Surface chemistry of InP quantum dots: a comprehensive study.
Advanced (1)H, (13)C, and (31)P solution and solid-state NMR studies combined with IR spectroscopy were used to probe, at the molecular scale, the composition and the surface chemistry of indium phosphide (InP) quantum dots (QDs) prepared via a non-coordinating solvent strategy. This nanomaterial can be described as a core-multishell object: an InP core, with a zinc blende bulk structure, is surrounded first by a partially oxidized surface shell, which is itself surrounded by an organic coating. This organic passivating layer is composed, in the first coordination sphere, of tightly bound palmitate ligands which display two different bonding modes. A second coordination sphere includes an unexpected dialkyl ketone and residual long-chain non-coordinating solvents (ODE and its isomers) which interact through weak intermolecular bonds with the alkyl chains of the carboxylate ligands. We show that this ketone is formed during the synthesis process via a decarboxylative coupling route and provides oxidative conditions which are responsible for the oxidation of the InP core surface. This phenomenon has a significant impact on the photoluminescence properties of the as-synthesized QDs and probably accounts for the failure of further growth of the InP core.
Université de Toulouse, INSA, UPS, CNRS, LPCNO (Laboratoire de Physique et Chimie des Nano-Objets), 135 avenue de Rangueil, F-31077 Toulouse, France.
Arnaud
A
Cros-Gagneux
Fabien
F
Delpech
Céline
C
Nayral
Alfonso
A
Cornejo
Yannick
Y
Coppel
Bruno
B
Chaudret