Metal-assisted chemical etching is a relatively new top-down approach allowing a highly controlled and precise fabrication of Si and Si/Ge superlattice nanowires. It is a simple method with the ability to tailor diverse nanowire parameters like diameter, length, density, orientation, doping level, doping type, and morphology. In a typical metal-assisted chemical etching procedure, a Si substrate is covered by a lithographic noble metal film and etched in a solution containing HF and an oxidant (typically H 2 O 2 ). In general, the function of the metal is to catalyze the reduction of H 2 O 2 , which delivers electronic holes necessary for the oxidation and subsequent dissolution of the Si oxide by HF. However, the details of the etching process using contiguous metal thin films, especially the mass transport of reactants and byproducts are still not well understood. In this study, the etching mechanism was systematically investigated. Several models of metal-assisted chemical etching using a contiguous metal film as a catalyst were developed and tested by performing different well-controlled etching experiments. The experiments helped to identify two processes fundamental for the formation of Si nanowires. First, a thin porous layer is formed beneath the metal film during etching, which facilitates the transport of the electrolyte (HF and H 2 O 2 ). Second, the porous layer is continuously etched away in an electropolishing process, which occurs in direct contact with the metal film. Our results lead to an improved understanding of the fundamentals of the metal-assisted chemical etching on a microscopic scale. It potentially paves a way to integrate lithography with metal-assisted chemical etching for fabrication of Si nanowires with adjustable surface patterns.

Because of their importance in fundamental research and possible applications in nanotechnology and nanoelectronics, semiconductor nanowires have attracted much interest. In addition to the growth itself, the control of the size and location is an essential problem. Here we show the growth of ordered arrays of vertically aligned silicon nanowires by molecular beam epitaxy using prepatterned arrays of gold droplets on Si(111) substrates. The ordered arrays of gold particles were produced by nanosphere lithography.

ZnO nanowires and nanobelts are two representatives of one-dimensional semiconductor nanomaterials possessing potential applications as optoelectronic and sensor devices. In this study, we applied a vapour-transport-deposition method to synthesize both types of nanostructures using relatively low temperatures (860 • C) by controlling the source materials. We found that the resulting product under similar growth conditions can be switched between [0001]-axial nanowires and 1120-axial nanobelts simply by adding indium to the source. The former appear as ordered vertical arrays of pure ZnO while the latter are belts without spatial ordering. Both represent defect-free single crystals grown via the vapour-liquid-solid mechanism using nanosphere lithography-fabricated catalyst Au templates. Examination of the early growth stage suggests that the dissolution of In into Au influences the nucleation of ZnO at the solid-liquid interface, and subsequently defines the structure and crystallographic orientation of the nanobelts. The optical properties of both nanostructures are studied by photoluminescence and resonant Raman scattering, which indicate consistently that the doped nanobelts have a higher carrier concentration than the nanowires.

The charge transport mechanism during metal-assisted chemical etching of Si nanowires with contiguous metal films has been investigated. The experiments give a better insight how the charges and reaction products can penetrate to the etching front. The formation of a layer of porous Si between the metal film and the bulk Si is a prerequisite for the etching process. The electronic holes (positive charges) necessary for the etching of porous Si are generated at the surface of the metal in contact with the oxidative agent. Because of the insulating character of the thin walls of the porous Si, the transport of the electronic holes through this layer is not possible. Instead, it is found that the transport of electronic holes proceeds primarily by means of the Ag/Ag(+) redox pair circulating in the electrolyte and diffusing through the etched pores in the Si. The charge transport occurs without the ionic contribution at the positions where the metal is in direct contact with the Si. Here, an electropolishing process takes place, leading to an extensive removal of the Si and sinking in of the film into the Si substrate.

Stability of surface coatings against environmental stress, such as pH, high ionic strength, mechanical forces, and so forth, is crucial for biomedical application of implants. Here, a novel extracellular-matrix-like polyelectrolyte multilayer (PEM) system composed of collagen I (Col I) and oxidized glycosaminoglycans (oGAGs) was stabilized by intrinsic cross-linking due to formation of imine bonds between aldehydes of oxidized chondroitin sulfate (oCS) or hyaluronan (oHA) and amino groups of Col I. It was also found that Col I contributed significantly more to overall mass in CS-Col I than in HA-Col I multilayer systems and fibrillized particularly in the presence of native and oxidized CS. Adhesion and proliferation studies with murine C3H10T1/2 embryonic fibroblasts demonstrated that covalent cross-linking of oGAG with Col I had no adverse effects on cell behavior. By contrast, it was found that cell size and polarization was more pronounced on oGAG-based multilayer systems, which corresponded also to the higher stiffness of cross-linked multilayers as observed by studies with quartz crystal microbalance (QCM). Overall, PEMs prepared from oGAG and Col I give rise to stable PEM constructs due to intrinsic cross-linking that may be useful for making bioactive coatings of implants and tissue engineering scaffolds.