A Simple Route to Alloyed Quaternary Nanocrystals Ag-In-Zn-S with Shape and Size Control

A convenient method of the preparation of alloyed quaternary Ag-In-Zn-S nanocrystals is elaborated, in which a multicomponent mixture of simple and commercially available precursors, namely, silver nitrate, indium(III) chloride, zinc stearate, 1-dodecanethiol, and sulfur, is used with 1-octadecene as a solvent. The formation of quaternary nanocrystals necessitates the use of an auxiliary sulfur precursor, namely, elemental sulfur dissolved in oleylamine, in addition to 1-dodecanethiol. Without this additional precursor binary ZnS nanocrystals are formed. The optimum reaction temperature of 180 degrees C was also established. In these conditions shape, size, and composition of the resulting nanocrystals can be adjusted in a controlled manner by changing the molar ratio of the precursors in the reaction mixture. For low zinc stearate contents anisotropic rodlike (ca.3 nm x 10 nm) and In-rich nanocrystals are obtained. This is caused by a significantly higher reactivity of the indium precursor as compared to the zinc one. With increasing zinc precursor content the reactivities of both precursors become more balanced, and the resulting nanocrystals are smaller (1.5-4.0 nm) and become Zn-rich as evidenced by transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometry investigations. Simultaneous increases in the zinc and sulfur precursor content result in an enlargement of nanocrystals (2.5 to 5.0 nm) and further increase in the molar ZnS content (up to 0.76). The prepared nanoparticles show stable photoluminescence with the quantum yield up to 37% for In and Zn-rich nanocrystals. Their hydrodynamic diameter in toluene dispersion, determined by dynamic light scattering, is roughly twice larger than the diameter of their inorganic core.