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.

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.

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.

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.

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.

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.

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.

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.

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.

Vertical epitaxial wire-on-wire growth of Ge/Si on Si(100) substrate.

Vertically aligned epitaxial Ge/Si heterostructure nanowire arrays on Si(100) substrates were prepared by a two-step chemical vapor deposition method in anodic aluminum oxide templates. n-Butylgermane vapor was employed as new safer precursor for Ge nanowire growth instead of germane. First a Si nanowire was grown by the vapor liquid solid growth mechanism using Au as catalyst and silane. The second step was the growth of Ge nanowires on top of the Si nanowires. The method presented will allow preparing epitaxially grown vertical heterostructure nanowires consisting of multiple materials on an arbitrary substrate avoiding undesired lateral growth.

Nanostructured gold films for SERS by block copolymer-templated galvanic displacement reactions.

Up to now, little effort has been made to exploit large-area high-throughput patterning by block copolymer (BCP) lithography to generate nanostructured substrates with periods well below 100 nm for surface-enhanced Raman scattering (SERS). We show that simple BCP-templated galvanic displacement reactions yield dense arrays of mushroom-shaped gold nanopillars with a period of 50 nm. The nanoporous BCP films used as templates were obtained by swelling-induced reconstruction of reverse micelle monolayers deposited on silicon wafers. Coupling of adjacent mushroom caps almost impinging on each other combined with their strong local curvature results in a high spatial density of hot spots in the narrow gaps between them. Thus, substrates characterized by high SERS efficiencies are obtained.

Ordered arrays of vertically aligned [110] silicon nanowires by suppressing the crystallographically preferred <100> etching directions.

The metal-assisted etching direction of Si(110) substrates was found to be dependent upon the morphology of the deposited metal catalyst. The etching direction of a Si(110) substrate was found to be one of the two crystallographically preferred 100 directions in the case of isolated metal particles or a small area metal mesh with nanoholes. In contrast, the etching proceeded in the vertical [110] direction, when the lateral size of the catalytic metal mesh was sufficiently large. Therefore, the direction of etching and the resulting nanostructures obtained by metal-assisted etching can be easily controlled by an appropriate choice of the morphology of the deposited metal catalyst. On the basis of this finding, a generic method was developed for the fabrication of wafer-scale vertically aligned arrays of epitaxial [110] Si nanowires on a Si(110) substrate. The method utilized a thin metal film with an extended array of pores as an etching catalyst based on an ultrathin porous anodic alumina mask, while a prepatterning of the substrate prior to the metal depostion is not necessary. The diameter of Si nanowires can be easily controlled by a combination of the pore diameter of the porous alumina film and varying the thickness of the deposited metal film.

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.

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.

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.

Ex situ n and p doping of vertical epitaxial short silicon nanowires by ion implantation.

Vertical epitaxial short (200-300 nm long) silicon nanowires (Si NWs) grown by molecular beam epitaxy on Si(111) substrates were separately doped p- and n-type ex situ by implanting with B, P and As ions respectively at room temperature. Multi-energy implantations were used for each case, with fluences of the order of 10(13)-10(14) cm(-2), and the NWs were subsequently annealed by rapid thermal annealing (RTA). Transmission electron microscopy showed no residual defect in the volume of the NWs. Electrical measurements of single NWs with a Pt/Ir tip inside a scanning electron microscope (SEM) showed significant increase of electrical conductivity of the implanted NWs compared to that of a nominally undoped NW. The p-type, i.e. B-implanted, NWs showed the conductivity expected from the intended doping level. However, the n-type NWs, i.e. P- and As-implanted ones, showed one to two orders of magnitude lower conductivity. We think that a stronger surface depletion is mainly responsible for this behavior of the n-type NWs.

Wafer-scale arrays of epitaxial ferroelectric nanodiscs and nanorings.

Wafer-scale arrays of well-ordered Pb(Zr(0.2)Ti(0.8))O3 nanodiscs and nanorings were fabricated on the entire area (10 mm x 10 mm) of the SrRuO3 bottom electrode on an SrTiO3 single-crystal substrate using the laser interference lithography (LIL) process combined with pulsed laser deposition. The shape and size of the nanostructures were controlled by the amount of PZT deposited through the patterned holes and the temperature of the post-crystallization steps. X-ray diffraction and transmission electron microscopy confirmed that (001)-oriented PZT nanostructures were grown epitaxially on the SrRuO3(001) bottom electrode layer covering the (001)-oriented single-crystal substrate. The domain structures of PZT nano-islands were characterized by reciprocal space mapping using synchrotron x-ray radiation. Ferroelectric properties of each PZT nanostructure were characterized by scanning force microscopy in the piezoresponse mode.

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.

Atomic layer deposition of Al2O3 and TiO2 multilayers for applications as bandpass filters and antireflection coatings.

Al(2)O(3) and TiO(2) thin films have been deposited on Si wafers, quartz, BK7 glass, and polycarbonate substrates by atomic layer deposition (ALD). The refractive indices and growth rates of the materials have been determined by spectroscopic ellipsometry and transmission electron microscopy. The influence of substrate temperature and precursor on the refractive indices has been investigated. The refractive index of TiO(2) significantly increases with temperature, whereas the Al(2)O(3) films are temperature insensitive. The films deposited using H(2)O(2) as oxygen source show a slightly higher refractive index than the films prepared with H(2)O. Multilayer narrow-bandpass filters and broadband antireflective coatings have been designed and produced by ALD.

Highly proton-conducting self-humidifying microchannels generated by copolymer brushes on a scaffold.

Filling in the gaps: Macroporous silicon membranes modified with sulfonated polymer brushes have been synthesized by pore-filling surface polymerization (see picture) to give proton-conducting channels with tailor-made, finely tuned physicochemical characteristics. These membranes display high conductivity values (ca. 10(-2) S cm(-1)) regardless of the humidity, thus surpassing the performance of nafion.