Impact of Plasmonic and Dielectric Substrates on the Whispering-Gallery Modes in Self-Assembled Fluorescent Semiconductor Polymer Microspheres.

In this work, the impact of metallic and dielectric conducting substrates, gold and indium tin oxide (ITO)-coated glass, on the whispering gallery modes (WGMs) of semiconductor π-conjugated polymer microspheres is investigated. Hyperspectral mapping was performed to obtain the excitation-position-dependent emission spectra of the microspheres. Substrate-dependent quenching of WGMs sensitive to mode polarization was observed and explained. On a glass substrate, both transverse-electric (TE) and transverse-magnetic (TM) WGMs are quenched due to frustrated total internal reflection. On a gold substrate, however, only the TM WGMs are allowed in symmetry to leak into surface plasmons. An atomically flat gold substrate with subwavelength slits was used to experimentally verify the leakage of WGMs into the surface plasmon polaritons (SPPs). This work provides insight into the damping mechanisms of WGMs in microspheres on metallic and dielectric substrates.

Surface Plasmon Resonance Enhanced Photoelectrochemical Sensing of Cysteine Based on Au Nanoparticle-Decorated ZnO@graphene Quantum Dots.

In this work, Au nanoparticle-decorated ZnO@graphene core-shell quantum dots (Au-ZnO@graphene QDs) were successfully prepared and firstly used to modify an ITO electrode for the construction of a novel photoelectrochemical biosensor (Au-ZnO@graphene QDs/ITO). Characterization of the prepared nanomaterials was conducted using transmission electron microscopy, steady-state fluorescence spectroscopy and the X-ray diffraction method. The results indicated that the synthesized ternary nanomaterials displayed excellent photoelectrochemical performance, which was much better than that of ZnO@graphene QDs and pristine ZnO quantum dots. The graphene and ZnO quantum dots formed an effective interfacial electric field, enhancing photogenerated electron-hole pairs separation and leading to a remarkable improvement in the photoelectrochemical performance of ZnO@graphene QDs. The strong surface plasmon resonance effect achieved by directly attaching Au nanoparticles to ZnO@graphene QDs led to a notable increase in the photocurrent response through electrochemical field effect amplification. Based on the specifical recognition between cysteine and Au-ZnO@graphene QDs/ITO through the specificity of Au-S bonds, a light-driven photoelectrochemical sensor was fabricated for cysteine detection. The novel photoelectrochemical biosensor exhibited outstanding analytical capabilities in detecting cysteine with an extremely low detection limit of 8.9 nM and excellent selectivity. Hence, the Au-ZnO@graphene QDs is a promising candidate as a novel advanced photosensitive material in the field of photoelectrochemical biosensing.

Modal Symmetry Controlled Second-Harmonic Generation by Propagating Plasmons.

A new concept for second-harmonic generation (SHG) in an optical nanocircuit is proposed. We demonstrate both theoretically and experimentally that the symmetry of an optical mode alone is sufficient to allow SHG even in centro-symmetric structures made of centro-symmetric material. The concept is realized using a plasmonic two-wire transmission-line (TWTL), which simultaneously supports a symmetric and an antisymmetric mode. We first confirm that emission of second-harmonic light into the symmetric mode of the waveguide is symmetry-allowed when the fundamental excited waveguide modes are either purely symmetric or antisymmetric. We further switch the emission into the antisymmetric mode when a controlled mixture of the fundamental modes is excited simultaneously. Our results open up a new degree of freedom into the designs of nonlinear optical components and should pave a new avenue toward multifunctional nanophotonic circuitry.

Designable Spectrometer-Free Index Sensing Using Plasmonic Doppler Gratings.

Typical nanoparticle-based plasmonic index sensors detect the spectral shift of localized surface plasmon resonance (LSPR) upon the change of the environmental index. Therefore, they require broadband illumination and spectrometers. The sensitivity and flexibility of nanoparticle-based index sensors are usually limited because LSPR peaks are usually broad and the spectral position cannot be freely designed. Here, we present a fully designable index sensing platform using plasmonic Doppler gratings (PDGs), which provide broadband and azimuthal angle dependent grating periodicity. Different from LSPR sensors, PDG index sensors are based on the momentum matching between photons and surface plasmons via the lattice momentum of the grating. Therefore, the index change is translated into the variation of the in-plane azimuthal angle for photon-to-plasmon coupling, which manifests as directly observable dark bands in the reflection image. The PDG can be freely designed to optimally match the range of index variation for specific applications. In this work, we demonstrate PDG index sensors for large (n = 1.00-1.52) and small index variations (n = 1.3330-1.3650). The tiny and nonlinear index change of the water-ethanol mixture has been clearly observed and accurately quantified. Since the PDG is a dispersive device, it enables on-site and single-color index sensing without a spectrometer and provides a promising spectroscopic platform for on-chip analytical applications.

