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At least 1,747 records · Page 97

3D Bacterial flagella as both synthetic biotemplates and ultrathin spacers for enhanced inter-particle coupling and solar energy harvesting

Linear light-absorbing nanomaterials are ideal for film-based solar harvesting applications as they form porous structures that can maximize the absorption and minimize the reflection of the solar light. Conventional 1D nanochains of plasmonic nanoparticle assemblies can achieve significantly broadened optical absorption through surface plasmon coupling, but their optical bands are still not broad enough to absorb through the solar spectrum and thus are not efficient solar absorbers. Here we discovered first by simulation that 3D structured nanochains of plasmonic nanoparticles presented a remarkably increased optical broadening effect and much longer redshift of the optical peaks due to the enhanced inter-particle coupling effect. Then we fabricated 3D nanochains by assembling gold nanoparticles (AuNPs) around 14 nm ultrathin bionanofibers, the bacterial flagella. Additionally, the ultrathin biotemplates enabled the 3D arrangement of 50 nm AuNPs along the nanofiber with a very small inter-particle gap, allowing the strong coupling of surface plasmons in a 3D manner. Consistent with the theoretical prediction, the 3D nanochains, when assembled into films, could effectively convert nearly the full spectrum of solar energy into heat, which was further efficiently converted into electricity through a thermoelectric generation unit. Our work represents a nanobiomaterial approach to highly efficient solar thermal power generation.

36 MATERIALS SCIENCE↗

Electron energy loss spectroscopy of gold nanoparticles on graphene

Plasmon excitation decay by absorption, scattering, and hot electron transfer has been distinguished from effects induced by incident photons for gold nanoparticles on graphene monolayer using electron energy loss spectroscopy (EELS). Gold nano-ellipses were evaporated onto lithographed graphene, which was transferred onto a silicon nitride transmission electron microscopy grid. Plasmon decay from lithographed nanoparticles measured with EELS was compared in the absence and presence of the graphene monolayer. Measured decay values compared favorably with estimated radiative and non-radiative contributions to decay in the absence of graphene. Graphene significantly enhanced low-energy plasmon decay, increasing mode width 38%, but did not affect higher energy plasmon or dark mode decay. This decay beyond expected radiative and non-radiative mechanisms was attributed to hot electron transfer, and had quantum efficiency of 20%, consistent with previous reports.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Temperature-dependent optical properties of titanium nitride

The refractory metal titanium nitride is promising for high-temperature nanophotonic and plasmonic applications, but its optical properties have not been studied at temperatures exceeding 400 °C. In this study, we perform in-situ high-temperature ellipsometry to quantify the permittivity of TiN films from room temperature to 1258 °C. We find that the material becomes more absorptive at higher temperatures but maintains its metallic character throughout visible and near infrared frequencies. X-ray diffraction, atomic force microscopy, and mass spectrometry confirm that TiN retains its bulk crystal quality and that thermal cycling increases the surface roughness, reduces the lattice constant, and reduces the carbon and oxygen contaminant concentrations. The changes in the optical properties of the material are highly reproducible upon repeated heating and cooling, and the room-temperature properties are fully recoverable after cooling. Using the measured high-temperature permittivity, we compute the emissivity, surface plasmon polariton propagation length, and two localized surface plasmon resonance figures of merit as functions of temperature. Our results indicate that titanium nitride is a viable plasmonic material throughout the full temperature range explored.

36 MATERIALS SCIENCE↗

Surface collective modes in the topological insulators Bi 2 Se 3 and Bi 0.5 Sb 1.5 Te 3-x Se x

In this study, we used low-energy, momentum-resolved inelastic electron scattering to study surface collective modes of the three-dimensional topological insulators Bi 2 Se 3 and Bi 0.5 Sb 1.5 Te 3-x Se x . Our goal was to identify the “spin plasmon” predicted by Raghu and co-workers [Phys. Rev. Lett. 104, 116401 (2010)]. Instead, we found that the primary collective mode is a surface plasmon arising from the bulk, free carriers in these materials. This excitation dominates the spectral weight in the bosonic function of the surface χ''(q,ω) at THz energy scales, and is the most likely origin of a quasiparticle dispersion kink observed in previous photoemission experiments. Our study suggests that the spin plasmon may mix with this other surface mode, calling for a more nuanced understanding of optical experiments in which the spin plasmon is reported to play a role.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Case studies in surface photochemistry on metal nanoparticles

