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Z-scheme heterojunctions are fundamentally promising yet practically appealing for photocatalytic hydrogen (H2) production owing to the enhanced redox power, spatial separation of charge carriers, and broad-spectrum solar light harvesting. The charge-transfer dynamics at Z-scheme heterojunctions can be accelerated by inserting charge-transfer mediators at the heterojunction interfaces. In this study, we introduce Au nanoparticle mediators in the Z-scheme W18O49/g-C3N4 heterostructure, which enables an improved H2 production rate of 3465 μmol/g·h compared with the direct Z-scheme W18O49/g-C3N4 (1785 μmol/g·h) under 1 sun irradiation. The apparent quantum yields of H2 production with W18O49/Au/g-C3N4 are 3.9% and 9.3% at 420 and 1200 nm, respectively. The improved photocatalytic H2 production activity of W18O49/Au/g-C3N4 is attributable to the triple-channel charge-transfer mechanism: channel I─Z-scheme charge transfer facilitates charge separation and increased redox power of the photoexcited electrons; channels II and III─the localized surface plasmon resonances from Au (channel II) and W18O49 (channel III) enable light harvesting extension from visible to near-infrared wavelengths.

Tunable extraordinary optical transmission (EOT) with graphene is realized using a novel metallic ring–rod nested structure in the terahertz frequency regime. The generated double-enhanced transmission peaks primarily originate from the excitation of localized surface plasmon resonances (LSPRs). On using graphene, the resonating surface plasmon distribution changes in the reaction plane, which disturbs the generation of LSPRs. By regulating the Fermi energy (Ef) of the graphene to reach a certain level, an adjustment from bimodal EOT to unimodal EOT is obtained. As the Ef of the graphene integrated beneath the rod increases to 0.5 eV, the transmittance of the peak at 2.42 THz decreases to 6%. Moreover, the transmission peak at 1.77 THz virtually disappears due to the Ef increasing to 0.7 eV when the graphene is placed beneath the ring. The significant tuning capabilities of the bimodal EOT indicate its promising application prospects in frequency-selective surfaces, communication, filtering, and radar.

Two-dimensional transition metal dichalcogenide (TMDC) nanocrystals (NCs) exhibit unique optical and electrocatalytic properties. However, the growth of uniform and high-quality NCs of monolayer TMDC remains a challenge. Until now, most of them are synthesized via a solution-based hydrothermal process or ultrasonic exfoliation method, in which the capping ligands introduced from organic solution often quench the optical and electrocatalytic properties of TMDC NCs. Moreover, it is difficult to homogeneously disperse the solution-based TMDC NCs on a substrate for device fabrication, since the dispersed NCs can easily aggregate. Here, we put forward a novel CVD method to grow closely spaced MoS2 NCs around 5 nm in lateral size. TEM and AFM characterizations demonstrate the monolayer and high-crystalline nature of MoS2 NCs. An obvious blue-shift with 130 meV in photoluminescence signals can be observed. The MoS2 NCs also show an outstanding surface-enhanced Raman scattering for organic molecules due to their localized surface plasmon and abundant edge sites and exhibit excellent electrocatalytic properties for the hydrogen-evolution reaction with a very low onset potential of ∼50 mV and Tafel slope of ∼57 mV/decade. Finally, we further demonstrate this kind of CVD method as a versatile platform for the growth of other TMDC NCs, such as WSe2 and MoSe2 NCs.

The performance improvement of solid-state triplet-triplet annihilation-based photon upconversion (TTA-UC) systems is required for the application to various solar devices. The performance can be improved by making use of the local strong electric field generated through the excitation of localized surface plasmon (LSP) resonance of metal nanostructures. However, since the improvement is effective only within the limited nanospace around nanoparticles (i.e., the near-field effect), a methodology for improving the performance over a wider spatial region is desirable. In this study, a significant improvement in the threshold light excitation intensity (Ith) (77% decrease) as the figure of merit and the upconverted emission intensity (6.3 times enhancement) in a solid-state TTA-UC film with a thickness of 3 μm was achieved by stacking the film with periodic Ag half-shell arrays. The highest-enhanced upconverted emission was obtained by tuning the diffuse reflectance peak, which results from the excitation of LSP resonance of the Ag half-shell arrays, to overlap well with the photoexcitation peak of the sensitizer in the TTA-UC film. The intensity of the enhanced upconverted emission was independent of the distance between the lower edge of the TTA-UC film and the surface of half-shell arrays in the nanometer order. These results suggest that the performance improvement was attributed to the photoexcitation enhancement of the sensitizer by elongating the excitation light path length inside the TTA-UC film, which was achieved through a strong backward scattering of the incident light based on the LSP resonance excitation (i.e., the far-field effect). In addition, the upconverted emission was improved using half-shell arrays comprising low-cost Al, although the enhancement factor was 3.5, which was lower than that of Ag half-shell arrays. The lower enhancement may be attributed to a decrease in the backward scattering of the excitation light owing to the intrinsic strong interband transition of Al at long visible wavelengths.

