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Title: 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:
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)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., 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 Lab. (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. https://doi.org/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 = {2020},
month = {1}
}

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