The authors give a survey of their work on photochemical processes at silver nanoparticles carried out in Berlin in the past decade. Using well established procedures for the preparation of silver nanoparticles (Ag NPs) supported on ultrathin alumina layers on NiAl single crystals, they have investigated the photoreactions of adsorbed (NO){sub 2} and of Xe induced by laser pulses. The authors examined the influences of photon energy (2.3, 3.5, and 4.7 eV) and polarization, mean particle size (2–10 nm), and pulse length (5 ns and 100 fs) on yields and cross sections, and on photoreaction mechanisms. Comparison with Ag(111) was made throughout. For the NO dimer layer, the authors find general agreement with known results on bulk Ag(111) in terms of possible reactions (NO desorption and NO monomer formation as well as conversion into adsorbed N{sub 2}O and O) and predominant mechanism (via transient negative ion formation, TNI); NO desorption is the strongest channel. However, on the NPs, the cross sections show selective enhancement in particular under conditions of excitation of the Mie plasmon due to the field enhancement caused by it, but—more weakly—also under off-resonant conditions which the authors interpret by excitation confinement in the NPs. For ns laser pulses, the desorption yield responds linearly to photon flux so that the cross sections are independent of laser fluence. Using fs laser pulses, nonlinear yield response is found under plasmon excitation which is interpreted as due to re-excitation of hot electrons in the NPs during a single laser pulse. The dynamics of the individual process, however, stay the same under almost all conditions, as indicated by constant energy distributions over translational, rotational, and vibrational energies of the desorbing NO molecules, even in the nonlinear range. Only for the highest photon energy (i.e., off-resonance) and the smallest particles, a new channel is observed with higher translational energy which is believed to proceed via transient positive ions. The branching into the various reaction channels is found to be different on Ag NPs from that on Ag(111) which is ascribed to differing enhancements for the various channels. While these results show that for a typical molecular reaction only the yields are modified on NPs, very different behavior is observed for desorption of adsorbed Xe. Here, low intensity excitation of the Mie plasmon leads to chaotic response which must be due to hot spot formation. As in this case no simple desorption mechanism (via transient negative or positive ions, or direct HOMO–LUMO excitation of the adsorbate) is expected, a direct action of the plasmon excitation is postulated. Some general conclusions are drawn from these case studies.

36 MATERIALS SCIENCE↗

Surface-Enhanced Raman Scattering (SERS) Studies of Disc-on-Pillar (DOP) Arrays: Contrasting Enhancement Factor with Analytical Performance

The use of nanomachining methods capable of reproducible construction of nano-arrayed devices have revolutionized the field of plasmonic sensing by the introduction of a diversity of rationally engineered designs. Significant strides have been made to fabricate plasmonic platforms with tailored interparticle gaps to improve their performance for surface-enhanced Raman scattering (SERS) applications. Over time, a dichotomy has emerged in the implementation of SERS for analytical applications, the construction of substrates, optimization of interparticle spacing as a means to optimize electromagnetic field enhancement at the localized surface plasmon level, and the substrate sensitivity over extended areas to achieve quantitative performance. Here, we assessed the enhancement factor of plasmonic Ag/SiO 2 /Si disc-on-pillar (DOP) arrays of variable pitch with its analytical performance for quantitative applications. Experimental data were compared with those from finite-difference time-domain (FDTD) simulations used in the optimization of the array dimensions. A self-assembled monolayer (SAM) of benzenethiol rendered highly reproducible signals (RSD ~4–10%) and SERS substrate enhancement factor (SSEF) values in the orders of 10 6 –10 8 for all pitches. Furthermore, spectra corresponding to rhodamine 6G (R6G) and 4-aminobenzoic acid demonstrated the advantages of using the more densely packed DOP arrays with a 160 nm pitch (gap= 40 nm) for quantitation in spite of the strongest SSEF was attained for a pitch of 520 nm corresponding to a 400 nm gap.

36 MATERIALS SCIENCE↗

New amphiphilic complexes with luminescent rare-earth ions

Organic compounds containing luminous rare-earth ions are of interest for numerous nanophotonic and plasmonic applications, including nanoscale lasers, biosensors, and optical magnetism studies. Optical studies of Eu 3+ complexes revealed that ultra-thin LB monolayers are highly luminescent even when deposited directly on plasmonic metal, which makes these materials very promising for plasmonic applications and studies, including control and enhancement of magnetic dipole emission with a plasmonic environment. In this work, we synthesize amphiphilic complexes with various rare-earth ions Nd 3+ , Yb 3+ , and DPT ligands and show that they all are suitable for monolayer or multilayer deposition with the Langmuir–Blodgett (LB) technique. Graphical abstract

36 MATERIALS SCIENCE↗

Unique optical excitations in topological insulators (Final Technical Report)

The overall objective of this research is to understand how light interacts with topological insulator (TI) films and layered structures. Unlike normal materials, the electrons in TI films are trapped at the top and bottom surfaces of the film. These electrons have unusual properties, including low mass and high velocity. Light shining on these trapped electrons will excite electron density waves, called plasmons, which inherit the unusual properties of the electrons. This project aims to understand how these plasmons interact with each other and how the plasmon properties change as the film dimensions change. By controlling the physical properties of the films, the optical response of the film can also be controlled. In addition to single TI films, the project will also investigate the properties of stacks of TI films layered with normal insulating films. Stacking these materials results in multiple layers of trapped electrons whose plasmons can interact in ever more complex ways. After these interactions are understood, we can begin to engineer complex TI structures to obtain designer optical phenomena in the far-infrared and THz, wavelength ranges of interest for environmental monitoring and chemical sensing. This research directly addresses DOE Grand Challenges, including understanding how properties of matter emerge from complex electronic correlations and learning how to control these properties as well as the mission of the Basic Energy Sciences program to understand and control matter at the electronic/atomic level.

