Anthony Shoji Hall

A One-Step, Solvothermal Reduction Method for Producing Reduced Graphene Oxide Dispersions in Organic Solvents

Refluxing graphene oxide (GO) in N-methyl-2-pyrrolidinone (NMP) results in deoxygenation and reduction to yield a stable colloidal dispersion. The solvothermal reduction is accompanied by a color change from light brown to black. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images of the product confirm the presence of single sheets of the solvothermally reduced graphene oxide (SRGO). X-ray photoelectron spectroscopy (XPS) of SRGO indicates a significant increase in intensity of the C=C bond character, while the oxygen content decreases markedly after the reduction is complete. X-ray diffraction analysis of SRGO shows a single broad peak at 26.24 degrees 2theta (3.4 A), confirming the presence of graphitic stacking of reduced sheets. SRGO sheets are redispersible in a variety of organic solvents, which may hold promise as an acceptor material for bulk heterojunction photovoltaic cells, or electromagnetic interference shielding applications.

Mesostructure-Induced Selectivity in CO2 Reduction Catalysis

Gold inverse opal (Au-IO) thin films are active for CO2 reduction to CO with high efficiency at modest overpotentials and high selectivity relative to hydrogen evolution. The specific activity for hydrogen evolution diminishes by 10-fold with increasing porous film thickness, while CO evolution activity is largely unchanged. We demonstrate that the origin of hydrogen suppression in Au-IO films stems from the generation of diffusional gradients within the pores of the mesostructured electrode rather than changes in surface faceting or Au grain size. For electrodes with optimal mesoporosity, 99% selectivity for CO evolution can be obtained at overpotentials as low as 0.4 V. These results establish electrode mesostructuring as a complementary method for tuning selectivity in CO2-to-fuels catalysis.

Microporous Brookite-Phase Titania Made by Replication of a Metal–Organic Framework

Metal-organic frameworks (MOFs) provide access to structures with nanoscale pores, the size and connectivity of which can be controlled by combining the appropriate metals and linkers. To date, there have been no reports of using MOFs as templates to make porous, crystalline metal oxides. Microporous titania replicas were made from the MOF template HKUST-1 by dehydration, infiltration with titanium isopropoxide, and subsequent hydrothermal treatment at 200 °C. Etching of the MOF with 1 M aqueous HCl followed by 5% H2O2 yielded a titania replica that retained the morphology of the parent HKUST-1 crystals and contained partially ordered micropores as well as disordered mesopores. Interestingly, the synthesis of porous titania from the HKUST-1 template stabilized the formation of brookite, a rare titania polymorph.

Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels

An electrodes performance for catalytic CO2 conversion to fuels is a complex convolution of surface structure and transport effects. Using well-defined mesostructured silver inverse opal (Ag-IO) electrodes, it is demonstrated that mesostructure-induced transport limitations alone serve to increase the turnover frequency for CO2 activation per unit area, while simultaneously improving reaction selectivity. The specific activity for catalyzed CO evolution systematically rises by three-fold and the specific activity for catalyzed H2 evolution systematically declines by ten-fold with increasing mesostructural roughness of Ag-IOs. By exploiting the compounding influence of both of these effects, we demonstrate that mesostructure, rather than surface structure, can be used to tune CO evolution selectivity from less than 5 % to more than 80 %. These results establish electrode mesostructuring as a powerful complementary tool for tuning both catalyst selectivity and efficiency for CO2 conversion into fuels.

Broadband light absorption with multiple surface plasmon polariton waves excited at the interface of a metallic grating and photonic crystal.

Light incident upon a periodically corrugated metal/dielectric interface can generate surface plasmon polariton (SPP) waves. This effect is used in many sensing applications. Similar metallodielectric nanostructures are used for light trapping in solar cells, but the gains are modest because SPP waves can be excited only at specific angles and with one linear polarization state of incident light. Here we report the optical absorptance of a metallic grating coupled to silicon oxide/oxynitride layers with a periodically varying refractive index, i.e., a 1D photonic crystal. These structures show a dramatic enhancement relative to those employing a homogeneous dielectric material. Multiple SPP waves can be activated, and both s- and p-polarized incident light can be efficiently trapped. Many SPP modes are weakly bound and display field enhancements that extend throughout the dielectric layers. These modes have significantly longer propagation lengths than the single SPP modes excited at the interface of a metallic grating and a uniform dielectric. These results suggest that metallic gratings coupled to photonic crystals could have utility for light trapping in photovoltaics, sensing, and other applications.