Degenerately doped metal-oxide nanocrystals (NCs) show localized surface plasmon resonances (LSPRs) that are tunable via their tunable excess charge-carrier densities. Modulation of excess charge carriers has also been used to control magnetism in colloidal doped metal-oxide NCs. The addition of excess delocalized conduction-band (CB) electrons can be achieved through aliovalent doping or by postsynthetic techniques such as electrochemistry or photodoping. Here, we examine the influence of charge-compensating aliovalent dopants on the potentials of excess CB electrons in free-standing colloidal degenerately doped oxide NCs, both experimentally and through modeling. Taking Sn4+:In2O3 (ITO) NCs as a model system, we use spectroelectrochemical techniques to examine differences between aliovalent doping and photodoping. We demonstrate that whereas photodoping introduces excess CB electrons by raising the Fermi level relative to the CB edge, aliovalent impurity substitution introduces excess CB electrons by stabilizing the CB edge relative to an externally defined Fermi level. Significant differences are thus observed electrochemically between spectroscopically similar delocalized CB electrons compensated by aliovalent dopants and those compensated by surface cations (e.g., protons) during photodoping. Theoretical modeling illustrates the very different potentials that arise from charge compensation via aliovalent substitution and surface charge compensation. Spectroelectrochemical titrations allow the ITO NC band-edge stabilization as a function of Sn4+ doping to be quantified. Extremely large capacitances are observed in both In2O3 and ITO NCs, making these NCs attractive for reversible charge-storage applications.

Recently, localized surface plasmon resonances (SPRs) of metallic nanoparticles (NPs) have been widely used to construct plasmonic nanohybrids for heterogeneous photocatalysis. For example, the combination of plasmonic Au NPs and TiO2 provides pure TiO2 visible-light activity. The SPR effect induces an electric field and consequently enhances light scattering and absorption, favoring the transfer of photon energy to hot carriers for catalytic reactions. Numerous approaches have been dedicated to the improvement of SPR absorption in photocatalysts. Here, we have designed a core@shell-satellite nanohybrid catalyst whereby an Ag NP core, as a plasmonic resonator featuring unique dual functions of strong scattering and near-field enhancement, is encapsulated by SiO2 and TiO2 layers in sequence, with Au NPs on the outer surface, Ag@SiO2@TiO2-Au, for efficient plasmonic photocatalysis. By varying the size and number of Ag NP cores, the Au SPR can be tailored over the visible and near-infrared spectral region to reabsorb the scattered photons. In the presence of the Ag core, the incident light is efficiently confined in the reaction suspension by undergoing multiple scattering, thus leading to an increase of the optical path to the photocatalysis. Moreover, using numerical analysis and experimental verifications, we demonstrate that the Ag core also induces a strong near-field enhancement at the Au-TiO2 interface via SPR coupling with Au. Consequently, the activity of the TiO2-Au plasmonic photocatalyst is significantly enhanced, resulting in a high H2 production rate under visible light. Thus, the design of a single structural unit with strong scattering and field enhancement, induced by a plasmonic resonator, is a highly effective strategy to boost photocatalytic activity.

In plasmonic catalysis, localized surface plasmons can be leveraged to drive chemical reactions. This approach is promising for catalyzing many challenging reactions at relatively low temperatures ...

We present a strong coupling system realized by coupling the localized surface plasmon mode in individual silver nanogrooves and propagating surface plasmon modes launched by periodic nanogroove arrays with varied periodicities on a continuous silver medium. When the propagating modes are in resonance with the localized mode, we observe a √N scaling of Rabi splitting energy, where N is the number of propagating modes coupled to the localized mode. Here, we confirm a giant Rabi splitting on the order of 450-660 meV (N = 2) in the visible spectral range, and the corresponding coupling strength is 160-235 meV. In some of the strong coupling cases studied by us, the coupling strength is about 10% of the mode energy, reaching the ultrastrong coupling regime.

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C-N bond and forming a new C-C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. This work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

We prepared MoS2 monolayers on Au nanodot (ND) and nanohole (NH) arrays. Both these sample arrays exhibited enhanced photoluminescence intensity compared with that of a bare SiO2/Si substrate. The ...

Ultrafast laser irradiation can induce morphological and structural changes in plasmonic nanoparticles. Gold nanorods (Au NRs), in particular, can be welded together upon irradiation with femtosecond laser pulses, leading to dimers and trimers through the formation of necks between individual nanorods. We used electron tomography to determine the 3D (atomic) structure at such necks for representative welding geometries and to characterize the induced defects. The spatial distribution of localized surface plasmon modes for different welding configurations was assessed by electron energy loss spectroscopy. Additionally, we were able to directly compare the plasmon line width of single-crystalline and welded Au NRs with single defects at the same resonance energy, thus making a direct link between the structural and plasmonic properties. In this manner, we show that the occurrence of (single) defects results in significant plasmon broadening.

