A Directed Route to Colloidal Nanoparticle Synthesis of the Copper Selenophosphate Cu₃PSe₄

Abstract

The first colloidal nanoparticle synthesis of the copper selenophosphate Cu3PSe4, a promising new material for photovoltaics, is reported. Because the formation of binary copper selenide impurities seemed to form more readily, two approaches were developed to install phosphorus bonds directly: 1) the synthesis of molecular P4Se3 and subsequent reaction with a copper precursor, (P‐Se)+Cu, and 2) the synthesis of copper phosphide, Cu3P, nanoparticles and subsequent reaction with a selenium precursor, (Cu‐P)+Se. The isolation and purification of Cu3P nanoparticles and subsequent selenization yielded phase‐pure Cu3PSe4. Solvent effects and Se precursor reactivities were elucidated and were key to understanding the final reaction conditions.

Colloidal Synthesis of Tunable Copper Phosphide Nanocrystals

“…According to recent theoretical calculations, the nonstoichiometry of the structure arises from copper vacancies within a phase-homogeneity range of 0.17 < x < 0.33 . The ability of the Cu 3– x P structure to host a wide composition range has been experimentally validated by elemental analysis , and solid-state 31 P nuclear magnetic resonance (NMR) spectroscopy. , The tolerance of the Cu 3– x P phase to cation migration without major structural reorganization has been exploited in its demonstration as a candidate anode material for lithium ion batteries , and in its use as a template in cation exchange to InP nanocrystals. , In recent years, the nanoscaling of Cu 3– x P has enabled its use in applications including catalysis, , supercapacitors, photodetection, and chemodynamic therapy and as a precursor to ternary copper chalcophosphate materials used in photovoltaics. , …”

Shaping non-noble metal nanocrystals via colloidal chemistry

“…heterostructures, multimetallic alloys, multi-cation oxides and chalcogenides), including the same elements, which are becoming increasingly popular because of the additional property tunability offered by combining domains with a different chemical nature within the same nanodomain. [92][93][94][95][96][97][98][99][100][101]…”

Binary and Ternary Colloidal Cu‐Sn‐Te Nanocrystals for Thermoelectric Thin Films

“…[24] Moreover, recent advances in synthesis of Cu 2−x S and Cu 2−x Se NCs show promise for accessing multicomponent homogenous or heterogeneous nanostructures. [25][26][27][28] In contrast, ternary copper tin telluride (Cu 2 SnTe 3 ) nanomaterials have rarely been synthesized through colloidal methods because of either narrow regions of phase diagrams that must be accessed or the imbalanced reaction affinity of metals to tellurium. [29,30] So far, Yang and coworkers used TeO 2 as Te precursor to synthesize nearly monodispersed Cu 2 SnTe 3 NCs.…”