Confined Chemical Fluid Deposition of Ferromagnetic Metalattices.

A magnetic, metallic inverse opal fabricated by infiltration into a silica nanosphere template assembled from spheres with diameters less than 100 nm is an archetypal example of a "metalattice". In traditional quantum confined structures such as dots, wires, and thin films, the physical dynamics in the free dimensions is typically largely decoupled from the behavior in the confining directions. In a metalattice, the confined and extended degrees of freedom cannot be separated. Modeling predicts that magnetic metalattices should exhibit multiple topologically distinct magnetic phases separated by sharp transitions in their hysteresis curves as their spatial dimensions become comparable to and smaller than the magnetic exchange length, potentially enabling an interesting class of "spin-engineered" magnetic materials. The challenge to synthesizing magnetic inverse opal metalattices from templates assembled from sub-100 nm spheres is in infiltrating the nanoscale, tortuous voids between the nanospheres void-free with a suitable magnetic material. Chemical fluid deposition from supercritical carbon dioxide could be a viable approach to void-free infiltration of magnetic metals in view of the ability of supercritical fluids to penetrate small void spaces. However, we find that conventional chemical fluid deposition of the magnetic late transition metal nickel into sub-100 nm silica sphere templates in conventional macroscale reactors produces a film on top of the template that appears to largely block infiltration. Other deposition approaches also face difficulties in void-free infiltration into such small nanoscale templates or require conducting substrates that may interfere with properties measurements. Here we report that introduction of "spatial confinement" into the chemical fluid reactor allows for fabrication of nearly void-free nickel metalattices by infiltration into templates with sphere sizes from 14 to 100 nm. Magnetic measurements suggest that these nickel metalattices behave as interconnected systems rather than as isolated superparamagnetic systems coupled solely by dipolar interactions.

Flexible Electronics: High Pressure Chemical Vapor Deposition of Hydrogenated Amorphous Silicon Films and Solar Cells (Adv. Mater. 28/2016).

On page 5939, J. V. Badding and co-workers describe the unrolling of a flexible hydrogenated amorphous silicon solar cell, deposited by high-pressure chemical vapor deposition. The high-pressure deposition process is represented by the molecules of silane infiltrating the small voids between the rolled up substrate, facilitating plasma-free deposition over a very large area. The high-pressure approach is expected to also find application for 3D nanoarchitectures.

High Pressure Chemical Vapor Deposition of Hydrogenated Amorphous Silicon Films and Solar Cells.

Thin films of hydrogenated amorphous silicon can be produced at MPa pressures from silane without the use of plasma at temperatures as low as 345 °C. High pressure chemical vapor deposition may open a new way to low cost deposition of amorphous silicon solar cells and other thin film structures over very large areas in very compact, simple reactors.

Silicon p-i-n junction fibers.

Flexible Si p-i-n junction fibers made by high pressure chemical vapor deposition offer new opportunities in textile photovoltaics and optoelectronics, as exemplified by their photovoltaic properties, gigahertz bandwidth for photodetection, and ability to waveguide light.

Confined high-pressure chemical deposition of hydrogenated amorphous silicon.

Hydrogenated amorphous silicon (a-Si:H) is one of the most technologically important semiconductors. The challenge in producing it from SiH(4) precursor is to overcome a significant kinetic barrier to decomposition at a low enough temperature to allow for hydrogen incorporation into a deposited film. The use of high precursor concentrations is one possible means to increase reaction rates at low enough temperatures, but in conventional reactors such an approach produces large numbers of homogeneously nucleated particles in the gas phase, rather than the desired heterogeneous deposition on a surface. We report that deposition in confined micro-/nanoreactors overcomes this difficulty, allowing for the use of silane concentrations many orders of magnitude higher than conventionally employed while still realizing well-developed films. a-Si:H micro-/nanowires can be deposited in this way in extreme aspect ratio, small-diameter optical fiber capillary templates. The semiconductor materials deposited have ~0.5 atom% hydrogen with passivated dangling bonds and good electronic properties. They should be suitable for a wide range of photonic and electronic applications such as nonlinear optical fibers and solar cells.

Self-transducing silicon nanowire electromechanical systems at room temperature.

Electronic readout of the motions of genuinely nanoscale mechanical devices at room temperature imposes an important challenge for the integration and application of nanoelectromechanical systems (NEMS). Here, we report the first experiments on piezoresistively transduced very high frequency Si nanowire (SiNW) resonators with on-chip electronic actuation at room temperature. We have demonstrated that, for very thin (~90 nm down to ~30 nm) SiNWs, their time-varying strain can be exploited for self-transducing the devices' resonant motions at frequencies as high as approximately 100 MHz. The strain of wire elongation, which is only second-order in doubly clamped structures, enables efficient displacement transducer because of the enhanced piezoresistance effect in these SiNWs. This intrinsically integrated transducer is uniquely suited for a class of very thin wires and beams where metallization and multilayer complex patterning on devices become impractical. The 30 nm thin SiNW NEMS offer exceptional mass sensitivities in the subzeptogram range. This demonstration makes it promising to advance toward NEMS sensors based on ultrathin and even molecular-scale SiNWs, and their monolithic integration with microelectronics on the same chip.

Suspended mechanical structures based on elastic silicon nanowire arrays.

We demonstrate a bottom-up/top-down combined method for the fabrication of horizontally suspended, well-oriented and size-controlled Si nanowire arrays. Mechanical beamlike structures composed of multiple ordered arrays consecutively linked by transversal microspacers are obtained by this method. Such structures are used to investigate the mechanical elasticity of the nanowire arrays by atomic force microscopy. Our results point out important differences in the morphology and mechanical behavior of the fabricated nanowire-based structures with respect to equivalent bulk material structures.