In the past couple of decades, the development of plasmonic nanosensors underwent rapid progress in the fields of fabrication, integration, and realized applications. Localized surface plasmon reso...

We investigate the intrinsic characteristics of resonance energy transfer (RET) coupled with localized surface plasmon polaritons (LSPPs) from the perspective of macroscopic quantum electrodynamics. To quantify the effect of LSPPs, we propose a numerical scheme that allows us to accurately calculate the rate of RET between a donor-acceptor pair near a nanoparticle. Our study shows that LSPPs can be used to enhance the RET rate significantly and control its frequency dependence by modifying a core/shell structure, which indicates the possibility of RET rate optimization. Moreover, we systematically explore the angle (distance) dependence of the RET rate and analyze its origin. According to different frequency regimes, the angle dependence of RET is dominated by different mechanisms, such as LSPPs, surface plasmon polaritons (SPPs), and anti-resonance. For the proposed core/shell structure, the characteristic distance of RET coupled with LSPPs (approximately 0.05 emission wavelength) is shorter than that of RET coupled with SPPs (approximately 0.1 emission wavelength), which may provide promising applications in energy science.

Regulation of enzymes is highly relevant toward orchestrating cell-free and stepwise biotransformations, thereby maximizing their overall performance. Plasmonic nanomaterials offer a great opportunity to tune the functionality of enzymes through their remarkable optical properties. Localized surface plasmon resonances (LSPR) can be used to modify chemical transformations at the nanomaterial's surface, upon light irradiation. Incident light can promote energetic processes, which may be related to an increase of local temperature (photothermal effects) but also to effects triggered by generated hotspots or hot electrons (photoelectronic effects). As a consequence, light irradiation of the protein-nanomaterial interface affects enzyme functionality. To harness these effects to finely and remotely regulate enzyme activity, the physicochemical features of the nanomaterial, properties of the incident light, and parameters governing molecular interactions must be optimized. In this Perspective, we discuss relevant examples that illustrate the use of plasmonic nanoparticles to control enzyme function through LSPR excitation. Finally, we also highlight the importance of expanding the use of plasmonic nanomaterials to the immobilization of multienzyme systems for light-driven regulation of cell-free biosynthetic pathways. Although this concept is living its infancy, we encourage the scientific community to advance in the development of novel light-controlled biocatalytic plasmonic nanoconjugates and explore their application in biosensing, applied biocatalysis, and biomedicine.

Localized surface plasmon resonances (LSPRs) have attracted much recent attention for their potential in promoting chemical reactions with light. However, the mechanism of LSPR-induced chemical rea...

Recently, studies have been carried out on attempts to combine surface-enhanced Surface-enhanced Raman spectroscopy (SERS) substrates that can be based on either localized surface plasmon (LSP) or surface plasmon polaritons (SPP) structures. By combining these two systems, the drawbacks of each other can be solved. However, the manufacturing methods involved so far are sophisticated, labor-intensive, expensive, and also technically demanding. We propose a facile method for the fabrication of a flexible plasmonic nanoslit SERS sensor. We utilized the pattern on periodic optical disks (DVD-R) as a cheap substitute for printing the periodic pattern on PDMS with soft imprint lithography. Ag nanoslit (AgNS) was fabricated by serial bideposition using a dynamic oblique angle deposition (DOD) technique. The nanoslit structures were physically and optically characterized, and the experimental results were compared to the numerical simulation studies; Monte Carlo and the finite-difference time-domain (FDTD) simulation. The Ag nanoslit structure showed an excellent SERS enhancement, and its biosensing capability was demonstrated by the sensing of bilirubin.

The electron transfer mechanism of noble materials to semiconductor was enhanced for the first time by localized surface plasmon resonances (LSPRs) using in situ irradiated X-ray photoelectron spec...

Heavily doped metal oxide nanocrystals (NCs) possess tunable infrared localized surface plasmon resonances (LSPRs) that give them utility for several potential applications, including photothermal ...

