AgInS2-ZnS (ZAIS) nanocrystals are very good candidates for easily synthesized, highly efficient cadmium-free nano-phosphors. They can be employed for the development of next generation white-LED technologies, taking advantage of their nanometric size. This paper describes the combined use of time-resolved emission spectroscopy and photoluminescence quantum yield measurements to quantitatively compare the efficiency of each recombination pathway involved in the photoluminescence of ZAIS nanocrystals. This approach, applied to nanocrystals of different sizes, compositions and surface chemistry revealed the critical role of surface effects. Moreover, we developed a new type of surface passivation that increases the photoluminescence quantum yield of all nanocrystal compositions by 15 to 20%. This molecular surface passivation can be applied as a replacement or in addition to the already established ZnS shell passivation method.

The systematic measurement of the photoluminescence quantum yield and the recombination lifetime of a given phosphor allows for the quantification of both radiative and non-radiative recombination rates. This analysis therefore separates the two types of phenomena influencing the quantum efficiency of the phosphor. When associated with other materials characterizations, this powerful tool allows for the determination of the relationship between the structural properties and the efficiency of the photoluminescence process. This article presents this method and its direct application to emerging luminescent quaternary semiconductor nanocrystals. First, the direct effect of disorder on non-radiative recombination rate is demonstrated. Then, strong evidence concerning the nature of the donor and acceptor defects involved in the photoluminescence process of these materials are obtained using XPS.