Scott T. Retterer

Free-standing optical gold bowtie nanoantenna with variable gap size for enhanced Raman spectroscopy.

We describe plasmonic interactions in suspended gold bowtie nanoantenna leading to strong electromagnetic field (E) enhancements. Surface-enhanced Raman scattering (SERS) was used to demonstrate the performance of the nanoantenna. In addition to the well-known gap size dependence, up to 2 orders of magnitude additional enhancement is observed with elevated bowties. The overall behavior is described by a SERS enhancement factor exceeding 10(11) along with an anomalously weak power law dependence of E on the gap size in a range from 8 to 50 nm that is attributed to a plasmonic nanocavity effect occurring when the plasmonic interactions enter a strongly coupled regime.

Surface characterization and functionalization of carbon nanofibers

Carbon nanofibers are high-aspect ratio graphitic materials that have been investigated for numerous applications due to their unique physical properties such as high strength, low density, metallic conductivity, tunable morphology, chemical and environmental stabilities, as well as compatibility with organochemical modification. Surface studies are extremely important for nanomaterials because not only is the surface structurally and chemically quite different from the bulk, but its properties tend to dominate at the nanoscale due to the drastically increased surface-to-volume ratio. This review surveys recent developments in surface analysis techniques used to characterize the surface structure and chemistry of carbon nanofibers and related carbon materials. These techniques include scanning probe microscopy, infrared and electron spectroscopies, electron microscopy, ion spectrometry, temperature-programed desorption, and atom probe analysis. In addition, this article evaluates the methods used to modif...

High-Resolution PFPE-based Molding Techniques for Nanofabrication of High-Pattern Density, Sub-20 nm Features: A Fundamental Materials Approach

Several perfluoropolyether (PFPE)-based elastomers for high-resolution replica molding applications are explored. The modulus of the elastomeric materials was increased through synthetic and additive approaches while maintaining relatively low surface tension values (<25 mN/m). Using large area (>4 in.(2)) master templates, we experimentally show the relationship between mold resolution and material properties such as modulus and surface tension for materials used in this study. A composite mold approach was used to form flexible molds out of stiff, high modulus materials that allow for replication of sub-20 nm post structures. Sub-100 nm line grating master templates, formed using e-beam lithography, were used to determine the experimental stability of the molding materials. It was observed that as the feature spacing decreased, high modulus PFPE tetramethacrylate (TMA) composite molds were able to effectively replicate the nanograting structures without cracking or tear-out defects that typically occur with high modulus elastomers.

Diffusive Dynamics of Nanoparticles in Arrays of Nanoposts

The diffusive dynamics of dilute dispersions of nanoparticles of diameter 200-400 nm were studied in microfabricated arrays of nanoposts using differential dynamic microscopy and single particle tracking. Posts of diameter 500 nm and height 10 μm were spaced by 1.2-10 μm on a square lattice. As the spacing between posts was decreased, the dynamics of the nanoparticles slowed. Moreover, the dynamics at all length scales were best represented by a stretched exponential rather than a simple exponential. Both the relative diffusivity and the stretching exponent decreased linearly with increased confinement and, equivalently, with decreased void volume. The slowing of the overall diffusive dynamics and the broadening distribution of nanoparticle displacements with increased confinement are consistent with the onset of dynamic heterogeneity and the approach to vitrification.

Characterization and Detection of Uranyl Ion Sorption on Silver Surfaces using Surface Enhanced Raman Spectroscopy

The study of the chemical behavior of uranyl species and its rapid detection is of primary environmental and nonproliferation concern. Herein, we report on a surface enhanced Raman spectroscopic study of uranyl ion (UO(2)(2+)) sorption onto the thermally vapor deposited silver particle surface. The ability of vibrational spectroscopy to characterize surface phenomenon and the remarkable sensitivity of surface enhanced Raman spectroscopy (SERS) have been introduced as an appropriate combination for the surface characterization and detection of UO(2)(2+) onto the silver surface. The appearance of symmetric stretching frequency of UO(2)(2+) around 700 cm(-1) and the disappearance of the 854 cm(-1) band are attributed to the development of a chemical bond between silver surface and uranyl species. The effects of temperature, solute-surface interaction time, and pH have been studied using silver modified polypropylene filter (PPF) substrates. Results show that under appropriate conditions, the concentration of uranyl ion as low as 20 ng/mL can be easily detected using the discussed SERS approach without any surface modification of silver nanoparticles. Moreover, an alternative SERS approach of uranyl detection is demonstrated using nanolithographically fabricated SERS substrates.