Plasmonic color generation has attracted much research interest because of the unique optical properties of plasmonic nanocrystals that are promising for chromatic applications, such as flat-panel displays, smart windows, and wearable devices. Low-cost, monodisperse plasmonic nanocrystals supporting strong localized surface plasmon resonances are favorable for the generation of plasmonic colors. However, many implementations so far have either a single static state or complexities in the particle alignment and switching mechanism for generating multiple displaying states. Herein, we report on a facile and robust approach for realizing the electrochemical switching of plasmonic colors out of colloidal plasmonic nanocrystals. The metal nanocrystals are coated with a layer of polyaniline, whose refractive index and optical absorption are reversibly switched through the variation of an applied electrochemical potential. The change in refractive index and optical absorption results in the modulation of the plasmonic scattering intensity with a depth of 11 dB. The electrochemical switching process is fast (∼5 ms) and stable (over 1000 switching cycles). A device configuration is further demonstrated for switching plasmonic color patterns in a transparent electrochemical device, which is made from indium tin oxide electrodes and a polyvinyl alcohol solid electrolyte. Our control of plasmonic colors provides a favorable platform for engineering low-cost and high-performance miniaturized optical devices.

Localized surface plasmon resonances optically excited in metallic nanoparticles (NPs) produce beneficial thermal and nonthermal effects. Nonthermal effects, such as enhancing and localizing fields...

A central theme of nanocrystal (NC) research involves synthesis of dimension-controlled NCs and studyof size-dependent scaling laws governing their optical, electrical, magnetic, and thermodynamic properties. Here, we describe the synthesis of monodisperse CdO NCs that exhibit high quality-factor (up to 5.5) mid-infrared (MIR) localized surface plasmon resonances (LSPR) and elucidate the inverse scaling relationship between carrier concentration and NC size. The LSPR wavelength is readily tunable between 2.4 and ∼6.0 μm by controlling the size of CdO NCs. Structural and spectroscopic characterization provide strong evidence that free electrons primarily originate from self-doping due to NC surface-induced nonstoichiometry. The ability to probe and to control NC stoichiometry and intrinsic defects will pave the way toward predictive synthesis of doped NCs with desirable LSPR characteristics.

Mesoporous silica features open and accessible pores that can intake substances from the outside. The combination of mesoporous silica with plasmonic nanostructures represents an interesting platform for an optical sensor based on the dependence of plasmonic modes on the refractive index of the medium in which metallic nanoparticles are embedded. However, so far only a limited number of plasmonic nanostructures are combined with mesoporous silica, including random dispersion of metallic nanoparticles and flat metallic thin films. In this study, we make a mesoporous silica layer on an aluminum nanocylinder array. Such plasmonic arrangements support both localized surface plasmon resonances (LSPRs) and extended modes which are the result of the hybridization of LSPRs and photonic modes extending into the mesoporous layer. We investigate in situ optical reflectance of this system under controlled pressure of isopropanol vapor. Upon exposure, the capillary condensation in the mesopores results in a gradual spectral shift of the reflectance. Our analysis demonstrates that such shifts depend largely on the nature of the modes; that is, the extended modes show larger shifts compared to localized ones. Our materials represent a useful platform for the field of environmental sensing

We developed a convenient, facile, low cost and ‘‘green” method to synthesize nanoparticles (NPs) with deep-ultraviolet localized surface plasmon resonances (LSPR) based on laser ablation of aluminum target in liquid. The nanoparticles had an Al-Al2O3@C core-shell structure, and the LSPR peak ranged from 240nm to 250nm with the increasing of laser radiation time. It is found that the LSPR peak of the NPs is related to the presence of Al2O3 based on experimental characterization and theoretical simulation. The carbon shell can reduce the oxidation of Al nanoparticles and enhance the stability, which is significant important to achieve the deep-ultraviolet LSPR. Moreover, we demonstrated the enhancement of the blue fluorescence intensity from CsPbBr3-xClx by the Al-Al2O3@C NPs, due to the stronger excitations for CsPbBr3-xClx by the enhancement of localized electromagnetic field from LSPR.

Visualization of surface plasmon polariton (SPP) propagation at dielectric/metal interfaces is indispensable in providing opportunities for the precise designing and controlling of the functionalities of future plasmonic nanodevices. Here, we report the visualization of SPPs propagating along the buried organic/metal interface of fullerene (C60)/Au(111), through dual-colored two-photon photoemission electron microscopy (2P-PEEM) which precisely visualizes the SPP propagation of plasmonic metal nanostructures. Although SPPs excited by near-infrared photons at the few monolayer C60/Au(111) interface are clearly visualized as interference beat patterns between the SPPs and incident light, faithfully reflecting SPP properties modulated by the overlayer, photoemission signals are suppressed for thicker C60 films, due to less valence electrons participating in 2P-photoemission processes. With the use of silver (Agn (n = 21 and 55)) nanoclusters, which exhibit enhancement of overall photoemission intensities due to localized surface plasmons functioning as SPP sensitizers, it is revealed that the 2P-PEEM is applicable to the imaging of SPPs for thick C60/Au(111) interfaces, where SPP properties are hardly modulated by the added small amount (∼0.1 monolayer) of Agn sensitizers.

