Redox Chemistries for Vacancy Modulation in Plasmonic Copper Phosphide Nanocrystals

Copper phosphide (Cu_3-P) nanocrystals are promising materials for nanoplasmonics due to their substoichiometric composition, enabling the generation and stabilization of excess delocalized holes and leading to localized surface plasmon resonance (LSPR) absorption in the near-IR. We present three Cu-coupled redox chemistries that allow postsynthetic modulation of the delocalized hole concentrations and corresponding LSPR absorption in colloidal Cu_3-P nanocrystals. Changes in the structural, optical, and compositional properties are evaluated by powder X-ray diffraction, electronic absorption spectroscopy, ³¹P magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. The redox chemistries presented herein can be used to access nanocrystals with LSPR energies of 660-890 meV, a larger range than has been possible through synthetic tuning alone. In addition to utilizing previously reported redox chemistries used for copper chalcogenide nanocrystals, we show that the largest structural and LSPR modulation is achieved using a divalent metal halide and trioctylphosphine. Specifically, nanocrystals treated with zinc iodide and trioctylphosphine have the smallest unit-cell volume (295.2 ų) reported for P6₃cm Cu_3-P, indicating more Cu vacancies than have been previously observed. Overall, these redox chemistries present valuable insight into controlling the optical and structural properties of Cu_3-P.