This review gives an overview of the synthesis, photophysical properties, surface characterization/functionalization and some applications of chalcopyrite-type nanocrystals.

The presented research is focused on the synthesis of alloyed Ag−In−Zn−S colloidal nanocrystals from a mixture of simple metal precursors such as AgNO 3 , InCl 3 , zinc stearate combined with 1-dodecanethiol (DDT), 1-octadecene (ODE), and sulfur dissolved in oleylamine (OLA). In particular, the focus is on the effect of the solvent (ODE vs 1,2dichlorobenzene (DCB)) and the type of sulfur precursor (S/ OLA vs S/n-octylamine (OCA)) on the metal precursors reactivates and on the chemical composition, crystal structure, and luminescent properties of the resulting nanocrystals. The replacement of ODE by DCB as a solvent lowers the reactivity of metal precursors and results in a 3-fold decrease of the photoluminescence quantum yields (Q.Y.) values (from 67% to 21%). This negative effect can be fully compensated by the use of S/OCA as a source of sulfur instead of S/OLA (Q.Y. increases from 21% to 64%). NMR studies of the isolated organic phase indicate that the S/OLA precursor generates two types of ligands being products of (Z)-1-amino-9-octadecene (OLA) hydrogenation. These are "surface bound" 1-aminooctadecane (C 18 H 37 NH 2 ) and crystal bound, i.e., alkyl chain covalently bound to the nanocrystal surface via surfacial sulfur (C 18 H 37 -NH-S crystal). Highly luminescent Ag−In−Zn−S nanocrystals exhibit a cation-enriched (predominantly indium) surface and are stabilized by a 1-aminooctadecane ligand, which shows more flexibility than OLA. These investigations were completed by hydrophilization of nanocrystals obtained via exchange of the primary ligands for 11-mercaptoundecanoic acid, (MUA) with only a 2-fold decrease of photoluminescence Q.Y. in the most successful case (from 67% to 31%). Finally, through ligand exchange, an electroactive inorganic/organic hybrid was obtained, namely, Ag−In−Zn−S/7-octyloxyphenazine-2-thiol, in which its organic part fully retained its electrochemical activity.