Hans D. Robinson

Aluminum plasmonic nanostructures for improved absorption in organic photovoltaic devices

We model the absorption enhancement in organic photovoltaic devices induced by incorporating Al, Ag, and Au nanoparticles in the active layer. We find that Al nanoparticles should yield significantly greater enhancement than Ag or Au. This is because the much higher plasma frequency of Al ensures a better overlap between plasmon resonance and absorption band of organic semiconductors. Our predictions are verified experimentally by demonstrating enhanced absorbance in a poly(3-hexylthiophene-2,5-diyl): [6,6]-phenyl C61 butyric acid methyl ester layer with embedded functionalized Al nanoparticles.

Restricted meniscus convective self-assembly

Convective (or evaporation-induced) self-assembly is a standard technique for depositing uniform, poly-crystalline coatings of nanospheres across multiple square centimeters on the timescale of minutes. In this paper, we present a variation of this technique, where the drying meniscus is restricted by a straight-edge located approximately 100 microm above the substrate adjacent to the drying zone. Surprisingly, we find this technique to yield films at roughly twice the growth rate compared to the standard technique. We attribute this to differing rates of diffusion of vapor from the drying crystal in the two cases. We also investigate the crystal growth rate dependence on ambient relative humidity and find, contrary to some previous reports, that the growth rate depends strongly on the humidity. We introduce a model which indicates that while the length of the drying zone may increase with humidity, this alone cannot compensate for the simultaneous reduction in evaporation rate, so a lower humidity must always lead to a higher growth speed. Comparing the model to our experimental results, we find that the length of the drying zone is constant and mostly independent of parameters such as humidity and surface tension.

Probing the photonic density of states using layer-by-layer self-assembly

The process of spontaneous emission can be dramatically modified by optical microstructures and nanostructures. We have studied the modification of fluorescence dynamics using a variable thickness polymer spacer layer fabricated using layer-by-layer self-assembly with nanometer accuracy. The change in fluorescence lifetime with spacer layer thickness agrees well with theoretical predictions based on the modified photonic density of states (PDOS), and yields consistent values for the fluorophores intrinsic fluorescence lifetime and quantum yield near a dielectric as well as a plasmonic interface. Based on this observation, we further demonstrate that self-assembled fluorophores can be used to probe the modified PDOS near optical microstructures and nanostructures.

Irreversible adsorption of gold nanospheres on fiber optical tapers and microspheres

We study the adsorption of gold nanospheres onto cylindrical and spherical glass surfaces from quiescent particle suspensions. The surfaces consist of tapers and microspheres fabricated from optical fibers and were coated with a polycation, enabling irreversible nanosphere adsorption. Our results fit well with theory, which predicts that particle adsorption rates depend strongly on surface geometry and can exceed the planar surface deposition rate by over two orders of magnitude when particle diffusion length is large compared to surface curvature. This is particularly important for plasmonic sensors and other devices fabricated by depositing nanoparticles from suspensions onto surfaces with non-trivial geometries.

Negative thermal expansion in a zirconium tungstate/epoxy composite at low temperatures

We have investigated a composite of cubic α-ZrW2O8 and epoxy with a high ceramic loading for its thermal expansion properties at cryogenic temperatures. The composite was fabricated by allowing the ceramic to sediment in the epoxy resin before curing, using only the dense bottom fraction of the composite for further measurements. Density measurements and thermogravimetric analysis showed that the samples repeatably consisted of approximately 60xa0vol% tungstate without significant voids. The coefficient of thermal expansion was measured by dilatometry at temperatures from 25 to 300xa0K, and we found negative thermal expansion occurring at temperatures below about 100xa0K. The observed behavior is consistent with predictions produced by a variational model, which shows that the high ceramic loading is necessary to reliably achieve negative thermal expansion in the composite. The composite has potential applications as compensators for unwanted thermal expansion at low temperatures and for fiber-optic cryogenic temperature sensors.

