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Redox Chemistries for Vacancy Modulation in Plasmonic Copper Phosphide Nanocrystals
Alexander G Rachkov1, Kevin Chalek2, Hang Yin1
1Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
ACS Nano
|February 7, 2024
Summary
Copper phosphide nanocrystals show tunable near-IR plasmonics. Post-synthesis redox treatments expand tuning range, enabling new optical properties in these nanomaterials.
Area of Science:
- Materials Science
- Nanotechnology
- Physical Chemistry
Background:
- Copper phosphide (Cu3-P) nanocrystals exhibit localized surface plasmon resonance (LSPR) in the near-infrared due to substoichiometric composition and delocalized holes.
- Controlling delocalized hole concentration is key to tuning LSPR absorption in Cu3-P.
Purpose of the Study:
- To investigate postsynthetic redox chemistries for modulating delocalized hole concentrations in colloidal Cu3-P nanocrystals.
- To expand the tunable range of LSPR absorption beyond what is achievable through synthesis alone.
Main Methods:
- Utilized three Cu-coupled redox chemistries for postsynthetic treatment of Cu3-P nanocrystals.
- Evaluated structural, optical, and compositional changes using powder X-ray diffraction, electronic absorption spectroscopy, 31P MAS SSNMR, and elemental analysis.
Main Results:
- Achieved postsynthetic modulation of LSPR absorption in the range of 660-890 meV.
- Identified divalent metal halide and trioctylphosphine as effective agents for significant structural and LSPR modulation.
- Observed the smallest reported unit-cell volume for P63cm Cu3-P nanocrystals treated with zinc iodide and trioctylphosphine, indicating increased copper vacancies.
Conclusions:
- Demonstrated the efficacy of redox chemistries in precisely controlling optical and structural properties of Cu3-P nanocrystals.
- Provided valuable insights into the relationship between copper vacancies, structure, and plasmonic properties.
- Expanded the accessible LSPR tuning range for Cu3-P nanocrystals through postsynthetic modification.
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