Controlling condensation and frost growth with chemical micropatterns

In-plane frost growth on chilled hydrophobic surfaces is an inter-droplet phenomenon, where frozen droplets harvest water from neighboring supercooled liquid droplets to grow ice bridges that propagate across the surface in a chain reaction. To date, no surface has been able to passively prevent the in-plane growth of ice bridges across the population of supercooled condensate. Here, we demonstrate that when the separation between adjacent nucleation sites for supercooled condensate is properly controlled with chemical micropatterns prior to freezing, inter-droplet ice bridging can be slowed and even halted entirely. Since the edge-to-edge separation between adjacent supercooled droplets decreases with growth time, deliberately triggering an early freezing event to minimize the size of nascent condensation was also necessary. These findings reveal that inter-droplet frost growth can be passively suppressed by designing surfaces to spatially control nucleation sites and by temporally controlling the onset of freezing events.

Grating couplers on porous silicon planar waveguides for sensing applications

We study the use of polymer gratings as light couplers into porous silicon planar waveguides for sensing applications. Experimental evidence of a guided mode in a grating-coupled porous silicon structure is presented, along with a study of its detuning due to waveguide infiltration with a chemical linker. All the measurements are in good agreement with simulations obtained by means of a Fourier modal method, where the porous silicon birefringence is considered. These results demonstrate that this system is potentially useful for chemical and biological sensing applications.

Self-propelled sweeping removal of dropwise condensate

Dropwise condensation can be enhanced by superhydrophobic surfaces on which the condensate drops spontaneously jump upon coalescence. However, the self-propelled jumping in prior reports is mostly perpendicular to the substrate. Here, we propose a substrate design with regularly spaced micropillars. Coalescence on the sidewalls of the micropillars leads to self-propelled jumping in a direction nearly orthogonal to the pillars and therefore parallel to the substrate. This in-plane motion in turn produces sweeping removal of multiple neighboring drops. The spontaneous sweeping mechanism may greatly enhance dropwise condensation in a self-sustained manner.

Asymmetric Wettability of Nanostructures Directs Leidenfrost Droplets

Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers ≥40 at T ≥ 325 °C. The directionality for these droplets is opposite to the direction previously exhibited by macro- and microscale Leidenfrost ratchets where movement against the tilt of the ratchet was observed. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of the widely accepted mechanism of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, linking asymmetric surface wettability to preferential directionality of dynamic Leidenfrost droplets on nanostructured surfaces.

Development and Fabrication of Nanoporous Silicon-based Bioreactors within a Microfluidic Chip

Multi-scale lithography and cryogenic deep reactive ion etching techniques were used to create ensembles of nanoporous, picolitre volume, reaction vessels within a microfluidic system. The fabrication of these vessels is described and how this process can be used to tailor vessel porosity by controlling the width of slits that constitute the vessel pores is demonstrated. Control of pore size allows the containment of nucleic acids and enzymes that are the foundation of biochemical reaction systems, while allowing smaller reaction constituents to traverse the container membrane and continuously supply the reaction. In this work, a 5.4 kb DNA plasmid was retained within the reaction vessels and labeled under microfluidic control with ethidium bromide as an initial proof-of-principle. Subsequently, a coupled enzyme reaction, in which glucose oxidase (GOX) and horseradish peroxidase (HRP) were contained and fed with a substrate solution of glucose and Amplex Red to produce fluorescent resorufin, was carried out under microfluidic control and monitored using fluorescent microscopy. The fabrication techniques presented are broadly applicable and can be adapted to produce devices in which a variety of high aspect ratio, nanoporous silicon structures can be integrated within a microfluidic network. The devices shown here are amenable to being scaled in number and organized to implement more complex reaction systems for applications in sensing and actuation as well as fundamental studies of biological reaction systems.