Unveiling the Nanocluster Conversion Pathway for Highly Monodisperse InAs Colloidal Quantum Dots.

ABSTRACT

Colloidal quantum dots (CQDs) have garnered significant attention in nanoscience and technology, with a particular emphasis on achieving high monodispersity in their synthesis. Recent advances in understanding the chemistry of reaction intermediates such as magic-sized nanoclusters (MSC) have paved the way for innovative synthetic strategies. Notably, monodisperse CQDs of various compositions, including indium phosphide, indium arsenide, and cadmium chalcogenide, have been successfully prepared using nanocluster intermediates as single-source precursors. Still, the early stage conversion chemistry of these nanoclusters preceding CQD formation has not been fully unveiled yet. Herein, we report the first-order conversion of amorphous nanoclusters (AMCs) to InAs MSCs prior to the formation of CQDs. We find that MSC, isolated via gel-permeation chromatography, is more stable than purified AMCs, as demonstrated in various chemical and thermolytic reactions. While the surface of InAs AMCs and MSC is similarly bound with carboxylate ligands, detailed structural analyses employing synchrotron X-ray scattering and X-ray absorption spectroscopy unveil subtle distinctions arising from the distinct surface properties and structural disorder characteristics of InAs nanoclusters. We propose that InAs AMCs undergo a surface reduction and structural ordering process, resulting in the formation of an InAs MSC in a thermodynamically local minimum state. Furthermore, we demonstrate that both types of nanoclusters serve as viable precursors, providing a similar monomer supply rate at elevated temperatures of around 300 °C. This study offers invaluable insights into the interplay of structure and chemical stability in binary nanoclusters, enhancing our ability to design these nanoclusters as precursors for highly monodisperse CQDs.