This thesis is devoted to the study of the growth of Zinc Selenide (ZnSe) nanowires (NWs) by Au-assisted molecular beam epitaxy (MBE). The growth process consists in many steps which were individually investigated by means of in-situ and ex-situ spectroscopic and microscopic techniques. First, the formation of nanoparticles upon annealing of a thin Au film deposited on different substrates was studied by X-ray photoemission spectroscopy, grazing incident X-ray diffraction and scanning electron microscopy. The nanoparticles were used as seeds for the 1-dimensional ZnSe crystal growth by MBE through evaporation of Zn and Se from elemental solid sources. The obtained NWs were characterized by scanning and transmission electron microscopy and their optical properties were assessed by means of photoluminescence and cathodoluminescence measurements.
This systematic investigation approach allowed us to understand the NWs growth mechanism and, as a consequence, to obtain the control over the NWs properties. Indeed, it was found that an interplay between substrate, seed particles and beam fluxes takes place and strongly affects the NWs growth mode. In particular, a chemical interaction between substrate and Au may occur during the annealing, changing chemical composition and physical state of the nanoparticles before the NWs growth. The vapour composition, i.e. the Zn-to-Se beam pressure ratio, can also modify the nanoparticles composition and the NWs growth mechanism. Therefore, by changing the growth conditions, it was possible to grow ZnSe NWs through different mechanisms, with important consequences on their properties, in terms of morphology, crystal quality and optical properties.
Understanding the growth mechanism and its effects on the wires properties allowed us to achieve the control over the growth process and the selective growth of ZnSe nanowires with the desired properties. Vertically oriented ZnSe NWs with a defect-free hexagonal crystal structure were obtained on GaAs(111)B substrates, having either Au-Ga alloy nanoparticles or Au nanocrystals on their tips. Uniformly thin and straight blue-emitting ZnSe NWs were also grown on various substrates, after optimizing gold film thickness, annealing and growth temperature. The possible integration of such nanostructores in novel nanodevices was proposed and preliminary demonstrated.
