Ligand Effect in 1‐Octanethiol Passivation of InP/ZnSe/ZnS Quantum Dots—Evidence of Incomplete Surface Passivation during Synthesis

Abstract The lack of anionic carboxylate ligands on the surface of InP/ZnSe/ZnS quantum dots (QDs), where zinc carboxylate ligands can be converted to carboxylic acid or carboxylate ligands via proton transfer by 1‐octanethiol, is demonstrated. The as‐synthesized QDs initially have an under‐coordinated vacancy surface, which is passivated by solvent ligands such as ethanol and acetone. Upon exposure of 1‐octanethiol to the QD surface, 1‐octanethiol effectively induces the surface binding of anionic carboxylate ligands (derived from zinc carboxylate ligands) by proton transfer, which consequently exchanges ethanol and acetone ligands that bind on the incomplete QD surface. These systematic chemical analyses, such as thermogravimetric analysis‐mass spectrometry and proton nuclear magnetic resonance spectroscopy, directly show the interplay of surface ligands, and it associates with QD light‐emitting diodes (QD‐LEDs). It is believed that this better understanding can lead to industrially feasible QD‐LEDs.