High Compression-Induced Conductivity in a Layered Cu–Br Perovskite
Abstract
We show that the onset pressure for appreciable conductivity in layered copper-halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu–Cl perovskites require pressures >50 GPa to show a conductivity of 10^-4 Scm^-1, whereas here a Cu–Br congener, (EA)2CuBr4 (EA=ethylammonium), exhibits conductivity as high as 2 X 10^-3 Scm^-1 at only 2.6 GPa, and 0.17 Scm^-1 at 59 GPa. Substitution of higher-energy Br 4p for Cl 3p orbitals lowers the charge-transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High-pressure X-ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression-induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression-induced conductivity of Cu-halide perovskites to more technologically accessible pressures.
- Authors:
-
- Stanford Univ., CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); Stanford Univ., CA (United States)
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). The Molecular Foundry (TMF) and Advanced Light Source (ALS); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Univ. of Illinois, Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP)
- OSTI Identifier:
- 1605180
- Alternate Identifier(s):
- OSTI ID: 1594191; OSTI ID: 1764060
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231; SC0012704; NA0002006; NA0003975
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 10; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; conducting materials; high-pressure chemistry; Jahn–Teller distortion; layered copper halide perovskite; semiconductors
Citation Formats
Jaffe, Adam, Mack, Stephanie A., Lin, Yu, Mao, Wendy L., Neaton, Jeffrey B., and Karunadasa, Hemamala I. High Compression-Induced Conductivity in a Layered Cu–Br Perovskite. United States: N. p., 2020.
Web. doi:10.1002/anie.201912575.
Jaffe, Adam, Mack, Stephanie A., Lin, Yu, Mao, Wendy L., Neaton, Jeffrey B., & Karunadasa, Hemamala I. High Compression-Induced Conductivity in a Layered Cu–Br Perovskite. United States. https://doi.org/10.1002/anie.201912575
Jaffe, Adam, Mack, Stephanie A., Lin, Yu, Mao, Wendy L., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Fri .
"High Compression-Induced Conductivity in a Layered Cu–Br Perovskite". United States. https://doi.org/10.1002/anie.201912575. https://www.osti.gov/servlets/purl/1605180.
@article{osti_1605180,
title = {High Compression-Induced Conductivity in a Layered Cu–Br Perovskite},
author = {Jaffe, Adam and Mack, Stephanie A. and Lin, Yu and Mao, Wendy L. and Neaton, Jeffrey B. and Karunadasa, Hemamala I.},
abstractNote = {We show that the onset pressure for appreciable conductivity in layered copper-halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu–Cl perovskites require pressures >50 GPa to show a conductivity of 10^-4 Scm^-1, whereas here a Cu–Br congener, (EA)2CuBr4 (EA=ethylammonium), exhibits conductivity as high as 2 X 10^-3 Scm^-1 at only 2.6 GPa, and 0.17 Scm^-1 at 59 GPa. Substitution of higher-energy Br 4p for Cl 3p orbitals lowers the charge-transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High-pressure X-ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression-induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression-induced conductivity of Cu-halide perovskites to more technologically accessible pressures.},
doi = {10.1002/anie.201912575},
journal = {Angewandte Chemie (International Edition)},
number = 10,
volume = 59,
place = {United States},
year = {Fri Jan 24 00:00:00 EST 2020},
month = {Fri Jan 24 00:00:00 EST 2020}
}
Web of Science
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Pressure effects on Jahn-Teller distortion in perovskites: The roles of local and bulk compressibilities
journal, March 2012
- Aguado, Fernando; Rodríguez, Fernando; Valiente, Rafael
- Physical Review B, Vol. 85, Issue 10
Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu–Cl Hybrid Perovskite
journal, January 2015
- Jaffe, Adam; Lin, Yu; Mao, Wendy L.
- Journal of the American Chemical Society, Vol. 137, Issue 4
The role of Jahn–Teller distortion in insulator to semiconductor phase transition in organic–inorganic hybrid compound (p-chloroanilinium) 2 CuCl 4 at high pressure
journal, January 2015
- Ghalsasi, Pallavi; Garg, Nandini; Deo, M. N.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 48
Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy
journal, March 2020
- Berger, Jan; Ondráček, Martin; Stetsovych, Oleksandr
- Nature Communications, Vol. 11, Issue 1
Lead-Free MA 2 CuCl x Br 4– x Hybrid Perovskites
journal, January 2016
- Cortecchia, Daniele; Dewi, Herlina Arianita; Yin, Jun
- Inorganic Chemistry, Vol. 55, Issue 3
The electronic structure of organic–inorganic hybrid compounds: (NH 4 ) 2 CuCl 4 , (CH 3 NH 3 ) 2 CuCl 4 and (C 2 H 5 NH 3 ) 2 CuCl 4
journal, June 2013
- Zolfaghari, P.; de Wijs, G. A.; de Groot, R. A.