Photoluminescence-Driven Broadband Transmitting Directional Optical Nanoantennas.

Optical nanoantennas mediate near and far optical fields. Operating a directional nanoantenna in transmitting mode is challenging because the antenna needs to be driven by a nanosized optical frequency generator, which must work at the antenna's resonance frequency and be precisely attached to the antenna's feed with correct polarization. Quantum emitters have been used as optical nanogenerators, but their precise positioning relative to the nanoantenna is technically challenging, setting up a barrier to the practical implementation. One unique source to drive nanoantenna is the photoluminescence from the material of the nanoantenna because the high operational frequency of the antenna reaches the regime for the electronic transitions in matter. Here, we exploit plasmon-modulated photoluminescence (PMPL) as an effective optical source to drive directional nanoantennas. We experimentally realize two technically challenging theoretical proposals, namely, an optical nanospectrometer based on Yagi-Uda nanoantennas and tunable broadband directional emission from log-periodic nanoantennas. Using photoluminescence from the nanoantenna as an optical source promotes practical implementation of transmitting optical nanoantennas.

Probing the acoustic vibrations of complex-shaped metal nanoparticles with four-wave mixing.

We probe the acoustic vibrations of silver nanoprisms and gold nano-octahedrons in aqueous solution with four-wave mixing. The nonlinear optical response shows two acoustic vibrational modes: an in-plane mode of nanoprisms with vertexial expansion and contraction; an extensional mode of nano-octahedrons with longitudinal expansion and transverse contraction. The particles were also analyzed with electron microscopy and the acoustic resonance frequencies were then calculated by the finite element analysis, showing good agreement with experimental observations. The experimental mode frequencies also fit with theoretical approximations, which show an inverse dependence of the mode frequency on the edge length, for both nanoprisms and nano-octahedrons. This technique is promising for in situ monitoring of colloidal growth.

Facet-Dependent and Light-Assisted Efficient Hydrogen Evolution from Ammonia Borane Using Gold-Palladium Core-Shell Nanocatalysts.

Au-Pd core-shell nanocrystals with tetrahexahedral (THH), cubic, and octahedral shapes and comparable sizes were synthesized. Similar-sized Au and Pd cubes and octahedra were also prepared. These nanocrystals were used for the hydrogen-evolution reaction (HER) from ammonia borane. Light irradiation can enhance the reaction rate for all the catalysts. In particular, Au-Pd THH exposing {730} facets showed the highest turnover frequency for hydrogen evolution under light with 3-fold rate enhancement benefiting from lattice strain, modified surface electronic state, and a broader range of light absorption. Finite-difference time-domain (FDTD) simulations show a stronger electric field enhancement on Au-Pd core-shell THH than those on other Pd-containing nanocrystals. Light-assisted nitro reduction by ammonia borane on Au-Pd THH was also demonstrated. Au-Pd tetrahexahedra supported on activated carbon can act as a superior recyclable plasmonic photocatalyst for hydrogen evolution.

Mode conversion in high-definition plasmonic optical nanocircuits.

Symmetric and antisymmetric guided modes on a plasmonic two-wire transmission line have distinct properties and are suitable for different circuit functions. Being able to locally convert the guided modes is important for realizing multifunctional optical nanocircuits. Here, we experimentally demonstrate successful local conversion between the symmetric and the antisymmetric modes in a single-crystalline gold plasmonic nanocircuit with an optimally designed mode converter for optical signals at 194.2 THz. Mode conversion may find applications in controlling nanoscale light-matter interaction.

A Photoelectrochemical Sensor for the Sensitive Detection of Cysteine Based on Cadmium Sulfide/Tungsten Disulfide Nanocomposites.

