InP/ZnS core/shell quantum dots (QDs), recognized as
highly promising
heavy-metal-free emitters, are increasingly being utilized in lighting
and display applications. Their synthesis in a tubular flow reactor
enables production in a highly efficient, scalable, and reproducible
manner, particularly when combined with a single-source shell precursor,
such as zinc diethyldithiocarbamate (Zn(S2CNEt2)2). However, the photoluminescence quantum yield (PLQY)
of QDs synthesized with this route remains significantly lower compared
with those synthesized in batch reactors involving multiple steps
for the shell growth. Our study identifies the formation of absorbing,
yet nonemissive ZnS nanoparticles during the ZnS shell formation process
as a main contributing factor to this discrepancy. By varying the
shelling conditions, especially the shelling reaction temperature
and InP core concentration, we investigated the formation of pure
ZnS nanoparticles and their impact on the optical properties, particularly
PLQY, of the resultant InP/ZnS QDs through ultraviolet–visible
(UV–vis) absorption, steady-state and time-resolved photoluminescence
(PL) spectroscopy, scanning transmission electron microscopy (STEM),
and analytical ultracentrifugation (AUC) measurements. Our results
suggest that process conditions, such as lower shelling temperatures
or reduced InP core concentrations (resulting in a lower external
surface area), encourage homogeneous nucleation of ZnS. This reduces
the availability of shell precursors necessary for effective passivation
of the InP core surfaces, ultimately resulting in lower PLQYs. These
findings explain the origin of persistently underperforming PLQY of
InP/ZnS QDs synthesized from this synthesis route and suggest further
optimization strategies to improve their emission for lighting and
display applications.