Anisotropic gold nanostructures are attracting attention due to the strong correlation between their shape and the localized surface plasmon resonances, which allows tuning their optical responses ...

Photodetectors based on two-dimensional (2D) materials such as monolayer MoS2 are attractive because they can be directly integrated into the current metal-oxide semiconductor (CMOS) structures. Unfortunately, such devices suffer from low responsivity due to low absorption by the monolayer MoS2. Combining MoS2 with plasmonic nanostructures is an alternative solution for enhancing the absorption of the 2D semiconductor, and this can drastically increase the photoresponsivity of the corresponding photodetector. Herein, a device incorporating a grating-patterned nanoparticle structure is fabricated using traditional photolithography together with an annealing step. We demonstrate that this new structure leads to a strong enhancement in the photocurrent due to the coupling of the MoS2 to localized surface plasmons in the nanoparticle grating. Compared to a simple Au nanoparticle array, the nanoparticle grating structure generates a 100% increase in optical absorption. Thus, under 532 nm illumination, the composite nanoparticle grating/monolayer MoS2 integrated photodetector shows a 111-fold increase in the photocurrent compared to the same device in the absence of nanoparticles. The gateless responsivity can be up to 38.57 A/W and a specific detectivity of 9.89 × 109 Jones is realized. Moreover, photothermal flux derivations indicate that, in addition to the expected increase due to light-generated carrier multiplication, the thermal effects of plasmons provide a significant contribution to the photocurrent enhancement.

In this article, the excitation of dipolar localized surface plasmon resonances (LSPRs) in both the far- and near-field regions is described in terms of the relevant static, dynamic, and radiative ...

Plasmonic complementary structures are interesting model systems that combine propagating and localized surface plasmon resonances and allow the fundamental study of their hybridization. In the simplest form, such structures are formed by stacking arrays of nanodisks and nanoholes with matching dimensions. Here, we produce such hole-disk arrays in an experimentally easy and parallel colloidal lithography process with accurate control over vertical alignment and separation between the individual disks and holes. Importantly, our process readily enables symmetry breaking and the design of asymmetric hole-disk arrays with controlled lateral offset between each hole-disk pair. We investigate the coupling between the parental resonances of the two elements as a function of feature size and separation distance and provide a plasmon hybridization scheme to rationalize the resonances. We find that for the asymmetric hole-disk structure, a new, hybrid resonance arises as a peak in the transmission spectra, which i...

Using time-dependent orbital-free density functional theory, we performed large-scale quantum mechanical simulations to examine localized surface plasmon resonances in sodium nanorods. The dependence of optical absorption wavelength, spectral width, and field enhancement on the dimensions of the nanorods, including the diameter, length, and aspect ratio, as well as polarization direction is examined for both longitudinal and tranverse plasmonic resonances. The longitudinal resonance is characterized by a dipolar charge oscillation with negligible charge spill-out from the surface and its spectral wavelength is linearly related to the aspect ratio. The spectral width is found to be dependent on both the nanorod size and the aspect ratio, in contrast to previous classical results. The spectrum of the transverse plasmons is much wider than that of the longitudinal plasmons owing to the presence of multipolar oscillations and strong electron spill-out effect. No linear relationship between the spectral wavele...

Plasmonic nanostructures were initially developed for sensing and nanophotonic applications but, recently, have shown great promise in chemistry, optoelectronics, and nonlinear optics. While smooth plasmonic films, supporting surface plasmon polaritons, and individual nanostructures, featuring localized surface plasmons, are easy to fabricate and use, the assemblies of nanostructures in optical antennas and metamaterials provide many additional advantages related to the engineering of the mode structure (and thus, optical resonances in the given spectral range), field enhancement, and local density of optical states required to control electronic and photonic interactions. Focusing on two of the many applications of plasmonic metamaterials, in this Account, we review our work on the sensing and nanochemistry applications of metamaterials based on the assemblies of plasmonic nanorods under optical, as well as electronic interrogation. Sensors are widely employed in modern technology for the detection of events or changes in their local environment. Compared to their electronic counterparts, optical sensors offer a combination of high sensitivity, fast response, immunity to electromagnetic interference, and provide additional options for signal retrieval, such as optical intensity, spectrum, phase, and polarization. Owing to the ability to confine and enhance electromagnetic fields on subwavelength scales, plasmonics has been attracting increasing attention for the development of optical sensors with advantages including both nanometer-scale spatial resolution and single-molecule sensitivity. Inherent hot-electron generation in plasmonic nanostructures under illumination or during electron tunneling in the electrically biased nanostructures provides further opportunities for sensing and stimulation of chemical reactions, which would otherwise not be energetically possible. We first provide a brief introduction to a metamaterial sensing platform based on arrays of strongly coupled plasmonic nanorods. Several prototypical sensing examples based on this versatile metamaterial platform are presented. Record-high refractive index sensitivity of gold nanorod arrays in biosensing based on the functionalization of the nanorod surface for selective absorption arises because of the modification of the electromagnetic coupling between the nanorods in the array. The capabilities of nanorod metamaterials for ultrasound and hydrogen sensing were demonstrated by precision coating of the nanorods with functional materials to create core-shell nanostructures. The extension of this metamaterial platform to nanotube and nanocavity arrays, and metaparticles provides additional flexibility and removes restrictions on the illumination configurations for the optical interrogation. We then discuss a nanochemical platform based on the electrically driven metamaterials to stimulate and detect chemical reactions in the tunnel junctions constructed with the nanorods by exploiting elastic tunneling for the activation of chemical reactions via generated hot-electrons and inelastic tunneling for the excitation of plasmons facilitating optical monitoring of the process. This represents a new paradigm merging electronics, plasmonics, photonics and chemistry at the nanoscale, and creates opportunities for a variety of practical applications, such as hot-electron-driven nanoreactors and high-sensitivity sensors, as well as nanoscale light sources and modulators. With a combination of merits, such as the ability to simultaneously support both localized and propagating modes, nanoporous texture, rapid and facile functionalization, and low cost and scalability, plasmonic nanorod metamaterials provide an attractive and versatile platform for the development of optical sensors and nanochemical platforms using hot-electrons with high performance for applications in fundamental research and chemical and pharmaceutical industries.