36 MATERIALS SCIENCE↗

Fabrication of Periodic Gold Nanocup Arrays Using Colloidal Lithography

Within recent years, the field of plasmonics has exploded as researchers have demonstrated exciting applications related to chemical and optical sensing in combination with new nanofabrication techniques. A plasmon is a quantum of charge density oscillation that lends nanoscale metals such as gold and silver unique optical properties. In particular, gold and silver nanoparticles exhibit localized surface plasmon resonances—collective charge density oscillations on the surface of the nanoparticle—in the visible spectrum. Here, we focus on the fabrication of periodic arrays of anisotropic plasmonic nanostructures. These half-shell (or nanocup) structures can exhibit additional unique light-bending and polarization dependent optical properties that simple isotropic nanostructures cannot. Researchers are interested in the fabrication of periodic arrays of nanocups for a wide variety of applications such as low-cost optical devices, surface-enhanced Raman scattering, and tamper indication. We present a scalable technique based on colloidal lithography in which it is possible to easily fabricate large periodic arrays of nanocups using spin-coating and self-assembled commercially available polymeric nanospheres. Electron microscopy and optical spectroscopy from the visible to near-IR was performed to confirm successful nanocup fabrication. We conclude with a demonstration of the transfer of nanocups to a flexible, conformal adhesive film.

nano↗

Inelastic tunnel diodes

Power is extracted from plasmons, photons, or other guided electromagnetic waves at infrared to midultraviolet frequencies by inelastic tunneling in metal-insulator-semiconductor-metal diodes. Inelastic tunneling produces power by absorbing plasmons to pump electrons to higher potential. Specifically, an electron from a semiconductor layer absorbs a plasmon and simultaneously tunnels across an insulator into metal layer which is at higher potential. The diode voltage determines the fraction of energy extracted from the plasmons; any excess is lost to heat.

Anderson, L. M.↗

Surface-PlasmonoDielectric-polaritonic devices and systems

There is provided a structure for supporting propagation of surface plasmon polaritons. The structure includes a plasmonic material region and a dielectric material region, disposed adjacent to a selected surface of the plasmonic material region. At least one of the plasmonic material region and the dielectric material region have a dielectric permittivity distribution that is specified as a function of depth through the corresponding material region. This dielectric permittivity distribution is selected to impose prespecified group velocities, v.sub.gj, on a dispersion relation for a surface polaritonic mode of the structure for at least one of a corresponding set of prespecified frequencies, .omega..sub.j, and corresponding set of prespecified wavevectors, where j=1 to N.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Sensor devices comprising a metal-organic framework material and methods of making and using the same

Disclosed herein are embodiments of sensor devices comprising a sensing component able to determine the presence of, detect, and/or quantify detectable species in a variety of environments and applications. The sensing components disclosed herein can comprise MOF materials, plasmonic nanomaterials, or combinations thereof. In an exemplary embodiment, light guides can be coupled with the sensing components described herein to provide sensor devices capable of increased NIR detection sensitivity in determining the presence of detectable species, such as gases and volatile organic compounds. In another exemplary embodiment, optical properties of the plasmonic nanomaterials combined with MOF materials can be monitored directly to detect analyte species through their impact on external conditions surrounding the particle or as a result of charge transfer to and from the plasmonic material as a result of interactions with the plasmonic material and/or the MOF material.

36 MATERIALS SCIENCE↗

Spasers to speed up CMOS processors

A processor includes a transistor pair of a first transistor and a second transistor. The first transistor of the transistor pair is coupled to a Spaser and configured to output a drive current to the Spaser to pump the Spaser. Responsive to the drive current, the Spaser outputs surface plasmon polaritons (SPPs) which are fed to a plasmonic interconnect wire. The plasmonic interconnect wire propagates the SPPs. Further, the SPPs propagated on the plasmonic interconnect wire are detected by a phototransistor. Responsive to detecting the SPPs, the phototransistor generates an output current that is fed to a gate terminal of the second transistor to charge the second transistor.

