We combine atomic layer lithography and glancing-angle ion polishing to create wafer-scale metamaterials composed of dense arrays of ultrasmall coaxial nanocavities in gold films. This new fabrication scheme makes it possible to shrink the diameter and increase the packing density of 2 nm-gap coaxial resonators, an extreme subwavelength structure first manufactured via atomic layer lithography, both by a factor of 100 with respect to previous studies. We demonstrate that the nonpropagating zeroth-order Fabry-Pérot mode, which possesses slow light-like properties at the cutoff resonance, traps infrared light inside 2 nm gaps (gap volume ∼ λ3/106). Notably, the annular gaps cover only 3% or less of the metal surface, while open-area normalized transmission is as high as 1700% at the epsilon-near-zero (ENZ) condition. The resulting energy accumulation alongside extraordinary optical transmission can benefit applications in nonlinear optics, optical trapping, and surface-enhanced spectroscopies. Furthermore, because the resonance wavelength is independent of the cavity length and dramatically red shifts as the gap size is reduced, large-area arrays can be constructed with λresonance ≫ period, making this fabrication method ideal for manufacturing resonant metamaterials.

We present large-scale reproducible fabrication of multifunctional ultrasharp metallic structures on planar substrates with capabilities including magnetic field nanofocusing and plasmonic sensing. Objects with sharp tips such as wedges and pyramids made with noble metals have been extensively used for enhancing local electric fields via the lightning-rod effect or plasmonic nanofocusing. However, analogous nanofocusing of magnetic fields using sharp tips made with magnetic materials has not been widely realized. Reproducible fabrication of sharp tips with magnetic as well as noble metal layers on planar substrates can enable straightforward application of their material and shape-derived functionalities. We use a template-stripping method to produce plasmonic-shell-coated nickel wedge and pyramid arrays at the wafer-scale with tip radius of curvature close to 10 nm. We further explore the magnetic nanofocusing capabilities of these ultrasharp substrates, deriving analytical formulas and comparing the results with computer simulations. These structures exhibit nanoscale spatial control over the trapping of magnetic microbeads and nanoparticles in solution. Additionally, enhanced optical sensing of analytes by these plasmonic-shell-coated substrates is demonstrated using surface-enhanced Raman spectroscopy. These methods can guide the design and fabrication of novel devices with applications including nanoparticle manipulation, biosensing, and magnetoplasmonics.

With strong light-matter interaction in their atomically thin layered structures, two-dimensional (2D) materials have been widely investigated for optoelectronic applications such as photodetectors and photovoltaic devices. Depending on the aim of optoelectronic applications, different device structures have been employed. Lateral phototransistor structures have been employed for high optical gain, while vertical photodiode structures have been employed for fast response and low power operation. Herein, we demonstrate a multimodal photodetector platform based on 2D materials, combining both a phototransistor and a photodiode and taking the corresponding desirable characteristics from each structure within a single device. In this platform, a multilayered transition-metal dichalcogenide flake is transferred on top of metal electrodes, and a transparent gate electrode is employed. The channel region of the flake between electrodes operates as a phototransistor providing a high gain mode, while the electrode region in the same flake operates as a vertical Schottky photodiode providing a fast response mode. These modes can be dynamically selected by controlling the drain voltage and gate voltage.

University of Minnesota Masters of Science thesis. May 2015. Major: Electrical Engineering. Advisor: Sang-Hyun Oh. 1 computer file (PDF); iv, 47 pages.

Purpose To evaluate multiple MRI parameters in a surgical model of osteochondrosis (OC) in goats. Methods Focal ischemic lesions of two different sizes were induced in the epiphyseal cartilage of the medial femoral condyles of goats at 4 days of age by surgical transection of cartilage canal blood vessels. Goats were euthanized and specimens harvested 3, 4, 5, 6, 9 and 10 weeks post-op. Ex vivo MRI scans were conducted at 9.4 Tesla for mapping the T1, T2, T1ρ, adiabatic T1ρ and TRAFF relaxation times of articular cartilage, unaffected epiphyseal cartilage, and epiphyseal cartilage within the area of the induced lesion. After MRI scans, safranin O staining was conducted to validate areas of ischemic necrosis induced in the medial femoral condyles of six goats, and to allow comparison of MRI findings with the semi-quantitative proteoglycan assessment in corresponding safranin O-stained histological sections. Results All relaxation time constants differentiated normal epiphyseal cartilage from lesions of ischemic cartilage necrosis, and the histological staining results confirmed the proteoglycan (PG) loss in the areas of ischemia. In the scanned specimens, all of the measured relaxation time constants were higher in the articular than in the normal epiphyseal cartilage, consistently allowing differentiation between these two tissues. Conclusions Multiparametric MRI provided a sensitive approach to discriminate between necrotic and viable epiphyseal cartilage and between articular and epiphyseal cartilage, which may be useful for diagnosing and monitoring OC lesions and, potentially, for assessing effectiveness of treatment interventions.