Nonstoichiometric Cu2–xS nanocrystals (NCs) have been synthesized by hot-injection method after changing the copper to sulfur ratio. Optical studies confirmed well-defined localized surface plasmon...

Gold nanoparticles (AuNPs) have unique optical properties because of their characteristic localized surface plasmon resonances (LSPRs). Upon the excitation of LSPR, AuNPs can affect the adjacent or...

We investigated electron emission induced by an intense mid-infrared (MIR) field from a nanoscale aluminum-coated grating. The total photoelectron yields clearly show a resonant-like behavior when ...

Light emission excited by stable tunnel junctions has attracted interest for potential use in optoelectronic device integration. However, these electrically driven sources cannot provide a high ele...

Electrochemical surface-enhanced Raman scattering measurements of single layer graphene provide unique information on resonant excitation induced by localized surface plasmons under controlled electron or hole doping. The highly confined electromagnetic field from the LSPs of the Au nanodimer structures prepared on defect-free graphene can generate holes and electrons of the electrochemical potentials beyond the limit of far-field light illumination. The electrochemical in situ SERS spectra prove nonzero wavevector excitation through the observation of normally forbidden Raman bands in graphene. The present findings point to a novel approach to breaking the limit of optoelectronic interactions and photochemical reactions of graphene and other semiconductors.

The distance dependence of localized surface plasmon (LSP)-coupled Forster resonance energy transfer (FRET) between Si quantum dots (QDs) is experimentally and theoretically investigated utilizing ...

Growth of anisotropic nanostructures enables the manipulation of optical properties across the electromagnetic spectrum by fine morphological tuning of the nanoparticles. Among them, stellated metallic nanostructures present enhanced properties owing to their complex shape, and hence, the control over the final morphology becomes of great importance. Herein, a seed-mediated method for the high-yield production of goldrich-copper concave branched nanostructures and their structural and optical characterization is reported. The synthesis protocol enabled excellent control and tunability of the final morphology, from concave pentagonal nanoparticles to five-fold branched nanoparticles, named "nanostars". The anisotropic shape was achieved via kinetic control over the synthesis conditions by selective passivation of facets using a capping agent and assisted by the presence of copper chloride ions, both having a crucial impact over the final structure. Optical extinction measurements of nanostars in solution indicated a broad spectral response, hiding the properties of the individual nanostars. Hence, single-particle scattering measurements of individual concave pentagonal nanoparticles and concave nanostars were performed to determine the origin of the multiple plasmon bands by correlation with their morphological features, following their growth evolution. Finite-difference time-domain calculations delivered insights into the geometry-dependent plasmonic properties of concave nanostars and their packed aggregates. Our results uncover the intrinsic scattering properties of individual nanostars and the origin of the broad spectral response, which is mostly due to z-direction packed aggregates.