- Journal of Physics: Condensed Matter, Vol. 25, Issue 29
Structures of the antiferrodistortive layer perovskites bis(phenethylammonium) tetrahalocuprate(II), halo = Cl−, Br−
journal, April 1990
- Willett, R. D.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 46, Issue 4
Pressure-induced phase transitions and templating effect in three-dimensional organic-inorganic hybrid perovskites
journal, July 2003
- Lee, Yongjae; Mitzi, David B.; Barnes, Paris W.
- Physical Review B, Vol. 68, Issue 2
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
Crystal structures of three new copper(II) halide layered perovskites: structural, crystallographic, and magnetic correlations
journal, December 1988
- Willett, Roger.; Place, Helen.; Middleton, Michael.
- Journal of the American Chemical Society, Vol. 110, Issue 26
Pressure‐induced disappearance of the in‐plane lattice distortion in layered cupric chloride: (C 2 H 5 NH 3 ) 2 CuCl 4
journal, August 1994
- Moritomo, Y.; Tokura, Y.
- The Journal of Chemical Physics, Vol. 101, Issue 3
Crystal Structures and Magnetic Properties of a Novel Layer Perovskite System: (3-Picoliniumylammonium)CuX4 (X = Cl, Br)
journal, July 1997
- Long, Greg S.; Wei, Mingyi; Willett, Roger D.
- Inorganic Chemistry, Vol. 36, Issue 14
Variation of the Jahn–Teller distortion with pressure in perovskite layers A2CuCl4. Influence on the charge-transfer band
journal, January 2007
- Rodríguez, F.; Aguado, F.; Valiente, R.
- physica status solidi (b), Vol. 244, Issue 1
Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3
journal, March 2017
- Jaffe, Adam; Lin, Yu; Mao, Wendy L.
- Journal of the American Chemical Society, Vol. 139, Issue 12
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Superconductivity up to 164 K in ( m =1, 2, and 3) under quasihydrostatic pressures
journal, August 1994
- Gao, L.; Xue, Y. Y.; Chen, F.
- Physical Review B, Vol. 50, Issue 6
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
An ultrasensitive molybdenum-based double-heterojunction phototransistor
text, January 2021
- , Feng; , Liu; , Zhu
- Zenodo
High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties
journal, April 2016
- Jaffe, Adam; Lin, Yu; Beavers, Christine M.
- ACS Central Science, Vol. 2, Issue 4
High-Pressure Study of Perovskite-Like Organometal Halide: Band-Gap Narrowing and Structural Evolution of [NH 3 -(CH 2 ) 4 -NH 3 ]CuCl 4
journal, January 2017
- Li, Qian; Li, Shourui; Wang, Kai
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 2
Detailed absorption, reflectance, and UV photoelectron spectroscopic and theoretical studies of the charge-transfer transitions of tetrachlorocuprate(2-) ion: correlation of the square-planar and the tetrahedral limits
journal, July 1983
- Desjardins, Sylvie R.; Penfield, Kevin W.; Cohen, Susan L.
- Journal of the American Chemical Society, Vol. 105, Issue 14
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
Correlation between the pressure-induced changes in the Hall coefficient and Tc in superconducting cuprates
journal, November 1991
- Murayama, C.; Iye, Y.; Enomoto, T.
- Physica C: Superconductivity, Vol. 183, Issue 4-6
Halide Perovskites under Pressure: Accessing New Properties through Lattice Compression
journal, June 2017
- Jaffe, Adam; Lin, Yu; Karunadasa, Hemamala I.
- ACS Energy Letters, Vol. 2, Issue 7
Electron-phonon coupling in charge-transfer and crystal-field states of Jahn-Teller CuCl 6 4 − systems
journal, October 1999
- Valiente, R.; Rodríguez, F.
- Physical Review B, Vol. 60, Issue 13
Suppression of Jahn–Teller Distortions and Origin of Piezochromism and Thermochromism in Cu–Cl Hybrid Perovskite
journal, June 2016
- Gupta, Sunny; Pandey, Tribhuwan; Singh, Abhishek Kumar
- Inorganic Chemistry, Vol. 55, Issue 13
Polarized, single-crystal, electronic spectral studies of hexachlorodicuprate(2-): excited-state effects of binuclear interaction
journal, January 1987
- Desjardins, Sylvie R.; Wilcox, Dean E.; Musselman, Ronald L.
- Inorganic Chemistry, Vol. 26, Issue 2
Experiments on simple magnetic model systems
journal, January 1974
- de Jongh, L. J.; Miedema, A. R.
- Advances in Physics, Vol. 23, Issue 1
Structural properties and phase transition of hole-orbital-ordered ( C 2 H 5 N H 3 ) 2 Cu Cl 4 studied by resonant and non-resonant x-ray scatterings under high pressure
journal, July 2005
- Ohwada, Kenji; Ishii, Kenji; Inami, Toshiya
- Physical Review B, Vol. 72, Issue 1
Experiments on simple magnetic model systems
journal, December 2001
- De Jongh, L. J.; Miedema, A. R.
- Advances in Physics, Vol. 50, Issue 8