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 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 determinedmore »
- Authors:
-
- Department of Chemistry; Stanford University; Stanford; USA
- Institute of Physics; University of Bayreuth; Bayreuth; Germany
- Department of Chemistry; Stanford University; Stanford; USA; Stanford Institute for Materials and Energy Sciences
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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 Name: Chemical Science Journal Volume: 10 Journal Issue: 48; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- 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 Kingdom: 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 Kingdom. https://doi.org/10.1039/C9SC03219C
Slavney, Adam H., Connor, Bridget A., Leppert, Linn, and Karunadasa, Hemamala I. Tue .
"A pencil-and-paper method for elucidating halide double perovskite band structures". United Kingdom. https://doi.org/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 Kingdom},
year = {Tue Jan 01 00:00:00 EST 2019},
month = {Tue Jan 01 00:00:00 EST 2019}
}
https://doi.org/10.1039/C9SC03219C
Web of Science
Works referenced in this record:
Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals
journal, March 2016
- Volonakis, George; Filip, Marina R.; Haghighirad, Amir Abbas
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
Perovskites as Substitutes of Noble Metals for Heterogeneous Catalysis: Dream or Reality
journal, September 2014
- Royer, Sébastien; Duprez, Daniel; Can, Fabien
- Chemical Reviews, Vol. 114, Issue 20
On minerals of the cryolite group recently found in Colorado
journal, October 1883
- Cross, C. W.; Hillebrand, W. F.
- American Journal of Science, Vol. s3-26, Issue 154
Symmetry-Based Tight Binding Modeling of Halide Perovskite Semiconductors
journal, September 2016
- Boyer-Richard, Soline; Katan, Claudine; Traoré, Boubacar
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
ReO3 Band Structure in the Tight-Binding Approximation
journal, June 1969
- Honig, J. M.; Dimmock, J. O.; Kleiner, W. H.
- The Journal of Chemical Physics, Vol. 50, Issue 12
Earth-Abundant Nontoxic Titanium(IV)-based Vacancy-Ordered Double Perovskite Halides with Tunable 1.0 to 1.8 eV Bandgaps for Photovoltaic Applications
journal, January 2018
- Ju, Ming-Gang; Chen, Min; Zhou, Yuanyuan
- ACS Energy Letters, Vol. 3, Issue 2
Strongly correlated perovskite fuel cells
journal, May 2016
- Zhou, You; Guan, Xiaofei; Zhou, Hua
- Nature, Vol. 534, Issue 7606
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009
- Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
- Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites
journal, April 2014
- Kim, M.; Im, J.; Freeman, A. J.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 19
Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites
journal, June 2017
- Meng, Weiwei; Wang, Xiaoming; Xiao, Zewen
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 13
A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3
journal, November 2013
- Li, Ming; Pietrowski, Martha J.; De Souza, Roger A.
- Nature Materials, Vol. 13, Issue 1
Cs 2 InAgCl 6 : A New Lead-Free Halide Double Perovskite with Direct Band Gap
journal, January 2017
- Volonakis, George; Haghighirad, Amir Abbas; Milot, Rebecca L.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 4
Computational Screening of Homovalent Lead Substitution in Organic–Inorganic Halide Perovskites
journal, December 2015
- Filip, Marina R.; Giustino, Feliciano
- The Journal of Physical Chemistry C, Vol. 120, Issue 1
Chemical Approaches to Addressing the Instability and Toxicity of Lead–Halide Perovskite Absorbers
journal, August 2016
- Slavney, Adam H.; Smaha, Rebecca W.; Smith, Ian C.
- Inorganic Chemistry, Vol. 56, Issue 1
Efficient and stable emission of warm-white light from lead-free halide double perovskites
journal, November 2018
- Luo, Jiajun; Wang, Xiaoming; Li, Shunran
- Nature, Vol. 563, Issue 7732
Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries
journal, June 2016
- Li, Yutao; Zhou, Weidong; Xin, Sen
- Angewandte Chemie International Edition, Vol. 55, Issue 34
Electronic Energy Bands in Strontium Titanate
journal, August 1964
- Kahn, A. H.; Leyendecker, A. J.
