Metal-assisted chemical etching of silicon: a review.

This article presents an overview of the essential aspects in the fabrication of silicon and some silicon/germanium nanostructures by metal-assisted chemical etching. First, the basic process and mechanism of metal-assisted chemical etching is introduced. Then, the various influences of the noble metal, the etchant, temperature, illumination, and intrinsic properties of the silicon substrate (e.g., orientation, doping type, doping level) are presented. The anisotropic and the isotropic etching behaviors of silicon under various conditions are presented. Template-based metal-assisted chemical etching methods are introduced, including templates based on nanosphere lithography, anodic aluminum oxide masks, interference lithography, and block-copolymer masks. The metal-assisted chemical etching of other semiconductors is also introduced. A brief introduction to the application of Si nanostructures obtained by metal-assisted chemical etching is given, demonstrating the promising potential applications of metal-assisted chemical etching. Finally, some open questions in the understanding of metal-assisted chemical etching are compiled.

Flexible replication technique for high-aspect-ratio nanostructures.

A flexible, nondestructive, and cost-effective replication technique for nanostructures is presented. The advantages of the process are: 1) it allows for tailoring structural parameters of the replica (e.g., line width) nearly independent of the structural geometry of the master; 2) it allows for replication of high-aspect-ratio structures also in polymer materials from solution (especially noncurable polymers) such as polystyrene and polymethylmethacrylate; 3) it includes an easy separation process, thus preserving the master for repeated use. Linear grating replicas with line widths ranging from 88 to 300 nm are obtained using a single nanostructured master. Nanofibers and complex nanopatterned replicas are achievable. The presented technique and its flexibility show that atomic layer deposition is a unique tool for the preparation of high-efficiency polarizer diffractive optics, photonics, electronics, and catalysts.

Disproportionation of thermoelectric bismuth telluride nanowires as a result of the annealing process.

P-type thermoelectric bismuth telluride nanowires were fabricated by pulsed electrodeposition in anodic aluminium oxide (AAO) membranes. Subsequently, the nanowires were annealed at 423, 523 and 673 K in an inert atmosphere for 4 h. With increasing temperature, it was observed that the Te compound incongruently sublimates due to its high vapor pressure, leading to disproportionation (from Bi(2)Te(3) to Bi(4)Te(3)via Bi(4)Te(5)). The crystalline structure of the nanowires was then investigated using XRD and SAED, with nanowire compositions investigated using an EDX attached to a TEM. The crystallinity of the nanowires was found to be enhanced with increased annealing temperature, and nanowires annealed at 673 K were stably maintained in the Bi(4)Te(3) phase. Additionally, the Seebeck coefficient was determined and the thermopower of nanowires annealed at a temperature of 423 K was shown to be slightly enhanced. Significantly suppressed Seebeck values for annealing temperatures of 523 K and 673 K were also observed.

The transition between conformal atomic layer epitaxy and nanowire growth.

Conformal atomic layer deposition of thin Sb(2)S(3) layers takes place epitaxially on suitable substrates at 90 degrees C. More elevated deposition temperatures increase the mobility of the solid and result in the diffusion of Sb(2)S(3) along surface energy gradients. On an Sb(2)Se(3) wire that presents the high-energy c facet at its extremity, this results in the axial elongation of the wire with a Sb(2)S(3) segment. When an Sb(2)S(3) wire whose c planes are exposed on the sides is used as the substrate, the homoepitaxy collects material laterally and yields a nano-object with a rectangular cross section.

Capillary condensation and evaporation in alumina nanopores with controlled modulations.

Capillary condensation in nanoporous anodic aluminum oxide presenting not interconnected pores with controlled modulations is studied using adsorption experiments and molecular simulations. Both the experimental and simulation data show that capillary condensation and evaporation are driven by the smallest size of the nanopore (constriction). The adsorption isotherms for the open and closed pores are almost identical if constrictions are added to the system. The latter result implies that the type of pore ending does not matter in modulated pores. Thus, the presence of hysteresis loops observed in adsorption isotherms measured in straight nanopores with closed bottom ends can be explained in terms of geometrical inhomogeneities along the pore axis. More generally, these results provide a general picture of capillary condensation and evaporation in constricted or modulated pores that can be used for the interpretation of adsorption in disordered porous materials.