42 ENGINEERING↗

Tunable graphene-based infrared reflectance filter having patterned nanoantenna layer and unpatterned graphene layer

An actively tunable optical filter can control the amplitude of reflected infrared light. The filter exploits the dependence of the excitation energy of plasmons in a continuous and unpatterned sheet of graphene, on the Fermi-level, which can be controlled by conventional electrostatic gating. An exemplary filter enables simultaneous modification of two distinct spectral bands whose positions are dictated by the device geometry and graphene plasmon dispersion. Within these bands, the reflected amplitude can be varied by over 15% and resonance positions can be shifted by over 90 cm−1. Electromagnetic simulations verify that tuning arises through coupling of incident light to graphene plasmons by a nanoantenna grating structure. Importantly, the tunable range is determined by a combination of graphene properties, device structure, and the surrounding dielectrics, which dictate the plasmon dispersion. Thus, the underlying design is applicable across a broad range of infrared frequencies.

Beechem, III, Thomas Edwin↗

Synthesis and application of a metal ion coordinating ionic liquid monomer: Towards size and dispersity control of nanoparticles formed within a structured polyelectrolyte

Here, the design, synthesis, and characterization of an amphiphilic ionic liquid (IL) monomer possessing a transition metal coordinating acrylamide moiety is described. Incorporation of the acrylamide moiety is achieved by converting l-histidine into an imidazolium, followed by alkylation to introduce a decyl chain, and acrylation of the α-amino group. The acrylamide containing IL monomer and a co-monomer, poly(ethylene glycol) diacrylate (PEGDA M n 575), self-assembles into a weakly ordered 2D hexagonal lyotropic mesophase in water (34 ± 2 (w/w)%). Upon photo-irradiation of the mesophase a nanostructured polyelectrolyte retaining the 2D hexagonal structure is produced. Doping the mesophase with Au 3+ ions prior to photo-irradiation produces plasmonic Au NP copolymer composites only at a threshold mole ratio of IL monomer to gold ions (i.e., onset at 1740:1 mole ratio). At higher monomer to Au 3+ mole ratios plasmonic NPs are not formed. Evaluation of the in-situ synthesized plasmonic Au NPs by SAXS and optical spectroscopy indicate they are smaller, more uniform spherical particles that resist aggregation upon swelling and de-swelling in ethanol when compared to previously reported composites employing an IL monomer that lacks a metal ion coordination site (e.g., 3-decyl-1-vinylimidazolium IL).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared Near-Field Spectroscopy of Gold Nanotriangle Fabry-Pérot Resonances

Here, in this work, we characterize the near-field response of individual gold nanotriangles over a broad, visible-to-infrared, spectral region (200–1500 meV) using high-resolution electron energy-loss spectroscopy (EELS) performed inside of a scanning transmission electron microscope (STEM). We begin by experimentally imaging the spatial and spectral extent of each nanotriangle’s plasmonic Fabry-Pérot modes and measuring the evolution of their resonance energies with increasing edge length; thereby providing detailed information on infrared plasmon dephasing times and dispersion relations. Numerical electromagnetic simulations of the electron probe are used to interpret these experimental results and to compare the near-field electromagnetic enhancement factors of gold nanotriangles and nanorods of equal resonant energy. Taken together, this combined experimental and theoretical study provides unique insights relevant to designing noble metal plasmonic nanoparticle systems for solar energy harvesting and sensing applications in the near- and mid-infrared.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron Beam Infrared Nano-Ellipsometry of Individual Indium Tin Oxide Nanocrystals

Leveraging recent advances in electron energy monochromation and aberration correction, we record the spatially resolved infrared plasmon spectrum of individual tin-doped indium oxide nanocrystals using electron energy-loss spectroscopy (EELS). Both surface and bulk plasmon responses are measured as a function of tin doping concentration from 1–10 atomic percent. Furthermore, these results are compared to theoretical models, which elucidate the spectral detuning of the same surface plasmon resonance feature when measured from aloof and penetrating probe geometries. We additionally demonstrate a unique approach to retrieving the fundamental dielectric parameters of individual semiconductor nanocrystals via EELS. This method, devoid from ensemble averaging, illustrates the potential for electron-beam ellipsometry measurements on materials that cannot be prepared in bulk form or as thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO 2 Reduction in Aqueous Electrolytes

We report the light-induced modification of catalytic selectivity for photoelectrochemical CO 2 reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO 2 reduction on the Cu surface, while charge separation is accomplished by hot-hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts increased selectivity for CO 2 reduction over hydrogen evolution in aqueous electrolytes. Specifically, we observed that plasmon-driven CO 2 reduction increased the production of carbon monoxide and formate, while simultaneously reducing the evolution of hydrogen. Our results demonstrate an optical route toward steering the selectivity of artificial photosynthetic systems with plasmon-driven photocathodes for photoelectrochemical CO 2 reduction in aqueous media.

25 ENERGY STORAGE↗