- Physical Review, Vol. 135, Issue 5A
Cu–In Halide Perovskite Solar Absorbers
journal, May 2017
- Zhao, Xin-Gang; Yang, Dongwen; Sun, Yuanhui
- Journal of the American Chemical Society, Vol. 139, Issue 19
The synthesis, structure and electronic properties of a lead-free hybrid inorganic–organic double perovskite (MA) 2 KBiCl 6 (MA = methylammonium)
journal, January 2016
- Wei, Fengxia; Deng, Zeyu; Sun, Shijing
- Materials Horizons, Vol. 3, Issue 4
�ber die Quantenmechanik der Elektronen in Kristallgittern
journal, July 1929
- Bloch, Felix
- Zeitschrift f�r Physik, Vol. 52, Issue 7-8
Hole Doping and Structural Transformation in CsTl 1– x Hg x Cl 3
journal, November 2014
- Retuerto, Maria; Yin, Zhiping; Emge, Thomas J.
- Inorganic Chemistry, Vol. 54, Issue 3
Solids and Surfaces: A Chemist's View of Bonding in Extended Structures
report, July 1988
- Hoffman, Roald
Photoelectron spectroscopy of tin compounds
journal, June 1973
- Grutsch, P. A.; Zeller, M. V.; Fehlner, T. P.
- Inorganic Chemistry, Vol. 12, Issue 6
Computational Study of Halide Perovskite-Derived A 2 BX 6 Inorganic Compounds: Chemical Trends in Electronic Structure and Structural Stability
journal, September 2017
- Cai, Yao; Xie, Wei; Ding, Hong
- Chemistry of Materials, Vol. 29, Issue 18
Solution-Processed Cesium Hexabromopalladate(IV), Cs 2 PdBr 6 , for Optoelectronic Applications
journal, April 2017
- Sakai, Nobuya; Haghighirad, Amir Abbas; Filip, Marina R.
- Journal of the American Chemical Society, Vol. 139, Issue 17
Tolerance Factor and Cooperative Tilting Effects in Vacancy-Ordered Double Perovskite Halides
journal, May 2018
- Maughan, Annalise E.; Ganose, Alex M.; Almaker, Mohammed A.
- Chemistry of Materials, Vol. 30, Issue 11
The Crystal Structure of Cesium Aurous Auric Chloride, Cs 2 AuAuCl 6 , and Cesium Argentous Auric Chloride, Cs 2 AgAuCl 6
journal, August 1938
- Elliott, Norman; Pauling, Linus
- Journal of the American Chemical Society, Vol. 60, Issue 8
Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach
journal, January 2016
- Deng, Zeyu; Wei, Fengxia; Sun, Shijing
- Journal of Materials Chemistry A, Vol. 4, Issue 31
Tuning the bandgap of Cs 2 AgBiBr 6 through dilute tin alloying
journal, January 2019
- Lindquist, Kurt P.; Mack, Stephanie A.; Slavney, Adam H.
- Chemical Science, Vol. 10, Issue 45
Understanding the physical properties of hybrid perovskites for photovoltaic applications
journal, July 2017
- Huang, Jinsong; Yuan, Yongbo; Shao, Yuchuan
- Nature Reviews Materials, Vol. 2, Issue 7
Defect-Induced Band-Edge Reconstruction of a Bismuth-Halide Double Perovskite for Visible-Light Absorption
journal, March 2017
- Slavney, Adam H.; Leppert, Linn; Bartesaghi, Davide
- Journal of the American Chemical Society, Vol. 139, Issue 14
Possible highT c superconductivity in the Ba?La?Cu?O system
journal, June 1986
- Bednorz, J. G.; M�ller, K. A.