Amyotrophic lateral sclerosis (ALS) is a devastating, fatal neurologic disease that primarily affects spinal cord anterior horn cells and their axons for which there is no treatment. Here we report the use of a recombinant natural human IgM that binds to the surface of neurons and supports neurite extension, rHIgM12, as a therapeutic strategy in murine models of human ALS. A single 200 µg intraperitoneal dose of rHIgM12 increases survival in two independent genetic-based mutant SOD1 mouse strains (SOD1G86R and SOD1G93A) by 8 and 10 days, delays the onset of neurologic deficits by 16 days, delays the onset of weight loss by 5 days, and preserves spinal cord axons and anterior horn neurons. Immuno-overlay of thin layer chromatography and surface plasmon resonance show that rHIgM12 binds with high affinity to complex gangliosides GD1a and GT1b. Addition of rHIgM12 to neurons in culture increases α-tubulin tyrosination levels, suggesting an alteration of microtubule dynamics. We previously reported that a single peripheral dose of rHIgM12 preserved neurologic function in a murine model of demyelination with axon loss. Because rHIgM12 improves three different models of neurologic disease, we propose the IgM may act late in the cascade of neuronal stress and/or death by a broad mechanism.

Gradient fields of optical, magnetic, or electrical origin are widely used for the manipulation of micro- and nanoscale objects. Among various device geometries to generate gradient forces, sharp metallic tips are one of the most effective. Surface roughness and asperities present on traditionally produced tips reduce trapping efficiencies and limit plasmonic applications. Template-stripped, noble metal surfaces and structures have sub-nm roughness and can overcome these limits. We have developed a process using a mix of conductive and dielectric epoxies to mount template-stripped gold pyramids on tungsten wires that can be integrated with a movable stage. When coupled with a transparent indium tin oxide (ITO) electrode, the conductive pyramidal tip functions as a movable three-dimensional dielectrophoretic trap which can be used to manipulate submicrometer-scale particles. We experimentally demonstrate the electrically conductive functionality of the pyramidal tip by dielectrophoretic manipulation of fluorescent beads and concentration of single-walled carbon nanotubes, detected with fluorescent microscopy and Raman spectroscopy.

We evaluate and compare the sensitivity of gold nanodisks on silica substrates and nanoholes made in silica-supported gold films, two of the most common sensor structures used in plasmonic biosensing. An alumina overcoat was applied by atomic layer deposition (ALD) to precisely control the interfacial refractive index and determine the evanescent plasmonic field decay length. The results are in good agreement with analytical models and biomolecular binding experiments for the two substrates. We found that nanodisks outperform nanoholes for thin dielectric coatings ( ∼20 nm). The optimum nanoplasmonic transducer element for a given biorecognition reaction can be chosen based on experimentally determined bulk sensitivities/noise levels and theoretically estimated evanescent field decay lengths.

We report distinctive nonlinear behavior of photoluminescence (PL) intensities from localized exciton states embedded in single-walled carbon nanotubes (SWNTs) at room temperature. We found that PL from the local states exhibits strong nonlinear behavior with increasing continuous-wave excitation power density, whereas free exciton PL shows only weak sublinear behavior. The strong nonlinear behavior was observed regardless of the origin of the local states and found to be nearly independent of the local state density. These results indicate that the strong PL nonlinearity arises from a universal mechanism to SWNTs with sparse local states. The significant nonlinear PL is attributed to rapid ground-state depletion of the local states caused by an efficient accumulation of photogenerated free excitons into the sparse local states through one-dimensional diffusional migration of excitons along the nanotube axis; this mechanism is verified by Monte Carlo simulations of exciton diffusion dynamics.

We demonstrate broadband non-resonant squeezing of terahertz (THz) waves through an isolated 2-nm-wide, 2-cm-long slit (aspect ratio of 107), representing a maximum intensity enhancement factor of one million. Unlike resonant nanogap structures, a single, effectively infinitely-long slit passes incident electromagnetic waves with no cutoff, enhances the electric field within the gap with a broad 1/f spectral response and eliminates interference effects due to finite sample boundaries and adjacent elements. To construct such a uniform, isolated slit that is much longer than the millimeter-scale spot of a THz beam, we use atomic layer lithography to pattern vertical nanogaps in a metal film over an entire 4-inch wafer. We observe an increasing field enhancement as the slit width decreases from 20 nm to 2 nm, in agreement with numerical calculations.

We present a study of free carrier photogeneration and multicarrier bound states, such as biexcitons and trions (charged excitons), in semiconducting single-walled carbon nanotubes. Pump-and-probe measurements performed with fs pulses reveal the effects of strong Coulomb interactions between carriers on their dynamics. Biexciton formation by optical transition from exciton population results in an induced absorption line (binding energy 130 meV). Exciton-exciton annihilation process is shown to evolve at high densities towards an Auger process that can expel carriers from nanotubes. The remaining carriers give rise to an induced absorption due to trion formation (binding energy 190 meV). These features show the dynamics of exciton and free carriers populations.

