Description:
<jats:title>Abstract</jats:title><jats:p>Understanding high‐order biexciton dynamics is important for the use of semiconductor quantum dots (QDs) in optoelectronic devices. The core–shell structure can be used to modulate biexciton dynamics by varying the shell thickness and core–shell energy band alignment. In this study, the biexciton dynamics in an unconventional case in which each QD is encapsulated by a submonolayer shell are demonstrated. The result of a transient absorption spectroscopic study shows that InP/ZnS core/shell QDs with submonolayer shell coverage exhibit a prolonged Auger lifetime. However, the QD size dependence of the Auger recombination time features two constant distinct stages instead of the typical monotonic volume scaling law in conventional QDs. It is attributed to the tradeoff between the enlarged QD size and quantum‐well confinement for the Auger processes. However, the abrupt change between the two stages is due to the change in the shell coverage. This study provides a reference for the application of core–shell QDs in optoelectronic devices in which full coverage of the shell is not achieved.</jats:p>