Ligand-Mediated Phase Control in Colloidal AgInSe2 Nanocrystals

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 1-dodecanethiol. The thiol plays a crucial role in formation of metastable AgInSe₂ nanocrystals, as it mediates an in-situ topotactic cation exchange from an orthorhombic Ag₂Se intermediate to a metastable orthorhombic phase of AgInSe₂. We provide a detailed mechanistic description of this cation exchange 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 1-dodecanethiol, a mixture of Ag₂Se nanocrystal intermediates form that convert through kinetically slow, non-topotactic exchange processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe₂. Finally, we offer new insight into the prediction of novel metastable multinary nanocrystal phases that do not exist on bulk phase diagrams.