Stilbenoids are of great interest on account of their many promising biological activities, especially in regards to prevention and potential treatment of many chronic diseases associated with aging. The simple stilbenoid monomer, E-resveratrol, has received the most attention due to early in vitro and in vivo biological activities in anti-aging assays. Since Vitis vinifera, primarily in the form of wine, is a major dietary source of these compounds, there is a tremendous amount of research on resveratrol in wine and grapes. Relatively few biological studies have been performed on other stilbenoids from Vitis, primarily due to the lack of commercial sources of many of these compounds. The diverse stilbenoids from this economically important genus are an untapped source of health promoting compounds and because of this, numerous efforts for isolation, identification and quantification of additional stilbenoids have been ongoing. Additionally, due to their role as phytoalexins, stilbenoids play an important role in the defense against pathogens. Therefore, the compounds produced by highly resistant strains are of great interest for the development of resistant crops, natural spray reagents, and as new dietary supplements or pharmaceuticals. Since closely related species are likely to have similar metabolic pathways, a more thorough understanding of the chemical diversity of stilbenoids within Vitis is useful in this endeavor. In this review, we focus on stilbenoids found in the Vitis genus with the aim of aiding future stilbenoid chemistry, particularly in V. vinifera and wine. Additionally, we discuss the efforts to quantify stilbenoids in Vitis, with a focus on non-resveratrol stilbenoid compounds.

We have overcome the cost and time consumption limitations of common lithography techniques used to control the self-assembly of block copolymers into highly ordered 2D arrays through the use of a guiding pattern created from a polymeric sub-layer. The guiding pattern is a sinusoidal surface-relief grating interferometrically inscribed onto an azobenzene containing copolymer sub-layer leading to a defect-free single grain of block copolymer domains.

We present evidence of all-optical trion generation and emission in pristine single-walled carbon nanotubes (SWCNTs). Luminescence spectra, recorded on individual SWCNTs over a large cw excitation intensity range, show trion emission peaks redshifted with respect to the bright exciton peak. Clear chirality dependence is observed for 22 separate SWCNT species, allowing for determination of electron-hole exchange interaction and trion binding energy contributions. Luminescence data together with ultrafast pump-probe experiments on chirality-sorted bulk samples suggest that exciton-exciton annihilation processes generate dissociated carriers that allow for trion creation upon a subsequent photon absorption event.

We have measured the dynamic alignment properties of single-walled carbon nanotube (SWNT) suspensions in pulsed high magnetic fields through linear dichroism spectroscopy. Millisecond-duration pulsed high magnetic fields up to 56 T as well as microsecond-duration pulsed ultrahigh magnetic fields up to 166 T were used. Because of their anisotropic magnetic properties, SWNTs align in an applied magnetic field, and because of their anisotropic optical properties, aligned SWNTs show linear dichroism. The characteristics of their overall alignment depend on several factors, including the viscosity and temperature of the suspending solvent, the degree of anisotropy of nanotube magnetic susceptibilities, the nanotube length distribution, the degree of nanotube bundling, and the strength and duration of the applied magnetic field. To explain our data, we have developed a theoretical model based on the Smoluchowski equation for rigid rods that accurately reproduces the salient features of the experimental data.

The tubular nature of single-walled carbon nanotube (SWCNT) crystals allows them to exhibit non-intuitive quantum phenomena when threaded by a magnetic flux, which breaks the time reversal symmetry and adds an Aharonov-Bohm phase to the circumferential boundary conditions on the electronic wave function. We demonstrate that such a symmetry-breaking magnetic field can dramatically "brighten" an optically-inactive, or dark, exciton state at low temperature. This phenomenon, magnetic brightening, can be understood as a consequence of interplay between the strong intervalley Coulomb mixing and field-induced lifting of valley degeneracy. Most recently, we made the direct observation of the dark excitonic state in individual SWCNTs using low-temperature micro-photoluminescence (PL) and and verified the importance of a parallel, tube-threading magentic field with ensemble spectroscopy. For micro-PL, a magnetic field up to 5 T, applied along the nanotube axis, brightened the dark state, leading to the emergence of a new emission peak. The peak rapidly grew in intensity with increasing field at the expense of the originally-dominant bright exciton peak and finally became dominant at fields > 3 T. The directly measured dark-bright splitting values were 1-4 meV for tube diameters 1.0-1.3 nm. For ensemble PL, we used fields up to 55 T in two collection geometries to demonstrate the importance of the tube-threading component. These experiments have provided one of the most critical tests for recently-proposed theories of 1-D excitons taking into account the strong 1-D Coulomb interactions and unique band structure on an equal footing.