A general method for assembling single colloidal particle lines.

We have developed a general method for assembling colloidal particles into one-dimensional lines of single particle thickness. Well-spaced, parallel single particle lines can be readily deposited on a substrate from a dilute Langmuir-Blodgett particle monolayer via a stick-slip motion of the water-substrate contact line. The particle density within the lines is controllable by the particle concentration in the monolayer as well as the pulling speed of the substrate. Lines of a great variety of materials and sizes, ranging from a few nanometers to a few micrometers, have been demonstrated. Multiple depositions create complex patterns such as cross lines, even of different particles. The ability of placing nanoparticles into one-dimensional arrays enables the construction of higher hierarchical device structures. For example, using gold nanoparticle seeds, vertical single nanowire arrays of silicon can be grown replicating the pattern of single particle lines.

Synthesis of bifunctional polymer nanotubes from silicon nanowire templates via atom transfer radical polymerization.

As a way to control the surface properties of nanowires and nanotubes, we present a method for growing polymer from the surface of silicon/silica core/shell nanowires. After modification of nanowire surfaces with polymer initiators, Atom Transfer Radical Polymerization (ATRP) was used to grow methacrylate polymer chains from the surface. The resulting structures were characterized by SEM, TEM, and EELS. After etching the silicon cores, the resulting polymer-coated nanotubes will have hydrophilic silica cores with hydrophobic polymer shells.

Selective growth of Si nanowire arrays via galvanic displacement processes in water-in-oil microemulsions.

Galvanic displacement processes are employed in water-in-oil microemulsions to deposit gold nanoclusters selectively on Si surfaces and sidewalls. The gold clusters then serve as catalysts to achieve selective growth of vertically and laterally aligned Si nanowire arrays by chemical vapor deposition via the vapor-liquid-solid growth mechanism. The size of the gold clusters is shown to have a good correlation with the microemulsion parameters, which in turn controls the size of the synthesized nanowires.

Controlled growth of Si nanowire arrays for device integration.

Silicon nanowires were synthesized, in a controlled manner, for their practical integration into devices. Gold colloids were used for nanowire synthesis by the vapor-liquid-solid growth mechanism. Using SiCl4 as the precursor gas in a chemical vapor deposition system, nanowire arrays were grown vertically aligned with respect to the substrate. By manipulating the colloid deposition on the substrate, highly controlled growth of aligned silicon nanowires was achieved. Nanowire arrays were synthesized with narrow size distributions dictated by the seeding colloids and with average diameters down to 39 nm. The density of wire growth was successfully varied from approximately 0.1-1.8 wires/microm2. Patterned deposition of the colloids led to confinement of the vertical nanowire growth to selected regions. In addition, Si nanowires were grown directly into microchannels to demonstrate the flexibility of the deposition technique. By controlling various aspects of nanowire growth, these methods will enable their efficient and economical incorporation into devices.

Dendritic nanowire ultraviolet laser array.

Self-organized dendritic crystal growth is explored to assemble uniform semiconductor nanowires into highly ordered one-dimensional microscale arrays that resemble comb structures. The individual ZnO nanowires have uniform diameters ranging from 10 to 300 nm. They are evenly spaced on a stem with a regular periodicity of 0.1-2 micrometer. Under optical excitation, each individual ZnO nanowire serves as a Fabry-Perot optical cavity, and together they form a highly ordered nanowire ultraviolet laser array.

Single-crystal gallium nitride nanotubes.

Since the discovery of carbon nanotubes in 1991 (ref. 1), there have been significant research efforts to synthesize nanometre-scale tubular forms of various solids. The formation of tubular nanostructure generally requires a layered or anisotropic crystal structure. There are reports of nanotubes made from silica, alumina, silicon and metals that do not have a layered crystal structure; they are synthesized by using carbon nanotubes and porous membranes as templates, or by thin-film rolling. These nanotubes, however, are either amorphous, polycrystalline or exist only in ultrahigh vacuum. The growth of single-crystal semiconductor hollow nanotubes would be advantageous in potential nanoscale electronics, optoelectronics and biochemical-sensing applications. Here we report an 'epitaxial casting' approach for the synthesis of single-crystal GaN nanotubes with inner diameters of 30-200 nm and wall thicknesses of 5-50 nm. Hexagonal ZnO nanowires were used as templates for the epitaxial overgrowth of thin GaN layers in a chemical vapour deposition system. The ZnO nanowire templates were subsequently removed by thermal reduction and evaporation, resulting in ordered arrays of GaN nanotubes on the substrates. This templating process should be applicable to many other semiconductor systems.

Artificial lamellar mesostructures to WS(2) nanotubes.

A direct pyrolysis method from artificial lamellar mesostructures to nanotubes was developed for the synthesis of tungsten disulfide (WS(2)) nanotubes. In this process, a tungsten sulfide artificial lamellar mesostructure composite with intercalated cetyltrimethylammonium cations (WS-L) was prepared on the basis of the recently developed template self-assembly of anionic tungstates (WS(4)(2-)) and cationic surfactant molecules (CTA(+)) in solution under appropriate conditions. After heating of this inorganic-surfactant lamellar composite material in an argon atmosphere to 850 degrees C, bulk quantities of uniform WS(2) nanotubes with diameters of 5-37.5 nm and lengths ranging from 0.2 to 5 microm were produced, which revealed a general rolling mechanism of layered sheets for tubule formation. The observations of transmission electron microscopy are in good agreement with the proposed rolling mechanism.