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Title: Is Cu 3– x P a Semiconductor, a Metal, or a Semimetal?

Abstract

Despite the recent surge in interest in Cu3–xP for catalysis, batteries, and plasmonics, the electronic nature of Cu3–xP remains unclear. Some studies have shown evidence of semiconducting behavior, whereas others have argued that Cu3–xP is a metallic compound. Here, we attempt to resolve this dilemma on the basis of combinatorial thin-film experiments, electronic structure calculations, and semiclassical Boltzmann transport theory. We find strong evidence that stoichiometric, defect-free Cu3P is an intrinsic semimetal, i.e., a material with a small overlap between the valence and the conduction band. On the other hand, experimentally realizable Cu3–xP films are always p-type semimetals natively doped by copper vacancies regardless of x. It is not implausible that Cu3–xP samples with very small characteristic sizes (such as small nanoparticles) are semiconductors due to quantum confinement effects that result in the opening of a band gap. We observe high hole mobilities (276 cm2/ (V s)) in Cu3–xP films at low temperatures, pointing to low ionized impurity scattering rates in spite of a high doping density. We report an optical effect equivalent to the Burstein–Moss shift, and we assign an infrared absorption peak to bulk interband transitions rather than to a surface plasmon resonance. From a materials processing perspective,more » this study demonstrates the suitability of reactive sputter deposition for detailed high-throughput studies of emerging metal phosphides.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado80401, United States, Department of Structure and Dynamics of Energy Materials, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109Berlin, Germany, National Centre for Nano Fabrication and Characterization (DTU Nanolab), Technical University of Denmark, 2800Kongens Lyngby, Denmark
  2. Department of Structure and Dynamics of Energy Materials, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109Berlin, Germany
  3. Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado80401, United States
Publication Date:
Research Org.:
Technical Univ. of Denmark, Lyngby (Denmark); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1916487
Alternate Identifier(s):
OSTI ID: 1924491; OSTI ID: 1957993
Report Number(s):
NREL/JA-5K00-85353
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Published Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Name: Chemistry of Materials Journal Volume: 35 Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Deposition; Diffraction; Doping; Energy; Thin films; Cu3-xP; Electronic structure; Semiconductors; Semimetal

Citation Formats

Crovetto, Andrea, Unold, Thomas, and Zakutayev, Andriy. Is Cu 3– x P a Semiconductor, a Metal, or a Semimetal?. United States: N. p., 2023. Web. doi:10.1021/acs.chemmater.2c03283.
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Crovetto, Andrea, Unold, Thomas, & Zakutayev, Andriy. Is Cu 3– x P a Semiconductor, a Metal, or a Semimetal?. United States. https://doi.org/10.1021/acs.chemmater.2c03283
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Crovetto, Andrea, Unold, Thomas, and Zakutayev, Andriy. Wed . "Is Cu 3– x P a Semiconductor, a Metal, or a Semimetal?". United States. https://doi.org/10.1021/acs.chemmater.2c03283.
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@article{osti_1916487,
title = {Is Cu 3– x P a Semiconductor, a Metal, or a Semimetal?},
author = {Crovetto, Andrea and Unold, Thomas and Zakutayev, Andriy},
abstractNote = {Despite the recent surge in interest in Cu3–xP for catalysis, batteries, and plasmonics, the electronic nature of Cu3–xP remains unclear. Some studies have shown evidence of semiconducting behavior, whereas others have argued that Cu3–xP is a metallic compound. Here, we attempt to resolve this dilemma on the basis of combinatorial thin-film experiments, electronic structure calculations, and semiclassical Boltzmann transport theory. We find strong evidence that stoichiometric, defect-free Cu3P is an intrinsic semimetal, i.e., a material with a small overlap between the valence and the conduction band. On the other hand, experimentally realizable Cu3–xP films are always p-type semimetals natively doped by copper vacancies regardless of x. It is not implausible that Cu3–xP samples with very small characteristic sizes (such as small nanoparticles) are semiconductors due to quantum confinement effects that result in the opening of a band gap. We observe high hole mobilities (276 cm2/ (V s)) in Cu3–xP films at low temperatures, pointing to low ionized impurity scattering rates in spite of a high doping density. We report an optical effect equivalent to the Burstein–Moss shift, and we assign an infrared absorption peak to bulk interband transitions rather than to a surface plasmon resonance. From a materials processing perspective, this study demonstrates the suitability of reactive sputter deposition for detailed high-throughput studies of emerging metal phosphides.},
doi = {10.1021/acs.chemmater.2c03283},
journal = {Chemistry of Materials},
number = 3,
volume = 35,
place = {United States},
year = {Wed Jan 25 00:00:00 EST 2023},
month = {Wed Jan 25 00:00:00 EST 2023}
}
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https://doi.org/10.1021/acs.chemmater.2c03283
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