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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:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). The Molecular Foundry (TMF) and Advanced Light Source (ALS); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Univ. of Illinois, Chicago, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515; NA0002006; NA0003975; SC0012704
OSTI ID:
1605180
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 10 Vol. 59; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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