Influence of Different Solvents and High-Electric-Field Cycling on Morphology and Ferroelectric Behavior of Poly(Vinylidene Fluoride-Hexafluoropropylene) Films.

P(VdF-HFP) films are fabricated via a solution casting doctor blade method using high (HVS) and low (LVS) volatile solvents, respectively. The structural properties and the ferroelectric behavior are investigated. The surface structure and crystal phase composition are found to be strongly dependent on the type of solvent. LVS leads to a rougher copolymer surface structure with large spherulites and a lower crystallinity in contrast with HVS. The crystalline phase of copolymer films fabricated with HVS consists almost exclusively of α-phase domains, whereas films from LVS solution show a large proportion of γ-phase domains, as concluded from Raman and X-ray diffraction spectra. Virgin films show no ferroelectric (FE) switching polarization at electric field amplitudes below 180 MV/m, independent of the solvent type, observed in bipolar dielectric displacement-electric field measurements. After applying electric fields of above 180 MV/m, a FE behavior emerges, which is significantly stronger for LVS films. In a repeated measurement, FE polarization switching already occurs at lower fields. A shielding effect may be related to this observation. Additionally, Raman bands of polar γ-phase increase by high-electric-field cycling for the LVS sample. The solvent used and the resulting crystal phase composition of the virgin sample is crucial for the copolymer behavior during bipolar electrical cycling.

Influence of the doping level on the porosity of silicon nanowires prepared by metal-assisted chemical etching.

A systematic method to control the porosity of silicon nanowires is presented. This method is based on metal-assisted chemical etching (MACE) and takes advantage of an HF/H2O2 etching solution and a silver catalyst in the form of a thin patterned film deposited on a doped silicon wafer. It is found that the porosity of the etched nanowires can be controlled by the doping level of the wafer. For low doping concentrations, the wires are primarily crystalline and surrounded by only a very thin layer of porous silicon (pSi) layer, while for highly doped silicon, they are porous in their entire volume. We performed a series of controlled experiments to conclude that there exists a well-defined critical doping concentration separating the crystalline and porous regimes. Furthermore, transmission electron microscopy investigations showed that the pSi has also a crystalline morphology on a length scale smaller than the pore size, determined from positron annihilation lifetime spectroscopy to be mesoscopic. Based on the experimental evidence, we devise a theoretical model of the pSi formation during MACE and apply it for better control of the nanowire morphology.

Nanoscaled surface patterns influence adhesion and growth of human dermal fibroblasts.

In general, there is a need for passivation of nanopatterned biomaterial surfaces if cells are intended to interact only with a feature of interest. For this reason self-assembled monolayers (SAM), varying in chain length, are used; they are highly effective in preventing protein adsorption or cell adhesion. In addition, a simple and cost-effective technique to design nanopatterns of various sizes and distances, the so-called nanosphere lithography (NSL), is discussed, which allows the control of cell adhesion and growth depending on the feature dimensions. Combining both techniques results in highly selective nanostructured surfaces, showing that single proteins selectively adsorb on activated nanopatterns. Additionally, adhesion and growth of normal human dermal fibroblasts (NHDF) is strongly affected by the nanostructure dimensions, and it is proven that fibronectin (FN) matrix formation of these cells is influenced, too. Moreover, the FN fibrils are linked to the hexagonally close-packed nanopatterns. As a result, the system presented here can be applied in tissue engineering and implant design due to the fact that the nanopattern dimensions give rise to further modifications and allow the introduction of chemical heterogeneity to guide stem cell differentiation in the future.

Ag-mediated charge transport during metal-assisted chemical etching of silicon 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.

Sub-20 nm Si/Ge superlattice nanowires by metal-assisted etching.

An effective and low-cost method to fabricate hexagonally patterned, vertically aligned Si/Ge superlattice nanowires with diameters below 20 nm is presented. By combining the growth of Si/Ge superlattices by molecular beam epitaxy, prepatterning the substrate by anodic aluminum oxide masks, and finally metal-assisted chemical wet etching, this method generates highly ordered hexagonally patterned nanowires. This technique allows the fabrication of nanowires with a high area density of 10(10) wires/cm(2), including the control of their diameter and length.

Silicon nanocolumns on nanosphere lithography templated substrates: effects of sphere size and substrate temperature.

Glancing angle ion beam sputter deposition was used to grow regular arrays of Si nanocolumns with a nominal height of 650 nm at room temperature on polystyrene nanospheres with sphere diameters between 260 nm and 3550 nm, and at elevated temperatures on SiO2 nanospheres with a sphere diameter of 360 nm. Top view and cross sectional scanning electron microscopy reveals that the Si nanocolumns resemble cylinder-like structures, terminated by a hemispherical cap. Diameter, height and inter-column-spacing are found to depend linearly on the nanosphere diameter, thus giving the possibility to grow arrays of vertical Si columns with distinct porosities. For the growth at elevated temperatures, it was found that while on non-patterned substrates diffusion effects lead to broadening and finally merging of initially separated nanocolumns, on nanosphere patterned substrates this broadening effect is only moderate. No merging of columns is observable in this case, but a decrease of the column height due to a temperature-driven inter-column densification.

Ordered arrays of silicon nanowires produced by nanosphere lithography and molecular beam epitaxy.

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.