M.G. Maas

Dielectrophoretic alignment of metal and metal oxide nanowires and nanotubes: A universal set of parameters for bridging prepatterned microelectrodes

Nanowires and nanotubes were synthesized from metals and metal oxides using templated cathodic electrodeposition. With templated electrodeposition, small structures are electrodeposited using a template that is the inverse of the final desired shape. Dielectrophoresis was used for the alignment of the as-formed nanowires and nanotubes between prepatterned electrodes. For reproducible nanowire alignment, a universal set of dielectrophoresis parameters to align any arbitrary nanowire material was determined. The parameters include peak-to-peak potential and frequency, thickness of the silicon oxide layer, grounding of the silicon substrate, and nature of the solvent medium used. It involves applying a field with a frequency >10(5) Hz, an insulating silicon oxide layer with a thickness of 2.5 μm or more, grounding of the underlying silicon substrate, and the use of a solvent medium with a low dielectric constant. In our experiments, we obtained good results by using a peak-to-peak potential of 2.1 V at a frequency of 1.2 × 10(5) Hz. Furthermore, an indirect alignment technique is proposed that prevents short circuiting of nanowires after contacting both electrodes. After alignment, a considerably lower resistivity was found for ZnO nanowires made by templated electrodeposition (2.2-3.4 × 10(-3) Ωm) compared to ZnO nanorods synthesized by electrodeposition (10 Ωm) or molecular beam epitaxy (MBE) (500 Ωm).

Hydrogen generation from photocatalytic silver|zinc oxide nanowires: towards multifunctional multisegmented nanowire devices.

Photoactive nanowires: A novel photo-electrochemical nanowire diode that catalyzes the conversion of methanol and water to hydrogen under UV light is demonstrated. The wire consists of a metal and a metal oxide segment that are connected via a Schottky barrier. Other functions, such as remote- controlled autonomous movement, can be easily added to these wires in a modular fashion

Patterning Functional Materials Using Channel Diffused Plasma-Etched Self-Assembled Monolayer Templates

A simple and cost-effective methodology for large-area micrometer-scale patterning of a wide range of metallic and oxidic functional materials is presented. Self-assembled monolayers (SAM) of alkyl thiols on Au were micropatterned by channel-diffused oxygen plasma etching, a method in which selected areas of SAM were protected from plasma oxidation via a soft lithographic stamp. The patterned SAMs were used as templates for site-selective electrodeposition, electroless deposition and solution-phase deposition of functional materials such as ZnO, Ni, Ag thin films, and ZnO nanowires. The patterned SAMs and functional materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), and tunneling AFM (TUNA).

Nanopatterning of functional materials by gas phase pattern deposition of self-assembled molecular thin films in combination with electrodeposition.

We present a general methodology to pattern functional materials on the nanometer scale using self-assembled molecular templates on conducting substrates. A soft lithographic gas phase edge patterning process using poly(dimethylsiloxane) molds was employed to form electrically isolating organosilane patterns of a few nanometer thickness and a line width that could be tuned by varying the time of deposition. Electrodeposition was employed to deposit patterns of Ni and ZnO on these prepatterned substrates. Deposition occurred only on patches of the substrate where no organosilane monolayer was present. The process is simple, inexpensive, and scalable to large areas. We achieved formation of metallic and oxide material patterns with a lateral resolution of 80 nm.

Electrodeposition in Capillaries: Bottom-up Micro- and Nanopatterning of Functional Materials on Conductive Substrates

A cost-effective and versatile methodology for bottom-up patterned growth of inorganic and metallic materials on the micro- and nanoscale is presented. Pulsed electrodeposition was employed to deposit arbitrary patterns of Ni, ZnO, and FeO(OH) of high quality, with lateral feature sizes down to 200-290 nm. The pattern was defined by an oxygen plasma-treated patterned PDMS mold in conformal contact with a conducting substrate and immersed in an electrolyte solution, so that the solid phases were deposited from the solution in the channels of the patterned mold. It is important that the distance between the entrance of the channels, and the location where deposition is needed, is kept limited. The as-formed patterns were characterized by high resolution scanning electron microscope, energy-dispersive X-ray analysis, atomic force microscopy, and X-ray diffraction.

Photocatalytic segmented nanowires and single-step iron oxide nanotube synthesis: templated electrodeposition as all-round tool

Templated electrodeposition was used to synthesize silver-zinc oxide nanowires and iron oxide (Fe2O3) nanotubes in polycarbonate track etched (PCTE) membranes. Metal/oxide segmented nanowires were made to produce hydrogen gas from a water/methanol mixture under ultraviolet irradiation. It was observed that gas production increased during irradiation. Iron oxide nanotubes were synthesized via a gel synthesis route, avoiding clogging of the membrane pores during growth. The nanotubes formed without thermal after-treatment. Transmission electron microscopy (TEM) analysis and selected area electron diffraction (SAED) revealed a completely amorphous iron oxide structure. By demonstrating the synthesis of photocatalytically active segmented nanowire and nanotubes without post-treatment steps, templated electrodeposition can be a versatile and low cost tool for nanowires with designed functionality or fast nanotube synthesis

Preparation and use of photocatalytically active segmented Ag|ZnO and coaxial TiO2-Ag nanowires made by templated electrodeposition.

Photocatalytically active nanostructures require a large specific surface area with the presence of many catalytically active sites for the oxidation and reduction half reactions, and fast electron (hole) diffusion and charge separation. Nanowires present suitable architectures to meet these requirements. Axially segmented Ag|ZnO and radially segmented (coaxial) TiO2-Ag nanowires with a diameter of 200 nm and a length of 6-20 µm were made by templated electrodeposition within the pores of polycarbonate track-etched (PCTE) or anodized aluminum oxide (AAO) membranes, respectively. In the photocatalytic experiments, the ZnO and TiO2 phases acted as photoanodes, and Ag as cathode. No external circuit is needed to connect both electrodes, which is a key advantage over conventional photo-electrochemical cells. For making segmented Ag|ZnO nanowires, the Ag salt electrolyte was replaced after formation of the Ag segment to form a ZnO segment attached to the Ag segment. For making coaxial TiO2-Ag nanowires, a TiO2 gel was first formed by the electrochemically induced sol-gel method. Drying and thermal annealing of the as-formed TiO2 gel resulted in the formation of crystalline TiO2 nanotubes. A subsequent Ag electrodeposition step inside the TiO2 nanotubes resulted in formation of coaxial TiO2-Ag nanowires. Due to the combination of an n-type semiconductor (ZnO or TiO2) and a metal (Ag) within the same nanowire, a Schottky barrier was created at the interface between the phases. To demonstrate the photocatalytic activity of these nanowires, the Ag|ZnO nanowires were used in a photocatalytic experiment in which H2 gas was detected upon UV illumination of the nanowires dispersed in a methanol/water mixture. After 17 min of illumination, approximately 0.2 vol% H2 gas was detected from a suspension of ~0.1 g of Ag|ZnO nanowires in a 50 ml 80 vol% aqueous methanol solution.