In
this work, CdSe/ZnS core/shell quantum dots (QDs) were synthesized.
Dilution of the as-synthesized QDs would lead to instability with
photoluminescence (PL) quenching. It was found that the addition of
tertiary phosphine and alkylthiol could recover the PL intensity of
diluted QDs and make these QDs stable. Specifically, the recovery
efficiency of tertiary phosphine was stronger than that of alkylthiol.
Trioctylphosphine (TOP) and octanethiol (OT) were chosen as the representative
ligands, respectively. Isothermal titration calorimetry (ITC) demonstrated
that interactions between both TOP/OT and QDs were exothermic and
spontaneous. The interaction between TOP and QDs was mainly driven
by van der Waals forces due to the branched structure. This interaction
had a negative entropy change, while the interaction between OT and
QDs had a positive entropy change. There were about ∼12 TOP
molecules and ∼17 OT molecules bound to a QD particle. The
binding constants of TOP/OT to QDs were 1.6 × 103 and
12.8 × 103 M–1, respectively. The
reaction rate between TOP and QDs was fast, and the addition of OT
could slow the reaction rate constant from 0.081 to 0.024 min–1. PL decay indicated that TOP and OT could increase
the radiative recombination of excitons. Furthermore, both TOP and
OT could greatly improve the brightness of the QD films, which was
a prerequisite for the efficient improvement of quantum dot light-emitting
diodes. This work explicitly investigated the dilution process of
QDs, explored the methods for keeping diluted QDs stable and bright,
and highlighted the importance of surface ligands.