Kyle M. McElhinny

Direct oriented growth of armchair graphene nanoribbons on germanium

Graphene can be transformed from a semimetal into a semiconductor if it is confined into nanoribbons narrower than 10 nm with controlled crystallographic orientation and well-defined armchair edges. However, the scalable synthesis of nanoribbons with this precision directly on insulating or semiconducting substrates has not been possible. Here we demonstrate the synthesis of graphene nanoribbons on Ge(001) via chemical vapour deposition. The nanoribbons are self-aligning 3° from the Ge〈110〉 directions, are self-defining with predominantly smooth armchair edges, and have tunable width to <10 nm and aspect ratio to >70. In order to realize highly anisotropic ribbons, it is critical to operate in a regime in which the growth rate in the width direction is especially slow, <5 nm h−1. This directional and anisotropic growth enables nanoribbon fabrication directly on conventional semiconductor wafer platforms and, therefore, promises to allow the integration of nanoribbons into future hybrid integrated circuits.

Edge-induced flattening in the fabrication of ultrathin freestanding crystalline silicon sheets

Silicon nanomembranes are suspended single-crystal sheets of silicon, tens of nanometers thick, with areas in the thousands of square micrometers. Challenges in fabrication arise from buckling due to strains of over 10−3 in the silicon-on-insulator starting material. In equilibrium, the distortion is distributed across the entire membrane, minimizing the elastic energy with a large radius of curvature. We show that flat nanomembranes can be created using an elastically metastable configuration driven by the silicon-water surface energy. Membranes as thin as 6 nm are fabricated with vertical deviations below 10 nm in a central 100 μm × 100 μm area.

Magneto-responsive liquid crystalline elastomer nanocomposites as potential candidates for dynamic cell culture substrates

Recently, liquid crystalline elastomers (LCEs) have been proposed as active substrates for cell culture due to their potential to attach and orient cells, and impose dynamic mechanical signals through the application of external stimuli. In this report, the preparation of anisotropic and oriented nematic magnetic-sensitized LCEs with iron oxide nanoparticles, and the evaluation of the effect of particle addition at low concentrations on the resultant structural, thermal, thermo-mechanical, and mechanical properties is presented. Phase transformations produced by heating in alternating magnetic fields were investigated in LCEs in contact with air, water, and a common liquid cell culture medium was also evaluated. The inclusion of nanoparticles into the elastomers displaced the nematic-to-isotropic phase transition, without affecting the nematic structure as evidenced by similar values of the order parameter, while reducing the maximum thermomechanical deformations. Remote and reversible deformations of the magnetic LCEs were achieved through the application of alternating magnetic fields, which induces the nematic-isotropic phase transition through nanoparticle heat generation. Formulation parameters can be modified to allow for remote actuation at values closer to the human physiological temperature range and within the range of deformations that can affect the cellular behavior of fibroblasts. Finally, a collagen surface treatment was performed to improve compatibility with NIH-3T3 fibroblast cultures, which enabled the attachment and proliferation of fibroblasts on substrates with and without magnetic particles under quiescent conditions. The LCEs developed in this work, which are able to deform and experience stress changes by remote contact-less magnetic stimulation, may allow for further studies on the effect of substrate morphology changes and dynamic mechanical properties during in vitro cell culture.

Optically Reconfigurable Monolayer of Azobenzene Donor Molecules on Oxide Surfaces

The structural configuration of molecules assembled at organic-inorganic interfaces within electronic materials strongly influences the functional electronic and vibrational properties relevant to applications ranging from energy storage to photovoltaics. Controlling and characterizing the structural state of an interface and its evolution under external stimuli is crucial both for the fundamental understanding of the factors influenced by molecular structure and for the development of methods for material synthesis. It has been challenging to create complete molecular monolayers that exhibit external reversible control of the structure and electronic configuration. We report a monolayer/inorganic interface consisting of an organic monolayer assembled on an oxide surface, exhibiting structural and electronic reconfiguration under ultraviolet illumination. The molecular monolayer is linked to the surface through a carboxylate link, with the backbone bearing an azobenzene functional group and the head group consisting of a rhenium-bipyridine group. Optical spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray reflectivity show that closely packed monolayers are formed from these molecules via the Langmuir-Blodgett technique. Reversible photoisomerization is observed in solution and in monolayers assembled on Si and quartz substrates. The reconfiguration of these monolayers provides additional means to control excitation and charge transfer processes that are important in applications in catalysis, molecular electronics, and solar energy conversion.

Structured Layer of Rhenium Dye on SiO2 and TiO2 Surfaces by Langmuir–Blodgett Technique

We demonstrate the Langmuir-Blodgett assembly of two rhenium-bipyridine complexes containing a flexible or an aromatic bridge, and transfer of the monolayer to SiO2 and single crystal TiO2 substrates. Both of the complexes (ReEC and Re2TC) have a hydrophilic carboxylic acid group, which preferentially anchors into the water subphase, and forms stable monolayers at surface pressures up to 40 mN/m. The optimum conditions for the formation of complete monolayers of both ReEC and Re2TC were identified through characterization of the morphology by atomic force microscopy (AFM), the thickness by ellipsometry, and the surface coverage by X-ray photoelectron spectroscopy (XPS). X-ray reflectivity measurements (XRR) are consistent with the orientation of the molecules normal to the substrate, and their extension to close to their calculated maximum length. Parameters derived from XRR analysis show that there is a higher packing density for Re2TC monolayers than for ReEC monolayers, attributable to the more rigid bridge in the Re2TC molecule.

Fabrication of flat SiGe heterostructure nanomembrane windows via strain-relief patterning

The lattice mismatch between SiGe and Si in heteroepitaxial Si/SiGe/Si trilayers leads to buckling when confined nanomembrane windows formed from these heterostructures are released from silicon-on-insulator substrates. We demonstrate that large areas in which the curvature and curvature-induced strain are reduced by an order of magnitude can be produced by patterning the windows to concentrate buckling in narrow arms with low flexural rigidity supporting a flat central region. Synchrotron x-ray thermal diffuse scattering shows that the improved flatness of patterned windows permits fundamental studies with fidelity similar to what can be achieved with flat single-component Si nanomembranes.

Three-dimensional phonon population anisotropy in silicon nanomembranes

Nanoscale single-crystals possess modified phonon dispersions due to the truncation of the crystal. The introduction of surfaces alters the population of phonons relative to the bulk and introduces anisotropy arising from the breaking of translational symmetry. Such modifications exist throughout the Brillouin zone, even in structures with dimensions of several nanometers, posing a challenge to the characterization of vibrational properties and leading to uncertainty in predicting the thermal, optical, and electronic properties of nanomaterials. Synchrotron x-ray thermal diffuse scattering studies find that freestanding Si nanomembranes with thicknesses as large as 21 nm exhibit a higher scattering intensity per unit thickness than bulk silicon. In addition, the anisotropy arising from the finite thickness of these membranes produces particularly intense scattering along reciprocal-space directions normal to the membrane surface compared to corresponding in-plane directions. These results reveal the dimensions at which calculations of materials properties and device characteristics based on bulk phonon dispersions require consideration of the nanoscale size of the crystal.