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At least 613 records · Page 34

Nanostructured electrochromic smart windows: traditional materials and NIR-selective plasmonic nanocrystals

Electrochromic devices, which dynamically change colour under applied potential, are widely studied for use in energy-efficient smart windows. To improve the viability of smart windows, many researchers are utilizing nanomaterials, which can provide electrochromic devices with improved colouration efficiencies, faster switching times, longer cycle lives, and potentially reduced costs. In an effort to demonstrate a new type of electrochromic device that goes beyond the capabilities of commonly used electrochromic materials, researchers have turned to plasmonic transparent conductive oxide (TCO) nanocrystals. Electrochemical injection of electrons into plasmonic TCO nanocrystal films induces a shift in the plasmon frequency and gives rise to the new functionality of selective optical modulation in the near-infrared region of the solar spectrum. These nanocrystals can be used as building blocks to enable creation of advanced electrochromic devices containing mesoporous electrodes or nanocrystal-in-glass composites. Such devices have been important in advancing the field towards achieving the ideal smart window with independent control over visible and NIR transmittance.

Runnerstrom, EL↗

A surface plasmon enabled liquid-junction photovoltaic cell

Plasmonic nanosystems have recently been shown to be capable of functioning as photovoltaics and of carrying out redox photochemistry, purportedly using the energetic electrons and holes created following plasmonic decay as charge carriers. Although such devices currently have low efficiency, they already manifest a number of favorable characteristics, such as their tunability over the entire solar spectrum and a remarkable resistance to photocorrosion. Here, we report a plasmonic photovoltaic using a 25 μm thick electrolytic liquid junction which supports the iodide/triiodide (I - /I 3 - ) redox couple. The device produces photocurrent densities in excess of 40 μA cm -2 , an open circuit voltage ( V oc ) of ~0.24 V and a fill factor of ~0.5 using AM 1.5 G solar radiation at 100 mW cm -2 . The photocurrent and the power conversion efficiency are primarily limited by the low light absorption in the 2-D gold nanoparticle arrays. The use of a liquid junction greatly reduces dielectric breakdown in the oxide layers utilized, which must be very thin for optimal performance, leading to a great improvement in the long-term stability of the cell's performance.

Lee, Woo-ram↗

Visualizing Surface Plasmons with Photons, Photoelectrons, and Electrons

Both photons and electrons may be used to excite surface plasmon polaritons, the collective charge density fluctuations at the surface of metal nanostructures. By virtue of their nanoscopic and dissipative nature, a detailed characterization of surface plasmon (SP) eigenmodes in real space-time ultimately requires joint sub-nanometer spatial and sub-femtosecond temporal resolution. The latter realization has driven significant developments in the past few years, aimed at interrogating both localized and propagating SP modes over the relevant length and time scales. In this mini-review, we briefly highlight different techniques we employ to visualize the enhanced electric fields associated with SPs. Specifically, we discuss recent hyperspectral optical microscopy, tip-enhanced Raman nano-spectroscopy, nonlinear photoemission electron microscopy, as well as correlated scanning transmission electron microscopy-electron energy loss spectroscopy measurements targeting prototypical plasmonic nanostructures and constructs. Through selected practical examples, we examine the information content in multidimensional images recorded by taking advantage of each of the aforementioned techniques. In effect, we illustrate how SPs can be visualized at the ultimate limits of space and time.

Environmental Molecular Sciences Laboratory↗

Intermediate selectivity in the oxidation of phenols using plasmonic Au/ZnO photocatalysts

Tunable reaction selectivity on a single catalyst is a continual goal in chemical syntheses. Herein, we report an unexpected light-directed intermediate selectivity using well-known plasmonic photocatalysts. We observed distinct intermediate selectivity behaviors between using UV and visible light irradiations. Chemical computations and quenching experiments suggest that the radicals generated by the plasmonic excitation govern the light-directed selectivity. As a result, the broader impact of this work ranges from selective yield of desirable intermediates for subsequent syntheses without tedious separation procedures, to arousing interest in examining new opportunities for plasmonic photocatalysts.