In this work, a CdS-nanoparticle-decorated WS2 nanosheet heterojunction was successfully prepared and first used to modify ITO electrodes for the construction of a novel photoelectrochemical sensor (CdS/WS2/ITO). The thin-film electrode was fabricated by combining electrophoretic deposition with successive ion layer adsorption and reaction techniques. The results indicated that the synthesized heterojunction nanomaterials displayed excellent photoelectrochemical performance which was much better than that of pristine CdS nanoparticles and 2D WS2 nanosheets. Owing to the formation of the surface heterojunction and the effective interfacial electric field, the enhanced separation of photogenerated electron-hole pairs led to a remarkable improvement in the photoelectrochemical activity of CdS/WS2/ITO. This heterojunction architecture can protect CdS against photocorrosion, resulting in a stable photocurrent. Based on the specific recognition between cysteine and CdS/WS2/ITO, through the specificity of Cd-S bonds, a visible-light-driven photoelectrochemical sensor was fabricated for cysteine detection. The novel photoelectrochemical biosensor exhibited outstanding analytical capabilities in detecting cysteine, with an extremely low detection limit of 5.29 nM and excellent selectivity. Hence, CdS-WS2 heterostructure nanocomposites are promising candidates as novel advanced photosensitive materials in the field of photoelectrochemical biosensing.

Correction: Design and characterization of a plasmonic Doppler grating for azimuthal angle-resolved surface plasmon resonances.

Correction for 'Design and characterization of a plasmonic Doppler grating for azimuthal angle-resolved surface plasmon resonances' by Kel-Meng See et al., Nanoscale, 2017, 9, 10811-10819, DOI: .

Spatially Resolving the Enhancement Effect in Surface-Enhanced Coherent Anti-Stokes Raman Scattering by Plasmonic Doppler Gratings.

Well-designed plasmonic nanostructures can mediate far and near optical fields and thereby enhance light-matter interactions. To obtain the best overall enhancement, structural parameters need to be carefully tuned to obtain the largest enhancement at the input and output frequencies. This is, however, challenging for nonlinear light-matter interactions involving multiple frequencies because obtaining the full picture of structure-dependent enhancement at individual frequencies is not easy. In this work, we introduce the platform of plasmonic Doppler grating (PDG) to experimentally investigate the enhancement effect of plasmonic gratings in the input and output beams of nonlinear surface-enhanced coherent anti-Stokes Raman scattering (SECARS). PDGs are designable azimuthally chirped gratings that provide broadband and spatially dispersed plasmonic enhancement. Therefore, they offer the opportunity to observe and compare the overall enhancement from different combinations of enhancement in individual input and output beams. We first confirm PDG's capability of spatially separating the input and output enhancement in linear surface-enhanced fluorescence and Raman scattering. We then investigate spatially resolved enhancement in nonlinear SECARS, where coherent interaction of the pump, Stokes, and anti-Stokes beams is enhanced by the plasmonic gratings. By mapping the SECARS signal and analyzing the azimuthal angle-dependent intensity, we characterize the enhancement at individual frequencies. Together with theoretical analysis, we show that while simultaneous enhancement in the input and output beams is important for SECARS, the enhancement in the pump and anti-Stokes beams plays a more critical role in the overall enhancement than that in the Stokes beam. This work provides an insight into the enhancement mechanism of plasmon-enhanced spectroscopy, which is important for the design and optimization of plasmonic gratings. The PDG platform may also be applied to study enhancement mechanisms in other nonlinear light-matter interactions or the impact of plasmonic gratings on the fluorescence lifetime.

Design and characterization of a plasmonic Doppler grating for azimuthal angle-resolved surface plasmon resonances.

We present a two-dimensional plasmonic Doppler grating (PDG) for broadband and azimuthal angle-resolved nanophotonic applications. The PDG consists of a set of non-concentric circular rings mimicking the wavefronts of a moving point source that exhibits the Doppler effect and thereby offers a continuous azimuthal angle-dependent lattice momentum for photon-plasmon coupling. The center and span of the working frequency window are fully designable for optimal performance in specific applications. We detail the design, fabrication and optical characterization of the PDG. The design of the Doppler grating provides a general platform for in-plane angle-resolved nanophotonic applications.

Robust room temperature valley polarization in monolayer and bilayer WS2.

