Electron Doping in Bottom-Up Engineered Thermoelectric Nanomaterials through HCl-Mediated Ligand Displacement

A simple and effective method to introduce precise amounts of doping in nanomaterials produced from the bottom-up assembly of colloidal nanoparticles (NPs) is described. The procedure takes advantage of a ligand displacement step to incorporate controlled concentrations of halide ions while removing carboxylic acids from the NP surface. Upon consolidation of the NPs into dense pellets, halide ions diffuse within the crystal structure, doping the anion sublattice and achieving n-type electrical doping. Through the characterization of the thermoelectric properties of nanocrystalline PbS, we demonstrate this strategy to be effective to control charge transport properties on thermoelectric nanomaterials assembled from NP building blocks. This approach is subsequently extended to PbTe_<i>x</i>Se_1–<i>x</i>@PbS core–shell NPs, where a significant enhancement of the thermoelectric figure of merit is achieved