36 MATERIALS SCIENCE↗

Understanding plasmon coupling in nanoparticle dimers using molecular orbitals and configuration interaction

Here, we perform a theoretical investigation of the electronic structure and optical properties of atomic nanowire and nanorod dimers using DFT and TDDFT. In both systems at separation distances larger than 0.75 nm, optical spectra show a single feature that resembles the bonding dipole plasmon (BDP) mode. A configuration interaction (CI) analysis shows that the BDP mode arises from constructive coupling of transitions, whereas the destructive coupling does not produce significant oscillator strength for such separation distances. At shorter separation distances, both constructive and destructive coupling produce oscillator strength due to wave-function overlap, which results in multiple features in the calculated spectra. Our analysis shows that a charge-transfer plasmon (CTP) mode arises from destructive coupling of transitions, whereas the BDP results from constructive coupling of the same transitions at shorter separation distances. Furthermore, the coupling elements between these transitions are shown to depend heavily on the amount of exact Hartree–Fock exchange (HFX) in the functional, which affects the splitting of CTP and BDP modes. With 50% HFX or more, the CTP and BDP modes mainly merge into a single feature in the spectra. These findings suggest that the effects of exact exchange must be assessed during the prediction of CTP modes in plasmonic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast relaxation dynamics in bimetallic plasmonic catalysts

Combining a plasmonic metal, such as gold, with other popular catalysts, such as Ni or Pt, can extend its benefits to many energy-extensive reactions catalyzed by those metals. The efficiency of a plasmon-enhanced catalytic reaction is mainly determined by the light absorption cross section and the photoexcited charge carrier relaxation dynamics of the nanoparticles. Here we have investigated the charge carrier relaxation dynamics of gold/nickel (Au/Ni) and gold/platinum (Au/Pt) bimetallic nanoparticles. We found that the addition of Ni or Pt to gold can reduce light absorption in gold nanoparticles. However, electron–phonon coupling rates of Au/Ni and Au/Pt nanoparticles are significantly faster than that of pure Au nanoparticles. This is due to the fact that both Ni and Pt possess significantly larger electron–phonon coupling constants and higher densities of states near the Fermi level in comparison with Au. Additionally, the phonon–phonon coupling rate of bimetallic Au/Pt and Au/Ni nanoparticles was significantly different from that of pure gold nanoparticles, due to the acoustic impedance mismatch at the nanoparticle/substrate interface. Our findings provide important insights into the rational design of bimetallic plasmonic catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design-controlled synthesis of IrO 2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties

We develop herein plasmonic–catalytic Au–IrO 2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO 2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO 2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO 2 , by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au–IrO 2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO 2 and to the activation of Ir–O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A versatile strategy for controlled assembly of plasmonic metal/semiconductor hemispherical nano-heterostructure arrays

Recent advances in manipulating plasmonic properties of metal/semiconductor heterostructures have opened up new avenues for basic research and applications. Herein, we present a versatile strategy for the assembly of arrays of plasmonic metal/semiconductor hemispherical nano-heterostructures (MSHNs) with control over spacing and size of the metal/semiconductor heterostructure array, which can facilitate a wide range of scientific studies and applications. The strategy combines nanosphere lithography for generating the metal core array with solution-based chemical methods for the semiconductor shell that are widely available and kinetically controllable. Periodic arrays of Au/Cu 2 O and Ag/Cu 2 O heterostructures are synthesized to demonstrate the approach and highlight the versatility and importance of the tunability of plasmonic properties. The morphology, structure, optical properties, and elemental compositions of the heterostructures were analyzed. Finally, this strategy can be important for understanding and manipulating fundamental nanoscale solid-state physical and chemical properties, as well as assembling heterostructures with desirable structure and functionality for applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Spin-controlled plasmonics via optical Rashba effect