Interface effects in plasmon-enhanced second- harmonic generation from self-assembled multilayer films

We have compared the plasmonic enhancement of second-order nonlinear optical (NLO) properties in two types of ionic self-assembled multilayer (ISAM) films combined with Ag nanoparticles fabricated using nanosphere lithography (NSL). The light-concentrating properties of the Ag particles lead to a marked increase in the NLO efficiencies of thin ISAM films. The induced enhancement is found to be much larger in conventional ISAM films than in films made with the hybrid covalent ISAM technique (HCISAM), even though the latter have a significantly larger intrinsic bulk second-order nonlinear susceptibility (χ(2)). The plasmonic enhancement of NLO effects is shown to be primarily an interface effect due to the short decay length of the plasmon modes. The importance of interface effects in the films has been investigated by surrounding thin ISAM and HCISAM films with NLO-inactive buffer layers, which confirmed the important role played by the interfaces, particularly for the HCISAM films.

A Fiber Bragg Grating Temperature Sensor for 2–400 K

We demonstrate fiber optic, multiplexible temperature sensing using a fiber Bragg grating (FBG) with an operational range of 2-400 K, and a temperature resolution better than 10 mK for temperatures <;12 K. This represents a significant reduction in the lowest usable temperature as well as a significant increase in sensitivity at cryogenic temperatures compared with previously reported multiplexible solutions. This is accomplished by mounting the section of the fiber with a FBG on a polytetrafluoroethylene coupon, which has a non-negligible coefficient of thermal expansion down to <;4 K. The sensors exhibit a good stability over multiple temperature cycles and acceptable sensor-to-sensor repeatability. Possible applications for this sensor include distributed temperature sensing across superconducting elements and cryogenic temperature measurements in environments where electrical measurements are impractical or unsafe.

High quality factor silica microspheres functionalized with self-assembled nanomaterials

With extremely low material absorption and exceptional surface smoothness, silica-based optical resonators can achieve extremely high cavity quality (Q) factors. However, the intrinsic material limitations of silica (e.g., lack of second order nonlinearity) may limit the potential applications of silica-based high Q resonators. Here we report some results in utilizing layer-by-layer self-assembly to functionalize silica microspheres with nonlinear and plasmonic nanomaterials while maintaining Q factors as high as 10(7). We compare experimentally measured Q factors with theoretical estimates, and find good agreement.

Two-Photon Activated Two-Photon Fluorescence and Binding of Azidocoumarin in a Gelatin Matrix

We study the creation of fluorescence patterns inside a gelatin gel by way of two-photon photoactivation of 7-azido-4-trifluoromethyl-1,2-benzopyrone (azidocomarin 151) contained in the gel matrix. As ultrafast light pulses are focused into the gel, onset of two-photon fluorescence, highly nonlinear in the applied optical power, is observed as azidocoumarin is converted into a fluorescent dye that binds to the gelatin. We fit the time dependence of the fluorescence to a model that incorporates the competition between coumarin photoactivation and photobleaching as well as the gradual degradation of the gel when it is exposed to the high intensity laser light. The model predicts that the initial rate of fluorescence onset should scale as the P4, where P is laser power, while the signal at long exposure time should scale as P3/2. The observed exponents are 4.18 and 1.34, respectively. The model allows us to estimate the cross section and quantum yield of two-photon induced photobleaching of azidocoumarin 151. The numerous technical uses of gelatin and the collagen from which it derives in areas ranging from photography to tissue engineering provide possible applications for the techniques described in this paper.

Light-Directed Patchy Particle Fabrication and Assembly from Isotropic Silver Nanoparticles

We demonstrate the creation of anisotropic patchy silver nanospheroids (AgNSs) using linearly polarized UV light and a photo-uncaging o-nitrobenzyl-based ligand, which anchors to the AgNSs by two gold-sulfur bonds. Exposure to a 1 J/cm2 dose of UV light induces a photo-uncaging reaction in the ligand that reveals a primary amine on the surface. By using linearly polarized UV light, we meter the exposure dose such that only the poles of the nanoparticle receive a full dose, limiting the photo-uncaging reaction primarily to the particles plasmonic hot spots. We reveal this anisotropy by preferentially adhering negatively charged gold nanospheres (AuNSs) to the AgNSs poles by using the electrostatic attraction between them and the positively charged primary amines generated by photo-uncaging. When the assembly is performed onto silver particles that are immobilized on a substrate, it results in nanoscale structures with a strong tendency to align with the polarization of the exposing light. This manifests in polarimetric spectroscopy as a linear dichroism aligned with the polarization direction.