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Title: High Compression-Induced Conductivity in a Layered Cu–Br Perovskite

Journal Article · · Angewandte Chemie (International Edition)
ORCiD logo [1];  [2];  [3];  [4];  [2]; ORCiD logo [5]
  1. Stanford Univ., CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); Stanford Univ., CA (United States)
  5. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
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In this work, 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 S cm–1, whereas here a Cu–Br congener, (EA)2CuBr4 (EA=ethylammonium), exhibits conductivity as high as 2×10–3 S cm–1 at only 2.6 GPa, and 0.17 S cm–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.

Research Organization:
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 Organization:
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)
Grant/Contract Number:
AC02-76SF00515; AC02-05CH11231; SC0012704; NA0002006; NA0003975
OSTI ID:
1605180
Alternate ID(s):
OSTI ID: 1594191; OSTI ID: 1764060
Journal Information:
Angewandte Chemie (International Edition), Vol. 59, Issue 10; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

References (33)

Generalized Gradient Approximation Made Simple journal October 1996
Pressure effects on Jahn-Teller distortion in perovskites: The roles of local and bulk compressibilities journal March 2012
Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu–Cl Hybrid Perovskite journal January 2015
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
Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy journal March 2020
Lead-Free MA 2 CuCl x Br 4– x Hybrid Perovskites journal January 2016
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
Structures of the antiferrodistortive layer perovskites bis(phenethylammonium) tetrahalocuprate(II), halo = Cl−, Br− journal April 1990
Pressure-induced phase transitions and templating effect in three-dimensional organic-inorganic hybrid perovskites journal July 2003
Influence of the exchange screening parameter on the performance of screened hybrid functionals journal December 2006
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction journal April 2020
Crystal structures of three new copper(II) halide layered perovskites: structural, crystallographic, and magnetic correlations journal December 1988
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
Crystal Structures and Magnetic Properties of a Novel Layer Perovskite System:  (3-Picoliniumylammonium)CuX4 (X = Cl, Br) journal July 1997
Variation of the Jahn–Teller distortion with pressure in perovskite layers A2CuCl4. Influence on the charge-transfer band journal January 2007
Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3 journal March 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Superconductivity up to 164 K in HgBa 2 Ca m − 1 Cu m O 2 m + 2 + δ ( m =1, 2, and 3) under quasihydrostatic pressures journal August 1994
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
An ultrasensitive molybdenum-based double-heterojunction phototransistor text January 2021
High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties journal April 2016
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
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
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data journal February 2009
Correlation between the pressure-induced changes in the Hall coefficient and Tc in superconducting cuprates journal November 1991
Halide Perovskites under Pressure: Accessing New Properties through Lattice Compression journal June 2017
Synthesis, Structure, and Properties of Organic-Inorganic Perovskites and Related Materials book January 2007
Electron-phonon coupling in charge-transfer and crystal-field states of Jahn-Teller CuCl 6 4 − systems journal October 1999
Suppression of Jahn–Teller Distortions and Origin of Piezochromism and Thermochromism in Cu–Cl Hybrid Perovskite journal June 2016
Polarized, single-crystal, electronic spectral studies of hexachlorodicuprate(2-): excited-state effects of binuclear interaction journal January 1987
Experiments on simple magnetic model systems journal January 1974
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
Experiments on simple magnetic model systems journal December 2001

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
conducting materials
high-pressure chemistry
Jahn–Teller distortion
layered copper halide perovskite
semiconductors