Wafer-scale fabrication of plasmonic crystals from patterned silicon templates prepared by nanosphere lithography.

By combining nanosphere lithography with template stripping, silicon wafers were patterned with hexagonal arrays of nanowells or pillars. These silicon masters were then replicated in gold by metal evaporation, resulting in wafer-scale hexagonal gratings for plasmonic applications. In the nanosphere lithography step, two-dimensional colloidal crystals of 510 nm diameter polystyrene spheres were assembled at the air-water interface and transferred to silicon wafers. The spheres were etched in oxygen plasma in order to define their size for masking of the silicon wafer. For fabrication of metallic nanopillar arrays, an alumina film was grown over the nanosphere layer and the spheres were then removed by bath sonication. The well pattern was defined in the silicon wafer by reactive ion etching in a chlorine plasma. For fabrication of metal nanowell arrays, the nanosphere monolayer was used directly as a mask and exposed areas of the silicon wafer were plasma-etched anisotropically in SF6/Ar. Both techniques could be used to produce subwavelength metal replica structures with controlled pillar or well diameter, depth, and profile, on the wafer scale, without the use of direct writing techniques to fabricate masks or masters.

Excitation of multiple surface-plasmon-polariton waves guided by the periodically corrugated interface of a metal and a periodic multilayered isotropic dielectric material

The excitation of multiple surface-plasmon-polariton (SPP) waves guided by the periodically corrugated interface of a homogeneous metal and a periodic multilayered isotropic dielectric (PMLID) material was studied theoretically. The solution of the underlying canonical boundary-value problem (with a planar interface) indicates that multiple SPP waves of different polarization states, phase speeds, and attenuation rates can be guided by the periodically corrugated interface. Accordingly, the boundary-value problem was formulated using rigorous coupled-wave analysis and solved using a numerically stable algorithm. A linearly polarized plane wave was considered obliquely incident on a PMLID material of finite thickness and backed by a metallic surface-relief grating. The total reflectance, total transmittance, and the absorptance were calculated as functions of the incidence angle for different numbers of unit cells in the PMLID material of fixed period. The excitation of SPP waves was indicated by those peaks in the absorptance curves that were independent of the number of unit cells, and these peaks were also correlated with the solutions of a dispersion equation obtained from the canonical boundary-value problem.

Optimization of the absorption efficiency of an amorphous-silicon thin-film tandem solar cell backed by a metallic surface-relief grating.

The rigorous coupled-wave approach was used to compute the plane-wave absorptance of a thin-film tandem solar cell with a metallic surface-relief grating as its back reflector. The absorptance is a function of the angle of incidence and the polarization state of incident light; the free-space wavelength; and the period, duty cycle, the corrugation height, and the shape of the unit cell of the surface-relief grating. The solar cell was assumed to be made of hydrogenated amorphous-silicon alloys and the back reflector of bulk aluminum. The incidence and the grating planes were taken to be identical. The AM1.5 solar irradiance spectrum was used for computations in the 400-1100 nm wavelength range. Inspection of parametric plots of the solar-spectrum-integrated (SSI) absorption efficiency and numerical optimization using the differential evolution algorithm were employed to determine the optimal surface-relief grating. For direct insolation, the SSI absorption efficiency is maximizable by appropriate choices of the period, the duty cycle, and the corrugation height, regardless of the shape of the corrugation in each unit cell of the grating. A similar conclusion also holds for diffuse insolation, but the maximum efficiency for diffuse insolation is about 20% smaller than for direct insolation. Although a tin-doped indium-oxide layer at the front and an aluminum-doped zinc-oxide layer between the semiconductor material and the backing metallic layer change the optimal depth of the periodic corrugations, the optimal period of the corrugations does not significantly change.

Experimental excitation of multiple surface-plasmon-polariton waves and waveguide modes in a one-dimensional photonic crystal atop a two-dimensional metal grating

The excitation of multiple SPP waves as Floquet harmonics was demonstrated in structures fabricated as one-dimensional photonic crystals (PCs) on top of two-dimensional gold gratings. Each period of the PC comprised nine layers of silicon oxynitrides of different compositions, and each PC had either two or three periods. Absorptances for obliquely incident

Experimental excitation of the Dyakonov–Tamm wave in the grating-coupled configuration

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