Observation of the optical Rashba effect in plasmonics is reported. Polarization helicity degeneracy removal, associated with the inversion symmetry violation, is attributed to the surface symmetry design via anisotropic nanoantennas with space-variant orientations. By utilizing the Rashba-induced momentum in a nanoscale kagome metastructure, we demonstrated a spin-based surface plasmon multidirectional excitation under a normal-incidence illumination. The spin-controlled plasmonics via spinoptical metasurfaces provides a route for spin-based surface-integrated photonic nanodevices and light-matter interaction control, extending the light manipulation capabilities.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Effect of graphene on plasmonic metasurfaces at infrared wavelengths

Significant enhancement of infrared transmittance by the presence of a graphene layer on a plasmonic metasurface (PLM) has been demonstrated. PLMs with different configurations were fabricated, and their transmittance with and without graphene was compared. Selective enhancement by graphene occurred at the plasmon resonance wavelength. The degree of enhancement was found to depend on the width of the gap between the periodic metal regions in the PLM. A maximum enhancement of ∼210% was achieved at a wavelength of 10 μm. The ability to achieve such a drastic increase in transmittance at the plasmon resonant wavelength is expected to lead to improvements in the performance of energy collecting devices and optical sensors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Quantum optics with single nanodiamonds flying over gold films: Towards a Robust quantum plasmonics

A nanodiamond (ND) hosting nitrogen-vacancy (NV) color centers is attached on the apex of an optical tip for near-field microscopy. Its fluorescence is used to launch surface plasmon-polaritons (SPPs) in a thin polycrystalline gold film. It is shown that the quantum nature of the initial source of light is preserved after conversion to SPPs. This opens the way to a deterministic quantum plasmonics, where single SPPs can be injected at well-defined positions in a plasmonic device produced by top-down approaches.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hybrid plasmonic waveguide in a metal V-groove

We propose and investigate a type of hybrid plasmonic waveguide in a metal V-groove. A high-permittivity nanowire was placed in the metal channel covered with a dielectric film of lower permittivity. Deeper sub-wavelength confinement and much longer propagation distance were achieved in comparison with conventional channel plasmonic waveguides. The overall performance was improved as compared with the conventional hybrid plasmonic structure based on a flat metal surface. Finite element analysis showed that both the mode propagation and field profile can be adjusted by changing the nanowire radius and film thickness. Some benefits, such as a reduced scattering loss caused by the surface roughness, are also expected owing to the unique mode profile. The proposed approach has potential for application in high-level photonic integration.

36 MATERIALS SCIENCE↗

Generation of high power pulsed terahertz radiation using a plasmonic photoconductive emitter array with logarithmic spiral antennas

An array of 3 × 3 plasmonic photoconductive terahertz emitters with logarithmic spiral antennas is fabricated on a low temperature (LT) grown GaAs substrate and characterized in response to a 200 fs optical pump from a Ti:sapphire mode-locked laser at 800 nm wavelength. A microlens array is used to split and focus the optical pump beam onto the active area of each plasmonic photoconductive emitter element. Pulsed terahertz radiation with record high power levels up to 1.9 mW in the 0.1–2 THz frequency range is measured at an optical pump power of 320 mW. The record high power pulsed terahertz radiation is enabled by the use of plasmonic contact electrodes, enhancing the photoconductor quantum efficiencies, and by increasing the overall device active area, mitigating the carrier screening effect and thermal breakdown at high optical pump power levels.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Resonant intersubband plasmon induced current in InGaAs quantum wells on GaAs

We present measurements of the current enhancement due to the coupling of two intersubband plasmons in In{sub 0.05}Ga{sub 0.95}As quantum wells. With changing bias, an emissive and an absorptive intersubband plasmon mode cross attractively and trapped electrons in the ground state gain enough energy from the plasma wave to be lifted up to the second subband, where they can contribute to the current. This effect can be directly observed as an increase of 33% in the current. A magnetic field applied parallel to the growth direction allows a control of the strength of the intersubband plasmon coupling up to a quenching.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Simulated study of plasmonic coupling in noble bimetallic alloy nanosphere arrays

