Facile Exchange of Tightly Bonded L-Type Oleylamine and Diphenylphosphine Ligands on Copper Indium Diselenide Nanocrystals Mediated by Molecular Iodine

摘要

Copper indium diselenide (CuInSe2) nanocrystals are a prototypical I-III-VI semiconductor quantum dot material, typically synthesized in oleylamine (OLAm) as a solvent and capping ligand, often with the addition of diphenylphosphine (DPP) to improve the reaction yield. Using H-1 nuclear magnetic resonance spectroscopy, we study the association of OLAm and DPP on CuInSe2 nanocrystals and find that they both behave as tightly bonded L-type ligands. There is no observable desorption of OLAm or DPP when a toluene-d(8) dispersion is heated to 100 degrees C, and no ligand exchange occurs when the nanocrystals are exposed to other L-type species like trioctylphosphine (TOP) or octadecanethiol (ODT), which can bind as either X-type or L-type. Molecular iodine (I-2), however, is found to readily displace both OLAm and DPP from the nanocrystal surface and facilitate efficient and complete ligand exchange with either TOP or ODT and appears to behave as a Lewis acid Z-type ligand. We also find that the X-type ligand, stearic acid, does not bond to the CuInSe2 nanocrystals under any circumstances.