Exchange of initial, predominantly stearate ligands for pyridine in the first step and butylamine (BA) or 11-mercaptoundecanoic acid (MUA) in the second one was studied for alloyed quaternary Cu–In–Zn–S nanocrystals. The NMR results enabled us to demonstrate, for the first time, direct binding of the pyridine labile ligand to the nanocrystal surface as evidenced by paramagnetic shifts of the three signals attributed to its protons to 7.58, 7.95 and 8.75 ppm. XPS investigations indicated, in turn, a significant change in the composition of the nanocrystal surface upon the exchange of initial ligands for pyridine, which being enriched in indium in the ‘as prepared’ form became enriched in zinc after pyridine binding. This finding indicated that the first step of ligand exchange had to involve the removal of the surface layer enriched in indium with simultaneous exposure of a new, zinc-enriched layer. In the second ligand exchange step (replacement of pyridine with BA or MUA) the changes in the nanocrystal surface compositions were much less significant. The presence of zinc in the nanocrystal surface layer turned out necessary for effective binding of pyridine as shown by a comparative study of ligand exchange in Cu–In–Zn–S, Ag–In–Zn–S and CuInS₂, carried out by complementary XPS and NMR investigations.

Ternary Ag–In–S or quaternary Ag–In–Zn–S nanocrystals were prepared from simple precursors (silver nitrate, indium(III) chloride, zinc stearate in a mixture of DDT and ODE) by injecting a solution of elemental sulfur into OLA. Ternary nanocrystals were modified by depositing either a ZnS or a CdS shell, yielding type I and type II core/shell systems exhibiting photoluminescence QY in the range of 12–16%. Careful optimization of the reaction conditions allowed alloyed quaternary Ag–In–Zn–S nanocrystals exhibiting tunable photoluminescence in the spectral range of 520–720 nm with a QY of 48% and 59% for green and red radiations, respectively, to be obtained. ¹H NMR analysis of the nanocrystal organic shell, after dissolution of its inorganic core, indicated that surfacial sulfur atoms were covalently bonded to aliphatic chains whereas surfacial cations were coordinated by amines and carboxylate anions. No thiol-type ligands were detected. Transfer of the prepared nanocrystals to water could be achieved in one step by exchanging the initial ligands for 11-mercaptoundecanoic ones resulting in a QY value of 31%. A new Ag–In–Zn–S nanocrystal preparation method was elaborated in which indium and zinc salts of fatty acids were used as cation precursors and DDT was replaced by thioacetamide. This original DDT-free method enabled similar tuning of the photoluminescence properties of the nanocrystals as in the previous method; however the measured photoluminescence QYs were three times lower. Hence, further optimization of the new method is required.

It is demonstrated that ternary Cu–Fe–S nanocrystals differing in composition (from Cu-rich to Fe-rich), structure (chalcopyrite or high bornite) and size can be obtained from a mixture of CuCl, FeCl₃, thiourea and oleic acid (OA) in oleylamine (OLA) using the heating up procedure. This new preparation method yields the smallest Cu–Fe–S nanocrystals ever reported to date (1.5 nm for the high bornite structure and 2.7 nm for the chalcopyrite structure). A comparative study of nanocrystals of the same composition (Cu_1.6Fe_1.0S_2.0) but different in size (2.7 nm and 9.3 nm) revealed a pronounced quantum confinement effect, confirmed by three different techniques: UV-vis spectroscopy, cyclic voltammetry and Mössbauer spectroscopy. The optical band gap increased from 0.60 eV in the bulk material to 0.69 eV in the nanocrystals of 9.3 nm size and to 1.39 eV in nanocrystals of 2.7 nm size. The same trend was observed in the electrochemical band gaps, derived from cyclic voltammetry studies (band gaps of 0.74 eV and 1.54 eV). The quantum effect was also manifested in Mössbauer spectroscopy by an abrupt change in the spectrum from a quadrupole doublet to a Zeeman sextet below 10 K, which could be interpreted in terms of the well defined energy states in these nanoparticles, resulting from quantum confinement. The Mössbauer spectroscopic data confirmed, in addition to the results of XPS spectroscopy, the co-existence of Fe(III) and Fe(II) in the synthesized nanocrystals. The organic shell composition was investigated by NMR (after dissolution of the inorganic core) and IR spectroscopy. Both methods identified oleylamine (OLA) and 1-octadecene (ODE) as surfacial ligands, the latter being formed in situ via an elimination–hydrogenation reaction occurring between OLA and the nanocrystal surface.