic Orbitals (LCAO) model that describes the full range of band structures for double perovskites. Our simple model allows for a direct connection between the inherently local bonding between atoms in the double perovskite and the resulting delocalized bands of the solid. In particular, we show how bands in halide double perovskites originate from the molecular orbitals of metal–hexahalide coordination complexes and describe how these molecular orbitals vary within a band. Our findings provide both an enhanced understanding of known perovskite compositions and predictive power for identifying new compositions with targeted properties. We present a table, which permits the position of the conduction band minimum and valence band maximum in most double perovskites to be immediately determined from the frontier atomic orbitals of the B-site metals. Using purely qualitative arguments based on orbital symmetries and their relative energies, the direct/indirect nature of the bandgap of almost all halide double perovskites can thus be correctly predicted. We hope that this theory provides an intuitive understanding of halide double perovskite band structures and enables lessons from molecular chemistry to be applied to these extended solids.},
doi = {10.1039/C9SC03219C},
journal = {Chemical Science},
number = 48,
volume = 10,
place = {United States},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9SC03219C

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