Ion-induced surface relaxation: controlled bending and alignment of nanowire arrays.

It is a well-known fact that a sphere offers less surface area, and thus less surface energy, than any other arrangement of the same volume. From this perspective, all other shapes are metastable objects. In this paper, we present and discuss a manifestation of this metastability: the spontaneous alignment of free-standing amorphous nanowires towards, and ultimately parallel to, a flux of directional ion irradiation. The behavior expected from surface energy reduction is the opposite of that predicted by both theory and experiment regarding defect generation in crystalline nanowires, but is consistent with other observations on non-crystalline materials. We verify our expectations by bending and aligning finely stranded amorphous silica nanowires, noting that such nanostructures are particularly susceptible to bending through ion-induced surface energy reduction. We offer support for this mechanism through bending rate studies, thermal annealing experiments and mathematical modeling. Experimentally, we also demonstrate selective reorientation of nanowires in patterned areas, as well as conformal coating of reoriented arrays with functional materials. These capabilities offer the prospect of exploiting engineered surface anisotropies in optical, fluidic and micromechanical applications.

Synthesis of linked carbon monolayers: films, balloons, tubes, and pleated sheets.

Because of their potential for use in advanced electronic, nanomechanical, and other applications, large two-dimensional, carbon-rich networks have become an important target to the scientific community. Current methods for the synthesis of these materials have many limitations including lack of molecular-level control and poor diversity. Here, we present a method for the synthesis of two-dimensional carbon nanomaterials synthesized by Mo- and Cu-catalyzed cross-linking of alkyne-containing self-assembled monolayers on SiO(2) and Si(3)N(4). When deposited and cross-linked on flat surfaces, spheres, cylinders, or textured substrates, monolayers take the form of these templates and retain their structure on template removal. These nanomaterials can also be transferred from surface to surface and suspended over cavities without tearing. This approach to the synthesis of monolayer carbon networks greatly expands the chemistry, morphology, and size of carbon films accessible for analysis and device applications.

Low-temperature vapour-liquid-solid (VLS) growth of vertically aligned silicon oxide nanowires using concurrent ion bombardment.

Vertically aligned silicon oxide nanowires can be synthesized over a large area by a low-temperature, ion-enhanced, reactive vapour-liquid-solid (VLS) method. Synthesis of these randomly ordered arrays begins with a thin indium film deposited on a Si or SiO(2) surface. At the processing temperature of 190 degrees C, the indium film becomes a self-organized seed layer of molten droplets, receiving atomic silicon from a DC magnetron sputtering source rather than from the gaseous precursors used in conventional VLS growth. Simultaneous vigorous ion bombardment aligns the objects vertically and expedites mixing of oxygen and silicon into the indium. Silicon oxide precipitates from each droplet in the form of multiple thin strands having diameters as small as 5 nm. These strands form a single loose bundle growing normal to the surface, eventually consolidating to form one nanowire. The vertical rate of growth can reach 300 nm min(-1) in an environment containing argon, hydrogen, and traces of water vapour. This paper discusses the physical and chemical factors leading to the formation of the nanostructures. It also demonstrates how the shape of the resulting nanostructures can be further controlled by sputtering, during both VLS growth and post-VLS processing. Key technological advantages of the developed process are nanowire growth at low substrate temperatures and the ability to form aligned nanostructure arrays, without the use of lithography or templates, on any substrate onto which a thin silicon film can be deposited.

CdCl2 Treatment-Induced Enhanced Conductivity in CdTe Solar Cells Observed Using Conductive Atomic Force Microscopy.

The rear surfaces of CdTe photovoltaic devices without back contacts, grown by close-spaced sublimation (CSS), were analyzed using conductive atomic force microscopy (C-AFM). As-deposited and CdCl2-treated CdTe samples were compared to clarify the effect of the treatment on charge flow through grains and grain boundaries. The CdCl2-treated samples exhibit a more homogeneous and enhanced current flow across the grains as compared to the as-deposited samples. The grain boundaries show variable current. Under high bias, grain boundaries dominate current flow when the main junction is reverse biased and with the conducting current in reverse breakdown. Under the opposite bias conditions, where the contact of the conductive tip to the surface is reverse biased and under breakdown conditions, the current flow is uniform with little contrast between grains and grain boundaries. The results are interpreted as resulting from the improved crystallinity of the CdTe with reduced p-type doping along the grain boundaries.

Scanning Probe Microwave Reflectivity of Aligned Single-Walled Carbon Nanotubes: Imaging of Electronic Structure and Quantum Behavior at the Nanoscale.

Single-walled carbon nanotubes (SWNTs) are 1-dimensional nanomaterials with unique electronic properties that make them excellent candidates for next-generation device technologies. While nanotube growth and processing methods have progressed steadily, significant opportunities remain in advanced methods for their characterization, inspection, and metrology. Microwave near-field imaging offers an extremely versatile "nondestructive" tool for nanomaterials characterization. Herein, we report the application of nanoscale microwave reflectivity to study SWNT electronic properties. Using microwave impedance microscopy (MIM) combined with microwave impedance modulation microscopy (MIM(2)), we imaged horizontal SWNT arrays, showing the microwave reflectivity from individual nanotubes is extremely sensitive to their electronic properties and dependent on the nanotube quantum capacitance under proper experimental conditions. It is shown experimentally that MIM can be a direct probe of the nanotube-free carrier density and the details of their electronic band structure. We demonstrate spatial mapping of local SWNT impedance (MIM), the density of states (MIM(2)), and the nanotube structural morphology (AFM) simultaneously and with lateral resolution down to <50 nm. Nanoscale microwave reflectivity could have tremendous impact, enabling optimization of enriched growth processes and postgrowth purification of SWNT arrays while aiding in the analysis of the quantum physics of these important 1D materials.

Molecular scale buckling mechanics in individual aligned single-wall carbon nanotubes on elastomeric substrates.

We have studied the scaling of controlled nonlinear buckling processes in materials with dimensions in the molecular range (i.e., approximately 1 nm) through experimental and theoretical studies of buckling in individual single-wall carbon nanotubes on substrates of poly(dimethylsiloxane). The results show not only the ability to create and manipulate patterns of buckling at these molecular scales, but also, that analytical continuum mechanics theory can explain, quantitatively, all measurable aspects of this system. Inverse calculation applied to measurements of diameter-dependent buckling wavelengths yields accurate values of the Young's moduli of individual SWNTs. As an example of the value of this system beyond its use in this type of molecular scale metrology, we implement parallel arrays of buckled SWNTs as a class of mechanically stretchable conductor.

Solvent-induced self-assembly of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates: molecular weight effect.

The effect of molecular weight on the solvent-induced self-assembly of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes on silicon wafers was studied. For a series of mixed brushes with a fixed PMMA M(n) and systematically changed PS M(n), a transition in water advancing contact angle (theta(a)) from 74 degrees, the value for a flat PMMA surface, to 91 degrees, the value for a flat PS film, was observed with increasing PS M(n) after treatment with CHCl(3). Atomic force microscopy studies showed smooth surfaces for all samples. While no significant changes in surface morphologies were observed after treatment with cyclohexane, a selective solvent for PS, contact angle and XPS studies indicated that the mixed brushes with a PS M(n) slightly smaller than that of PMMA underwent self-reorganization, exhibiting a different theta(a). Intriguing surface morphologies composed of relatively ordered nanoscale domains were found from mixed brushes with PS M(n) slightly smaller than or similar to that of PMMA after treatment with acetic acid, a selective solvent for PMMA. The nanodomains are speculated to be of a micellar structure, with PS chains forming a core shielded by PMMA chains.