Electrochemical tip-enhanced Raman spectroscopy (EC-TERS) appears as a promising in situ nanospectroscopic tool for characterization and understanding of the electrochemical interfacial processes at the nanometer scale and molecular level. However, the wide application of EC-TERS is hampered by its low sensitivity as a result of the optical path distortion due to the refractive index mismatch of the multilayer media (air, glass, and electrolyte). Here, we propose a new side-illumination EC-TERS setup by coupling a water immersion objective with a high numerical aperture to a scanning tunneling microscope scanning head customized with a large open space and a compact spectroelectrochemical cell. It not only effectively eliminates the optical distortion but also increases the sensitivity remarkably, which allows sensitive monitoring of the electrochemical redox processes of anthraquinone molecules. More importantly, EC-TERS is able to independently control the tip position and laser illumination position. By utilizing this feature, we reveal that the irreversible reduction reaction of anthraquinone observed in EC-TERS is induced by the synergistic effect of the negative potential and laser illumination rather than the localized surface plasmon. The highly improved sensitivity and the flexibility to control the tip and laser illumination position on the nanometer scale endows EC-TERS as an important tool for the fundamental understanding of the photo- or plasmon electrochemistry and the interfacial structure-activity relationship of important electrochemical systems.

Titanium nitride (TiN) continues to prove itself as an inexpensive, robust, and efficient alternative to gold in plasmonic applications. Notably, TiN has improved hot electron-harvesting and photocatalytic abilities compared to gold systems, which we recently attributed to the role of oxygen in TiN and its native semiconducting TiO2–x surface layer. Here, we explore the role of localized surface plasmon resonances (LSPRs) on electron harvesting across the TiN/TiO2–x interface and probe the resilience of TiN nanostructures under high-power laser illumination. To investigate this, we fabricate TiN strips, in which the lateral confinement allows for the polarization-selective excitation of the LSPR. Using ultrafast pump–probe spectroscopy, optical characterization, and Raman vibrational spectroscopy, we relate the differences and changes observed in the electron behavior to specific material properties. We observe plasmon-enhanced electron harvesting beyond what is expected resulting from the enhanced absorption of the plasmonic mode. We accredit this to the surface oxide damping the plasmon resonance, providing additional nonradiative loss channels. Subsequently, we show that low-power annealing of the surface oxide layer reduces the trap density at the interface and increases the initial harvested electron concentration. The unique properties of TiN make it important in the future development of plasmonic electron-harvesting applications.

Electron beam or photonic excitation of localized surface plasmon resonances (LSPRs) in gold nanoparticles and their subsequent nonradiative relaxation create a nonuniform charge distribution near the metal–semiconductor interface via hot-electron injection from gold nanoparticles to the monolayer MoS2 conduction band states. These charge domains induce lattice compression in the MoS2 lattice because of the inverse piezoelectric response arising due to the noncentrosymmetric nature of the crystal lattice. Our high-resolution transmission electron microscopy studies reveal that as much as 9–10% biaxial compressive strain is generated in free-standing monolayer MoS2 in the vicinity of gold nanoparticles, which relaxes rapidly within 50 nm from the edge of the gold nanoparticle. The metal interface-induced hot-electron injection via photonic excitation of LSPRs and the resultant lattice distortion also manifest in shifts as well as broadening of A1g(Γ) and E2g1(Γ) Raman modes of the monolayer MoS2 in presenc...

Photothermal therapy (PTT) based on two-dimensional (2D) nanomaterials has shown significant potential in cancer treatment. However, developing 2D nanomaterial-based theranostic agents with good biocompatibility and high therapeutic efficiency remains a key challenge. Bulk titanium (Ti) has been widely used as biomedical materials for their reputable biocompatibility, whereas nanosized Ti with a biological function remains unexplored. In this work, the 2D Ti nanosheets (NSs) are successfully exfoliated from nonlayer bulk Ti and utilized as an efficient theranostic nanoplatform for dual-modal computed tomography/photoacoustic (CT/PA) imaging-navigated PTT. Besides the excellent biocompatibility obtained by TiNSs as expected, they are found to show strong absorption ability with an extinction coefficient of 20.8 L g-1 cm-1 and high photothermal conversion ability with an efficiency of 61.5% owing to localized surface plasmon resonances, which exceeds most of other well-known photothermal agents, making it quite promising for PTT against cancer. Furthermore, the metallic property and light-heat-acoustic transformation endow 2D Ti with the strong CT/PA imaging signal and efficient cancer therapy, simultaneously. This work highlights the enormous potential of nanosized Ti in both the diagnosis and treatment of cancer. As a paradigm, this study also paves a new avenue for the elemental transition-metal-based cancer theranostics.

Copper sulfide nanocrystals have recently been studied due to their metal-like behavior and strong plasmonic response, which make them an attractive material for nanophotonic applications in the near-infrared spectral range; however, the nature of the plasmonic response remains unclear. We have performed a combined experimental and theoretical study of the optical properties of copper sulfide colloidal nanocrystals and show that bulk CuS resembles a heavily doped p-type semiconductor with a very anisotropic energy band structure. As a consequence, CuS nanoparticles possess key properties of relevance to nanophotonics applications: they exhibit anisotropic plasmonic behavior in the infrared and support optical modes with hyperbolic dispersion in the 670-1050 nm spectral range. We also predict that the ohmic loss is low compared to conventional plasmonic materials such as noble metals in the NIR. The plasmonic resonances can be tuned by controlling the size and shape of the nanocrystals, providing a playground for future nanophotonic applications in the near-infrared.