The plasmonic coupling between the interacting noble metal nanoparticles plays an important role to influence the optical properties of arrays. In this work, we have extended the Mie theory results of our recent communication to include the effect of particle interactions between the alloy nanoparticles by varying interparticle distance and number of particles. The localized surface plasmon resonance (LSPR) peak position, full width at half maxima (FWHM) and scattering efficiency of one dimensional (1D) bimetallic alloy nanosphere (BANS) arrays of earlier optimized compositions i.e. Ag{sub 0.75}Au{sub 0.25}, Au{sub 0.25}Cu{sub 0.75} and Ag{sub 0.50}Cu{sub 0.50} have been studied presently by using discrete dipole approximation (DDA) simulations. Studies have been made to optimize size of the nanosphere, number of spheres in the arrays, material and the interparticle distance. It has been found that both the scattering efficiency and FWHM (bandwidth) can be controlled in the large region of the electromagnetic (EM) spectrum by varying the number of interacting particles and interparticle distance. In comparison to other alloy arrays, Ag{sub 0.50}Cu{sub 0.50} BANS arrays (each of particle radius 50 nm) shows larger tunability of LSPR with wide bandwidth (essential condition for plasmonic solar cells)

36 MATERIALS SCIENCE↗

Growth of Au nanoparticle films and the effect of nanoparticle shape on plasmon peak wavelength

Metal nanoparticles (NPs) exhibit localized surface plasmon resonance (LSPR) and thus have potential for use in a wide range of applications. A facile technique for the preparation of NP films using an electron-cyclotron-resonance plasma sputtering method without a dewetting process is described. Field emission scanning electron microscopy (FE-SEM) observations revealed that the Au NPs grew independently as island-like particles during the first stage of sputtering and then coalesced with one another as sputtering time increased to ultimately form a continuous film. A plasmon absorption peak was observed via optical measurement of absorption efficiency. The LSPR peak shifted toward longer wavelengths (red shift) with an increase in sputtering time. The cause of this plasmon peak shift was theoretically investigated using the finite-difference time-domain calculation method. A realistic statistical distribution of the particle shapes based on FE-SEM observations was applied for the analysis, which has not been previously reported. It was determined that the change in the shape of the NPs from spheroidal to oval or slender due to coalescence with neighbouring NPs caused the LSPR peak shift. These results may enable the design of LSPR devices by controlling the characteristics of the nanoparticles, such as their size, shape, number density, and coverage.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Ultra-sharp plasmonic resonances from monopole optical nanoantenna phased arrays

Diffractively coupled plasmonic resonances possess both ultra-sharp linewidths and giant electric field enhancement around plasmonic nanostructures. They can be applied to create a new generation of sensors, detectors, and nano-optical devices. However, all current designs require stringent index-matching at the resonance condition that limits their applicability. Here, we propose and demonstrate that it is possible to relieve the index-matching requirement and to induce ultra-sharp plasmon resonances in an ordered vertically aligned optical nano-antenna phased array by transforming a dipole resonance to a monopole resonance with a mirror plane. Due to the mirror image effect, the monopole resonance not only retained the dipole features but also enhanced them. The engineered resonances strongly suppressed the radiative decay channel, resulting in a four-order of magnitude enhancement in local electric field and a Q-factor greater than 200.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Interaction of single quantum emitter and dark plasmon supported by a metal nanoring

We explore the interaction between a quantum emitter and a metal nanoring by numerical solution of coupled Maxwell-Liouville equations. When the quantum emitter and nanoring are subjected to an incident plane wave, coupling between the quantum emitter and a dark plasmon supported by the nanoring gives rise to a similar lineshape to the familiar Fano type. It results from the excitation of a dark plasmon via intermediary participation of the quantum emitter. The dark plasmon is characterized through the width and shift parameters of the emitter peak in the absorption spectrum of the nanoparticle. Our results are obtained with the help of finite-difference time-domain method and a recently proposed symmetry-adapted averaging approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