Hybrid polymer-silicon proton conducting membranes via a pore-filling surface-initiated polymerization approach.

An alternative approach for the creation of proton conducting platforms is presented. The methodology is based on the so-called "pore-filling concept", which relies on the filling of porous matrices with polyelectrolytes to obtain proton conducting platforms with high dimensional stability. Polymer-silicon composite membranes, with well-defined polyelectrolyte microdomains oriented normal to the plane of the membrane, were prepared using photoelectrochemically etched silicon as a microstructured scaffold. Ordered two-dimensional macroporous silicon structures were rendered proton conducting by filling the micropores via a surface-initiated atom transfer radical polymerization process. The morphological aspects, chemical stability, and performance of the hybrid assemblies were characterized by a set of techniques including scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, nuclear magnetic resonance and impedance spectroscopy, among others. The fabricated silicon-poly(sodium 2-acrylamide-2-methylpropane sulfonate) hybrid membranes displayed proton conductivities in the range of 1x10(-2) S/cm. This work illustrates the potential of hybrid polymer-silicon composite membranes synthesized by pore-filling surface-initiated polymerization to create proton conducting platforms in a simple and straightforward manner. Versatility and relative ease of preparation are two key aspects that make this approach an attractive alternative for the molecular design and preparation of proton conducting systems.

Sub-100 nm silicon nanowires by laser interference lithography and metal-assisted etching.

By combining laser interference lithography and metal-assisted etching we were able to produce arrays of silicon nanowires with uniform diameters as small as 65 nm and densities exceeding 2 x 10(7) mm(-2). The wires are single crystalline, vertically aligned, arranged in a square pattern and obey strict periodicity over several cm(2). The applied technique allows for a tailoring of nanowire size and density. Using a controlled and scalable process to fabricate sub-100 nm silicon nanowires is an important step towards the realization of cost-effective electronic and thermoelectric devices.

Reducing stress on cells with apoferritin-encapsulated platinum nanoparticles.

The great potential for medical applications of inorganic nanoparticles in living organisms is severely restricted by the concern that nanoparticles can harmfully interact with biological systems, such as lipid membranes or cell proteins. To enable an uptake of such nanoparticles by cells without harming their membranes, platinum nanoparticles were synthesized within cavities of hollow protein nanospheres (apoferritin). In vitro, the protein-platinum nanoparticles show good catalytic efficiency and long-term stability. Subsequently the particles were tested after ferritin-receptor-mediated incorporation in human intestinal Caco-2 cells. Upon externally induced stress, for example, with hydrogen peroxide, the oxygen species in the cells decreased and the viability of the cells increased.

Carrier profiling of individual Si nanowires by scanning spreading resistance microscopy.

Individual silicon nanowires (NWs) doped either by ion implantation or by in situ dopant incorporation during NW growth were investigated by scanning spreading resistance microscopy (SSRM). The carrier profiles across the axial cross sections of the NWs are derived from the measured spreading resistance values and calibrated by the known carrier concentrations of the connected Si substrate or epi-layer. In the case of the phosphorus ion-implanted and subsequently annealed NWs, the SSRM profiles revealed a radial core-shell distribution of the activated dopants. The carrier concentration close to the surface of a phosphorus-doped NW is found to be by a factor of 6-7 higher than the value in the core and on average only 25% of the implanted phosphorus is electrically active. In contrast, for the in situ boron-doped NW the activation rate of the boron atoms is significantly higher than for phosphorus atoms. Some specific features of SSRM experiments of Si NWs are discussed including the possibility of three-dimensional measurements.

Synthesis of silicon nanotubes with cobalt silicide ends using anodized aluminum oxide template.

Silicon nanotubes (SiNTs) are compatible with Si-based semiconductor technology. In particular, the small diameters and controllable structure of such nanotubes are remaining challenges. Here we describe a method to fabricate SiNTs intrinsically connected with cobalt silicide ends based on highly ordered anodic aluminum oxide (AAO) templates. Size and growth direction of the SiNTs can be well controlled via the templates. The growth of SiNTs is catalyzed by the Co nanoparticles reduced on the pore walls of the AAO after annealing, with a controllable thickness at a given growth temperature and time. Simultaneously, cobalt silicide forms on the bottom side of the SiNTs.

