Insights into the Structural Complexity of Colloidal CdSe Nanocrystal Surfaces: Correlating the Efficiency of Nonradiative Excited-State Processes to Specific Defects.

II-VI colloidal semiconductor nanocrystals (NCs), such as CdSe NCs, are often plagued by efficient nonradiative recombination processes that severely limit their use in energy-conversion schemes. While these processes are now well-known to occur at the surface, a full understanding of the exact nature of surface defects and of their role in deactivating the excited states of NCs has yet to be established, which is partly due to challenges associated with the direct probing of the complex and dynamic surface of colloidal NCs. Here, we report a detailed study of the surface of cadmium-rich zinc-blende CdSe NCs. The surfaces of these cadmium-rich species are characterized by the presence of cadmium carboxylate complexes (CdX2) that act as Lewis acid (Z-type) ligands that passivate undercoordinated selenide surface species. The systematic displacement of CdX2 from the surface by N,N,N',N'-tetramethylethylene-1,2-diamine (TMEDA) has been studied using a combination of 1H NMR and photoluminescence spectroscopies. We demonstrate the existence of two independent surface sites that differ strikingly in the binding affinity for CdX2 and that are under dynamic equilibrium with each other. A model involving coupled dual equilibria allows a full characterization of the thermodynamics of surface binding (free energy, as well as enthalpic and entropic terms), showing that entropic contributions are responsible for the difference between the two surface sites. Importantly, we demonstrate that cadmium vacancies only lead to important photoluminescence quenching when created on one of the two sites, allowing a complete picture of the surface composition to be drawn where each site is assigned to specific NC facet locale, with CdX2 binding affinity and nonradiative recombination efficiencies that differ by up to two orders of magnitude.