The Liquid–Liquid Interface as a Medium To Generate Nanocrystalline Films of Inorganic Materials

Abstract

Unlike the air-water interface, the organic-aqueous (liquid-liquid) interface has not been exploited sufficiently for materials synthesis. In this Account, we demonstrate how ultrathin nanocrystalline films of metals such as gold and silver as well as of inorganic materials such as semiconducting metal chalcogenides (e.g., CdS, CuS, CdSe) and oxides are readily generated at the liquid-liquid interface. What is particularly noteworthy is that single-crystalline films of certain metal chalcogenides are also obtained by this method. The as-prepared gold films at the toluene-water interface comprise fairly monodisperse nanocrystals that are closely packed, the nature and properties of the films being influenced by various reaction parameters such as reaction temperature, time, reactant concentrations, mechanical vibrations, and the viscosity of the medium. The surface plasmon band of gold is markedly red-shifted in the films due to electronic coupling between the particles. The shift of the surface plasmon band of the Au film toward higher wavelengths with an accompanying increase in intensity as a function of reaction time marks the growth of the film. Depending on the reaction temperature, the Au films show interesting electrical transport properties. Films of metals such as gold are disintegrated by the addition of alkanethiols, the effectiveness depending on the alkane chain length, clearly evidenced by shifts of the surface plasmon bands. A time evolution study of the polycrystalline Au and CdS films as well as the single-crystalline CuS films is carried out by employing atomic force microscopy. X-ray reflectivity studies reveal the formation of a monolayer of capped clusters having 13 gold atoms each, arranged in a hexagonal manner at the toluene-water interface. The measurements also reveal an extremely small value of the interfacial tension. Besides describing features of such nanocrystalline films and their mode of formation, their rheological properties have been examined. Interfacial rheological studies show that the nanocrystalline film of Ag nanoparticles, the single-crystalline CuS film, and the multilayered CdS film exhibit a viscoelastic behavior strongly reminiscent of soft-glassy systems. Though both CuS and CdS films exhibit a finite yield stress under steady shear, the CdS films are found to rupture at high shear rates. An important advantage of the study of materials formed at the liquid-liquid interface is that it provides a means to investigate the interface itself. In addition, it enables one to obtain substrate-free single-crystalline films of materials.