We report robust room temperature valley polarization in chemical-vapor-deposition (CVD) grown monolayer and bilayer WS2via polarization-resolved photoluminescence measurements using excitation below the bandgap. We show that excitation with energy slightly below the bandgap of the multi-valleyed transition metal chalcogenides can effectively suppress the random redistribution of excited electrons and, thereby, greatly enhance the efficiency of valley polarization at room temperature. Compared to mechanically exfoliated WS2, our CVD grown WS2 films also show enhancement in the coupling of spin, layer and valley degree of freedom and, therefore, provide improved valley polarization. At room temperature, using below-bandgap excitation and CVD grown monolayer and bilayer WS2, we have reached a record-high valley polarization of 35% and 80%, respectively, exceeding the previously reported values of 10% and 65% for mechanically exfoliated WS2 layers using resonant excitation. This observation provides a new direction to enhance valley control at room temperature.

Single-Crystalline Aluminum Nanostructures on a Semiconducting GaAs Substrate for Ultraviolet to Near-Infrared Plasmonics.

Aluminum, as a metallic material for plasmonics, is of great interest because it extends the applications of surface plasmon resonance into the ultraviolet (UV) region and is superior to noble metals in natural abundance, cost, and compatibility with modern semiconductor fabrication processes. Ultrasmooth single-crystalline metallic films are beneficial for the fabrication of high-definition plasmonic nanostructures, especially complex integrated nanocircuits. The absence of surface corrugation and crystal boundaries also guarantees superior optical properties and applications in nanolasers. Here, we present UV to near-infrared plasmonic resonance of single-crystalline aluminum nanoslits and nanoholes. The high-definition nanostructures are fabricated with focused ion-beam milling into an ultrasmooth single-crystalline aluminum film grown on a semiconducting GaAs substrate with a molecular beam epitaxy method. The single-crystalline aluminum film shows improved reflectivity and reduced two-photon photoluminescence (TPPL) due to the ultrasmooth surface. Both linear scattering and nonlinear TPPL are studied in detail. The nanoslit arrays show clear Fano-like resonance, and the nanoholes are found to support both photonic modes and localized surface plasmon resonance. We also found that TPPL generation is more efficient when the excitation polarization is parallel rather than perpendicular to the edge of the aluminum film. Such a counterintuitive phenomenon is attributed to the high refractive index of the GaAs substrate. We show that the polarization of TPPL from aluminum preserves the excitation polarization and is independent of the crystal orientation of the film or substrate. Our study gains insight into the optical property of aluminum nanostructures on a high-index semiconducting GaAs substrate and illustrates a practical route to implement plasmonic devices onto semiconductors for future hybrid nanodevices.

Facet-dependent optical properties of Pd-Cu2O core-shell nanocubes and octahedra.

Pd-Cu2O core-shell nanocubes and truncated octahedra with six average sizes for each particle shape have been synthesized from 29 nm Pd nanocubes. The nanocubes have average edge lengths of 64-124 nm, while the truncated octahedra are 107-183 nm in the opposite tip distance. The core and shell composition and lattice orientation have been determined, showing the formation of single-crystalline Cu2O shells. The surface plasmon resonance (SPR) band from the Pd nanocrystal cores is barely visible. However, the Cu2O shells display facet-dependent optical properties. The Cu2O absorption band for smaller Pd-Cu2O cubes is consistently more red-shifted than somewhat larger Pd-Cu2O truncated octahedra. This work again shows that the observed facet-dependent optical phenomenon in metal-Cu2O core-shell nanocrystals is derived from the Cu2O shells. The use of 40 nm Pd cubes as cores gave uniform and size-tunable Pd-Cu2O nanocubes and truncated octahedra that display the Pd SPR band. The Pd SPR band is consistently located at 650 nm for Pd-Cu2O truncated octahedra, and 670 nm for the cubes despite large variation in the shell thickness. Both the Cu2O absorption and the Pd plasmonic band exhibit facet-dependent optical properties.

Facile synthesis of Au-Pd core-shell nanocrystals with systematic shape evolution and tunable size for plasmonic property examination.