New opportunities for plasmonic applications at high temperatures have stimulated interest in refractory plasmonic materials that show greater stability at elevated temperatures than the more commonly used silver and gold (Au). Titanium nitride (TiN) has been identified as a promising refractory material, with deposition of TiN thin films through techniques ranging from plasma-enhanced atomic laser deposition to sputter deposition to pulsed laser deposition, on a variety of substrates, including MgO, polymer, SiO2, and sapphire. A variety of plasmonic devices have been evaluated, including gratings, nanorods, and nanodisks. An implicit metric for TiN behavior has been the comparison of its plasmonic performance to that of Au, in particular at various elevated temperatures. This paper carries out a one-to-one comparison of bowtie nanoantennas formed of TiN and Au (on both Si and MgO substrates), examining the far-field characteristics, related to the measured near-field resonances. In both cases, the optic...

When localized surface plasmons (LSPs) are coupled to extended surface plasmons (ESPs), higher density of particles causes stronger interaction, larger Rabi splitting (RS), and plasmonic energy ban...

Periodic arrays of plasmonic nanostructures are able to strongly confine light at the nanometer scale because of surface lattice resonances. These resonances are the result of electromagnetic coupling between single-particle localized surface plasmon resonances and Bragg resonances of the periodic lattice. Here, we investigate the effect of a finite size refractive index environment on the formation of surface lattice resonances by increasing the thickness of a polymer coating in nanometer-scale increments. Wet-chemically synthesized, spherical silver and gold nanoparticles with soft hydrogel shells are self-assembled into macroscopic, hexagonally ordered arrays on glass substrates using an interface-assisted approach. The resulting periodic plasmonic monolayers are subsequently coated by a polymer matching closely the refractive index of the glass support. The optical response of the plasmonic arrays is studied using far-field extinction spectroscopy and supported by numerical simulations. We show the formation of surface lattice resonances as well as higher order resonances in finite thickness polymer coatings. The resonance positions are determined by the interparticle spacing as well as the plasmonic material. Additionally, we demonstrate that a coating thickness of 450 nm is sufficient to support strong in-plane surface lattice resonances. This enables us to prepare macroscopic, free-standing polymer films with embedded plasmonic nanoparticle arrays, which feature strong surface lattice resonances.

We employ a broadband Ti:sapphire femtosecond oscillator to simultaneously launch two localized surface plasmon modes in rectangular plasmonic nanoholes. The resonant frequencies of these two modes...

Localized surface plasmon resonance (LSPR) in a silver (Ag) nanosphere dimer embedded in silicate glass was investigated using scanning transmission electron microscopy electron energy-loss spectro...

Hot carriers generated from the nonradiative decay of localized surface plasmons are capable of driving charge-transfer reactions at the surfaces of metal nanostructures. Photocatalytic devices utilizing plasmonic hot carriers are often based on metal nanoparticle/semiconductor heterostructures owing to their efficient electron-hole separation ability. The rapid thermalization of hot carriers generated at the metal nanoparticles yields a distribution of carrier energies that determines the capability of the photocatalytic device to drive redox reactions. Here, we quantify the thermalized hot carrier energy distribution generated at Au/TiO2 nanostructures using wavelength-dependent scanning electrochemical microscopy and a series of molecular probes with different redox potentials. We determine the quantum efficiencies and oxidizing power of the hot carriers from wavelength-dependent reaction rates and photocurrent across the metal/semiconductor interface. The wavelength-dependent reaction efficiency tracks the surface plasmon resonance spectrum of the Au nanoparticles, showing that the reaction is facilitated by plasmon excitation, while the responses from molecules with different redox potentials shed light on the energy distribution of the hot holes generated at metal nanoparticle/semiconductor heterostructures. The results provide important insight into the energies of the plasmon-generated hot carriers and quantum efficiencies of plasmonic photocatalytic devices.

Noble metals are currently the most common building blocks in plasmonics and thus define the available range of optical properties. Their alloying provides a viable strategy to engineer new materials with a tunable range of optical responses. Despite this attractive prospect, the link between composition and optical properties of many noble metal alloys is still not well understood. Here, electron energy-loss spectroscopy is employed to systematically study AuAg and AuPd nanoparticles of varying compositions. The localized surface plasmons, the bulk plasmons, and the permittivity functions of these two sets of alloys are investigated as functions of their composition. In the case of the more widely studied AuAg alloy system, good agreement is found with previous experimental and theoretical studies. The results on the less scrutinized AuPd system provide highly valuable experimental data that complements other experimental investigations and supports the development of theoretical models.