Titania nanostructures fabricated by atomic layer deposition using spherical protein cages.

An emerging nanofabrication technology is to synthesize nanoscale inorganic materials with narrow size distribution using biological systems, which are size-constrained, fairly robust, and easily removable. Apoferritin, a spherical and hollow protein complex, was subjected to atomic layer deposition of TiO(2). The growth of TiO(2) on the protein surface was investigated as a function of the precursor exposure and purge length. Thermal pretreatment and osmotic dehydration lead to controllable deposition both on the outer surface and within the inner cavity of apoferritin. Depending on the experimental conditions, either hollow spherical nanoparticles or core-shell nanoparticles comprising TiO(2) were identified.

Near-field investigations of nanoshell cylinder dimers.

Metallic nanoparticles are known to exhibit strong particle size dependent localized surface plasmon resonances due to their specific optical response described via the complex dielectric function. Using the two-dimensional finite element method, the near-field behavior of core-shell nanocylinder dimers with either a dielectric or a gold core and a silver shell was investigated. With a detailed analysis the positions of maximum field enhancement usable for highly sensitive spectroscopy were unveiled and the surface charge distributions of the different kinds of resonances were visualized. It is shown that the usual far-field spectra do not give reliable estimates of local electric field peaks. Furthermore one observes a distinct mode at the natural plasma frequency of the silver shell which is independent of the core material. This mode is identified as a volume plasmon mode.

Are volume plasmons excitable by classical light?

Volume plasmons are collective eigenmodes of the free-electron gas inside a metal. Because of their longitudinal character and the transversal nature of light, the photoexcitation of volume plasmons is forbidden in classical electrodynamics. Nevertheless, we show their existence for metallic nanoshells using analytical solutions of the classical scattering problem. Solely for the case of a vanishing real part of the shell permittivity, a local maximum at the natural plasma frequency appears in the extinction spectra. For explaining our observations, we suggest a simple physical picture which is supported by examples on silver and gold shells.

Unexpected long-term instability of ZnO nanowires "protected" by a TiO2 shell.

We revealed the aggravated instability of (0001)-oriented ZnO nanowires when they were deposited by a TiO(2) shell even under ambient conditions. Trace UV photons from daylight and moisture from air, which generally have negligible effects on "bare" ZnO nanowires, can obviously enhance their photocorrosion due to the high bandgap of TiO(2) as well as this conformal core-shell heterostructure.

Nanoporous pt-co alloy nanowires: fabrication, characterization, and electrocatalytic properties.

Nanoporous Pt-Co alloy nanowires were synthesized by electrodeposition of Co-rich Pt(1)Co(99) alloy into anodic aluminum oxide (AAO) membranes, followed by a dealloying treatment in a mild acidic medium. These nanowires consist of porous skeletons with tiny pores of 1-5 nm and crystalline ligaments of 2-8 nm. Morphological and compositional evolutions of the porous Pt-Co nanowires upon dealloying were investigated, and their formation mechanism is discussed. The nanoporous Pt-Co alloy nanowires are found to exhibit distinctly enhanced electrocatalytic activities toward methanol oxidation as compared to the current state-of-the-art Pt/C and PtCo/C catalysts, thus showing substantial promise as efficient anode electrocatalysts in direct methanol fuel cells.

Formation of straight 10 nm diameter silicon nanopores in gold decorated silicon.

We observe pore formation with diameters in the 10 nm range in silicon when it is covered with gold particles. This pore etching occurs when the sample is put in 5 wt % hydrofluoric acid (HF) solution for a few minutes. The pores form along the 100 direction, which is also the preferred direction of macro- and mesopores electrochemically etched into silicon. No etching occurs if the dissolved oxygen is removed from the aqueous HF solution or the gold is removed from the silicon surface. This leads to the assumption that the dissolved oxygen acts as an oxidant as in the case of stain etching with gold as cathodic material. A tentative model is suggested to explain why all of the observed nanopores have roughly the same diameter of about 10 nm. These pores can occur for inhomogeneously gold-covered planar silicon surfaces but also in MBE (molecular beam epitaxy) grown silicon nanowires since these nanowires are covered unintentionally with gold nanoclusters at their cylindrical surface.