A facile synthetic method has been developed for the formation of Au-Pd core-shell nanocrystals in aqueous solution in just 0.5-2 h at 50 °C with systematic shape evolution from cubic to truncated cubic, cuboctahedral, truncated octahedral, and octahedral structures using octahedral gold cores. By adjusting the amounts of H2PdCl4, ascorbic acid, and sometimes surfactants and gold cores added, the particle morphology can be finely tuned, and Pd shells with ultrathin thicknesses have been achieved. Gold cores of three different sizes (35, 45, and 74 nm in opposite corner distance) were used to obtain a full range of particle sizes and shapes for a most complete examination of their plasmonic properties. Visual observations made during particle synthesis reveal that Au-Pd cubes are formed at a faster rate than that for the growth of octahedra. For the smaller cubes, cuboctahedra, and truncated octahedra prepared using 35 and 45 nm gold cores, the surface plasmon resonance (SPR) absorption band from the gold cores can be seen only when the Pd shell thickness is just 1 nm at the thinnest points of the particles. For small-sized Au-Pd octahedra, this band is observable at a Pd shell thickness of around 5 nm. For larger Au-Pd nanocrystals synthesized from 74 nm gold cores, the Au SPR band is more recognizable for all particle shapes, although octahedra still exhibit the most obvious band. The band shifts slightly to the red going from cubes to octahedra. Simulation spectra have been performed, and they roughly match with the experimental spectra. Au-Pd octahedra with two different core sizes and shell thicknesses have been used for hydrogen sensing by comparing their UV-vis spectra before and after hydrogen incorporation forming PdH. The results show that the shell thickness is more important in producing a larger spectral red-shift after hydrogen absorption.

The modulation effect of transverse, antibonding, and higher-order longitudinal modes on the two-photon photoluminescence of gold plasmonic nanoantennas.

Plasmonic nanoantennas exhibit various resonant modes with distinct properties. Upon resonant excitation, plasmonic gold nanoantennas can generate strong two-photon photoluminescence (TPPL). The TPPL from gold is broadband and depolarized, and may serve as an ideal local source for the investigation of antenna eigenmodes. In this work, TPPL spectra of three arrays of single-crystalline gold nanoantennas are comprehensively investigated. We carefully compare the TPPL spectra with dark-field scattering spectra and numerically simulated spectra. We show the modulation effect of the transverse resonant mode and the nonfundamental longitudinal mode on the TPPL spectrum. We also demonstrate suppression of TPPL due to the subradiant antibonding modes and study the influence of antenna resonant modes on the overall TPPL yield. Our work provides direct experimental evidence on nanoantenna-mediated near-to-far-field energy coupling and gains insight into the emission spectrum of the TPPL from gold nanoantennas.

HNO3-assisted polyol synthesis of ultralarge single-crystalline Ag microplates and their far propagation length of surface plasmon polariton.

We developed a HNO3-assisted polyol reduction method to synthesize ultralarge single-crystalline Ag microplates routinely. The edge length of the synthesized Ag microplates reaches 50 µm, and their top facets are (111). The mechanism for dramatically enlarging single-crystalline Ag structure stems from a series of competitive anisotropic growths, primarily governed by carefully tuning the adsorption of Ag(0) by ethylene glycol and the desorption of Ag(0) by a cyanide ion on Ag(100). Finally, we measured the propagation length of surface plasmon polaritons along the air/Ag interface under 534 nm laser excitation. Our single-crystalline Ag microplate exhibited a propagation length (11.22 µm) considerably greater than that of the conventional E-gun deposited Ag thin film (5.27 µm).

The influence of shell thickness of Au@TiO2 core-shell nanoparticles on the plasmonic enhancement effect in dye-sensitized solar cells.

Plasmonic core-shell nanoparticles (PCSNPs) can function as nanoantennas and improve the efficiency of dye-sensitized solar cells (DSSCs). To achieve maximum enhancement, the morphology of PCSNPs needs to be optimized. Here we precisely control the morphology of Au@TiO2 PCSNPs and systematically study its influence on the plasmonic enhancement effect. The enhancement mechanism was found to vary with the thickness of the TiO2 shell. PCSNPs with a thinner shell mainly enhance the current, whereas particles with a thicker shell improve the voltage. While pronounced plasmonic enhancement was found in the near infrared regime, wavelength-independent enhancement in the visible range was observed and attributed to the plasmonic heating effect. Emission lifetime measurement confirms that N719 molecules neighboring nanoparticles with TiO2 shells exhibit a longer lifetime than those in contact with metal cores. Overall, PCSNPs with a 5 nm shell give the highest efficiency enhancement of 23%. Our work provides a new synthesis route for well-controlled Au@TiO2 core-shell nanoparticles and gains insight into the plasmonic enhancement in DSSCs.