Nucleation and Growth of Zinc Sulfide Nanoparticles in Ultrathin Polymer Films by Layer-by-Layer Polyionic Assemblies

In this work, zinc sulfide (ZnS) nanoparticles were formed by nucleation and growth in ultrathin films of polydiallyldi-methylammonium chloride (PDDA)–polystyrenesulfonate sodium salt (PSS) film produced by the Layer-by-Layer (LbL) deposition technique. Multilayer thin film assemblies, fabricated by sequential adsorption of polyelectrolytes on a quartz substrate, were used as a supramolecular reaction template to study the in-situ nucleation and growth of ZnS nanoparticles. ZnS nanoparticles were nucleated within the polymeric supramolecular structure through cyclic expo-sure to the solutions of Zn(NO3)2 and thiourea. The growth and nucleation of nanoparticles were accomplished by a cyclic repetition of reductive hydrolysis reactions. The growth of a thin film on a flat substrate via LbL was monitored by ultraviolet-visible (UV-Vis) spectroscopy. Analysis of the UV-visible absorption spectra of the films revealed that the nanoparticles grew with increasing number of cycles. The presence of ZnS nanoparticles were verified by transmission electron microscopy (TEM). Selected area electron diffraction (SAED) showed that the ZnS has a cubic spheralite structure.