Ligand-Mediated Phase Control in Colloidal AgInSe <sub>2</sub> Nanocrystals
Bryce A. Tappan, Matthew K. Horton, Richard L. Brutchey
Abstract
Synthetic studies of colloidal nanoparticles that crystallize in metastable structures represent an emerging area of interest in the development of novel functional materials, as metastable nanomaterials may exhibit unique properties when compared to their counterparts that crystallize in thermodynamically preferred structures. Herein, we demonstrate how phase control of colloidal AgInSe2 nanocrystals can be achieved by performing reactions in the presence or absence of coordinating ligands that can act as cation exchange mediators (i.e., oleylamine or 1-dodecanethiol). These coordinating ligands play a crucial role in the formation of metastable AgInSe2 nanocrystals, as they mediate in situ topotactic conversion of an orthorhombic Ag2Se intermediate to a metastable orthorhombic phase of AgInSe2. We provide a detailed mechanistic crystal chemistry description of this process to structurally elucidate how the orthorhombic phase of AgInSe2 forms. Density functional theory calculations suggest that the metastable orthorhombic phase of AgInSe2 is metastable by a small margin, at 10 meV/atom above the thermodynamic ground state. In the absence of oleylamine or 1-dodecanethiol, Ag2Se nanocrystal intermediates convert through kinetically slow, nontopotactic conversion processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe2. On the basis of these discoveries, we offer new insights into the prediction of novel metastable multinary nanocrystal phases that do not exist on bulk phase diagrams.