- Zeitschrift f�r Physik B Condensed Matter, Vol. 64, Issue 2
Mirrors of Bonding in Metal Halide Perovskites
journal, September 2018
- Goesten, Maarten G.; Hoffmann, Roald
- Journal of the American Chemical Society, Vol. 140, Issue 40
Simplified LCAO Method for the Periodic Potential Problem
journal, June 1954
- Slater, J. C.; Koster, G. F.
- Physical Review, Vol. 94, Issue 6
Optical and scintillation properties of pure and Ce3+-doped Cs2LiYCl6 and Li3YCl6:Ce3+ crystals
journal, October 1999
- Combes, C. M.; Dorenbos, P.; van Eijk, C. W. E.
- Journal of Luminescence, Vol. 82, Issue 4
Toxicity of organometal halide perovskite solar cells
journal, February 2016
- Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc
- Nature Materials, Vol. 15, Issue 3
Discrete Electronic Bands in Semiconductors and Insulators: Potential High-Light-Yield Scintillators
journal, May 2015
- Shi, Hongliang; Du, Mao-Hua
- Physical Review Applied, Vol. 3, Issue 5
Electronic structure engineering of elpasolites: Case of Cs2AgYCl6
journal, November 2013
- Du, Mao-Hua; Biswas, Koushik
- Journal of Luminescence, Vol. 143
Carrier Self-trapping and Luminescence in Intrinsically Activated Scintillator: Cesium Hafnium Chloride (Cs 2 HfCl 6 )
journal, May 2016
- Kang, By.; Biswas, Koushik
- The Journal of Physical Chemistry C, Vol. 120, Issue 22
Cs 2 AgBiX 6 (X = Br, Cl): New Visible Light Absorbing, Lead-Free Halide Perovskite Semiconductors
journal, February 2016
- McClure, Eric T.; Ball, Molly R.; Windl, Wolfgang
- Chemistry of Materials, Vol. 28, Issue 5
Defect Tolerance to Intolerance in the Vacancy-Ordered Double Perovskite Semiconductors Cs 2 SnI 6 and Cs 2 TeI 6
journal, June 2016
- Maughan, Annalise E.; Ganose, Alex M.; Bordelon, Mitchell M.
- Journal of the American Chemical Society, Vol. 138, Issue 27
Machine Learning Energies of 2 Million Elpasolite Crystals
journal, September 2016
- Faber, Felix A.; Lindmaa, Alexander; von Lilienfeld, O. Anatole
- Physical Review Letters, Vol. 117, Issue 13
Small-Band-Gap Halide Double Perovskites
journal, August 2018
- Slavney, Adam H.; Leppert, Linn; Saldivar Valdes, Abraham
- Angewandte Chemie International Edition, Vol. 57, Issue 39
Air-Stable Molecular Semiconducting Iodosalts for Solar Cell Applications: Cs2SnI6 as a Hole Conductor
journal, October 2014
- Lee, Byunghong; Stoumpos, Constantinos C.; Zhou, Nanjia
- Journal of the American Chemical Society, Vol. 136, Issue 43, p. 15379-15385
Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying
journal, June 2017
- Du, Ke-zhao; Meng, Weiwei; Wang, Xiaoming
- Angewandte Chemie International Edition, Vol. 56, Issue 28
A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications
journal, February 2016
- Slavney, Adam H.; Hu, Te; Lindenberg, Aaron M.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Designing indirect–direct bandgap transitions in double perovskites
journal, January 2017
- Tran, T. Thao; Panella, Jessica R.; Chamorro, Juan R.
- Materials Horizons, Vol. 4, Issue 4
Stability and electronic properties of new inorganic perovskites from high-throughput ab initio calculations
journal, January 2016
- Körbel, Sabine; Marques, Miguel A. L.; Botti, Silvana
- Journal of Materials Chemistry C, Vol. 4, Issue 15