Evolution of Surface Copper(II) Environments in Cu2–xSe Nanoparticles

Kaseman, Derrick C.; Jarvi, Austin Gamble; Gan, Xing Yee; Saxena, Sunil; Millstone, Jill E.

doi:10.1021/acs.chemmater.8b03967

Title: Evolution of Surface Copper(II) Environments in Cu_2–xSe Nanoparticles

Journal Article · 09 October 2018 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.8b03967 · OSTI ID:1485396

Kaseman, Derrick C. ^[1]; Jarvi, Austin Gamble ^[2]; Gan, Xing Yee ^[2];

^[2];

^[3]

Univ. of Pittsburgh, PA (United States). Dept. of Chemistry; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of Pittsburgh, PA (United States). Dept. of Chemistry
Univ. of Pittsburgh, PA (United States). Dept. of Chemistry. Dept. of Chemical Engineering. Dept. of Mechanical Engineering and Materials Science

Cu_2–xSe nanoparticles are part of a promising class of alternative plasmonic materials where the location, stability, and structural impact of charge carrier generation are crucial to their optoelectronic performance. Electron paramagnetic resonance spectroscopy is used to identify the location and dynamics of Cu²⁺ environments that form upon air-induced oxidation of Cu_2–xSe nanoparticles. The results indicate the formation of two distinct Cu²⁺ environments at or near the surface of the nanoparticle. The first environment can be assigned to Cu²⁺ bound to oleylamine capping ligands, and the second can be assigned to Cu²⁺ located in CuO domains. In addition, these experiments indicate that the observed Cu²⁺ environments are consistent with vacancy formation on the Cu sublattice, which are mobile (i.e., vacancy hopping) at temperatures down to 180 K. Taken together, our results elucidate time scales of air-mediated Cu oxidation in Cu_2–xSe nanoparticles, the chemical environments of the resulting Cu²⁺ species, and the impact of this oxidation on the overall particle crystallographic structure and optoelectronic properties.

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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Pittsburgh, PA (United States)

Sponsoring Organization:: Defense Threat Reduction Agency (DTRA) (United States); National Science Foundation (NSF) (United States); USDOE

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1485396

Report Number(s):: LA-UR-18-28650

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 20 Vol. 30; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Evolution of Surface Copper(II) Environments in Cu_2–xSe Nanoparticles