Tuning the Radiative Lifetime in InP Colloidal Quantum Dots by Controlling the Surface Stoichiometry.

InP nanocrystals exhibit a low photoluminescence quantum yield. As in the case of CdS, this is commonly attributed to their poor surface quality and difficult passivation, which give rise to trap states and negatively affect emission. Hence, the strategies adopted to improve their quantum yield have focused on the growth of shells, to improve passivation and get rid of the surface states. Here, we employ state-of-the-art atomistic semiempirical pseudopotential modeling to isolate the effect of surface stoichiometry from features due to the presence of surface trap states and show that, even with an atomistically perfect surface and an ideal passivation, InP nanostructures may still exhibit very long radiative lifetimes (on the order of tens of microseconds), broad and weak emission, and large Stokes’ shifts. Furthermore, we find that all these quantities can be varied by orders of magnitude, by simply manipulating the surface composition, and, in particular, the number of surface P atoms. As a consequence it should be possible to substantially increase the quantum yield in these nanostructures by controlling their surface stoichiometry.