A Close-Space Sublimation Driven Pathway for the Manipulation of Substrate-Supported Micro- and Nanostructures

Abstract

The ability to fabricate structures and engineer materials on the nanoscale leads to the development of new devices and the study of exciting phenomena. Nanostructures attached to the surface of a substrate, in a manner that renders them immobile, have numerous potential applications in a diverse number of areas. Substrate-supported nanostructures can be fabricated using numerous modalities; however the easiest and most inexpensive technique to create a large area of randomly distributed particles is by the technique of thermal dewetting. In this process a metastable thin film is deposited at room temperature and heated, causing the film to lower its surface energy by agglomerating into droplet-like nanostructures. The main drawbacks of nanostructure fabrication via this technique are the substantial size distributions realized and the lack of control over nanostructure placement. In this doctoral dissertation, a new pathway for imposing order onto the thermal dewetting process and for manipulating the size, placement, shape and composition of preformed templates is described. It sees the confinement of substrate-supported thin films or nanostructure templates by the free surface of a metal film or a second substrate surface. Confining the templates in this manner and heating them to elevated temperatures leads to changes in the characteristics of the nanostructures formed. Three different modalities are demonstrated which alters the preformed structures by: (i) subtracting atoms from the templates, (ii) adding atoms to the template or (iii) simultaneously adding and subtracting atoms. The ability to carry out such processes depends on the choice of the confining surface and the nanostructured templates used. A subtractive process occurs when an electroformed nickel mesh is placed in conformal contact with a continuous gold film while it dewets, resulting in the formation of a periodic array of gold microstructures on an oxide substrate surface. When heated the gold beneath the grid selectively attaches to it due to the surface energy gradient which drives gold from the low surface energy oxide surface to the higher surface energy nickel mesh. With this process being confined to areas adjacent to and in contact with the grid surface the film ruptures at well-defined locations to form isolated islands of gold and subsequently, a periodic array of microstructures. The process can be carried out on substrates of different crystallographic orientations leading to nanostructures which are formed epitaxially and have orientations based on underlying substrate orientations. The process can be extended by placing a metallic foil of Pt or Ni over preformed templates, in which case a reduction in the size of the initial structures is observed. Placing a foil on structures with random placement and a wide size distribution results, not only in a size reduction, but also a narrowed size distribution. Additive processes are carried out by using materials which possess high vapor pressures much below the sublimation temperature of the template materials. In this case a germanium substrate was used as a source of germanium adatoms while gold or silver nanostructures were used as heterogeneous nucleation sites. At elevated temperatures the adatoms collect in sufficient quantities to transform each site into a liquid alloy which, upon cooling, phase separates into elemental components sharing a common interface and, hence, resulting in the formation of heterodimers and hollowed metal nanocrescents upon etching away the Ge. A process which combined aspects of the additive and subtractive process was carried out by using a metallic foil with a high vapor pressure and higher surface energy than the substrate surface (in this case Pd foil). This process resulted in the initial preformed gold templates being annihilated and replaced by nanostructures of palladium, thereby altering their chemical composition. The assembly process relies on the concurrent sublimation of palladium and gold which results in the complete transfer of the templated gold from the substrate to the foil, but not before the templates act as heterogeneous nucleation sites for palladium adatoms arriving to the substrate surface. Thus, the process is not only subtractive, but also additive due to the addition of palladium and removal of gold.