Plasmonic Field Research Articles

Transition Metal Nitrides Are Heating Up the Field of Plasmonics

Metal nitride nanostructures have been predicted to exhibit plasmonic responses in the UV to IR region, which can enable their potential use as low-cost, chemically, and thermally stable materials in several applications. In the case of photothermal applications, nitrides have been shown, both numerically and experimentally, to perform better than the noble metals. Additionally superior thermal stability of the metal nitride materials offers compatibility with high temperature device fabrication techniques. The plasmon frequency for transition metal nitride materials can be tuned from the UV to IR region by varying the type of metal in the nitride and metal/nitrogen ratio. Recently, studies have focused on developing and applying free-standing metal nitride nanostructures. Most investigations have focused on TiN, but as of late focus has been shifting to investigate other nanostructured nitrides such as ZrN and HfN. This Perspective will highlight recent key findings on the synthesis of plasmonic metal nitrides; associated thermal stability and photothermal properties; and application in photothermal therapy, solar-driven water evaporation, and chemical reactions. An outlook on current knowledge gaps and challenges and future directions to further this field is also presented.

Intracellular gold nanoparticles influence light scattering and facilitate amplified spontaneous emission generation

Generation of amplified stimulated emission inside mammalian cells has paved the way for a novel bioimaging and cell sensing approach. Single cells carrying gain media (e.g., fluorescent molecules) are placed inside an optical cavity, allowing the production of intracellular laser emission upon sufficient optical pumping. Here, we investigate the possibility to trigger another amplified emission phenomenon (i.e., amplified spontaneous emission or ASE) inside two different cell types, namely macrophage and epithelial cells from different species and tissues, in the presence of a poorly reflecting cavity. Furthermore, the resulting ASE properties can be enhanced by introducing plasmonic nanoparticles. The presence of gold nanoparticles (AuNPs) in rhodamine 6G-labeled A549 epithelial cells results in higher intensity and lowered ASE threshold in comparison to cells without nanoparticles, due to the effect of plasmonic field enhancement. An increase in intracellular concentration of AuNPs in rhodamine 6G-labeled macrophages is, however, responsible for the twofold increase in the ASE threshold and a reduction in the ASE intensity, dominantly due to a suppressed in and out-coupling of light at high nanoparticle concentrations.

Direct and alternating magnon spin currents across a junction interface irradiated by linearly polarized laser

The developments in the field of quantum optics raise expectations that laser-matter coupling is a promising building block for magnonics. Here, we propose a method for the generation of direct and alternating spin currents of magnons across the junction interface irradiated by linearly polarized laser. In a junction of ferromagnetic insulators with a large electronic gap, the spin angular momentum is exchanged during the tunneling process of magnons across the junction interface. The advanced technology in the field of plasmonics and metamaterials realizes that spins irradiated by the laser field interact only with the magnetic component of the laser through the Zeeman coupling. Using an analytic perturbation theory, we provide a general formula for magnon transport induced by the inversion symmetry breaking across the junction interface. Then, we show that those spin currents are enhanced by the ferromagnetic resonance, and the period of the ac spin current is one-half of that of the laser magnetic field. Finally, we estimate the magnitude of the spin current, and find that it will be within experimental reach.

Multimetallic Metasurfaces for Enhanced Electrocatalytic Oxidations in Direct Alcohol Fuel Cells

AbstractPlasmonic metasurfaces enable unprecedented manipulation of light by using periodic arrangement of resonant unit cells or nanoantennas. Here, multimetallic metasurfaces made of self‐standing Ni/Au‐Pt nanostructured films are shown to significantly enhance an electrocatalytic oxidation reaction employed in direct alcohol fuel cells. The Ni/Au metasurfaces support photonic and plasmonic modes, which are leveraged for the site‐selective deposition of Pt electrocatalysts within the electromagnetic hot spots, where their reactivity can be strongly increased. The enhanced electrocatalytic activity for the methanol oxidation reaction (MOR) is primarily attributed to electronic effects due to the excitation of hot charge carriers and plasmonic near fields, as supported by electromagnetic simulations and kinetic isotopic experiments. Wavelength‐dependent photoelectrochemical investigations suggest that Ni/Au‐Pt metasurfaces enhances MOR over a broad spectral range and favors different light‐induced reaction mechanisms depending on the selected energy window.

Biological imaging applications using colloidal quantum dots with enhanced photoluminescence intensity

The combination of colloidal quantum dots (QDs) and metals yields plasmonic effects, which is promising for application in bio-imaging. On increasing the contact area between CdSe QDs and gold, the PL enhancement ratio increases because of enhanced coupling between the excitons of CdSe QDs and the surface plasmon fields of gold nanoplates; furthermore, a 1.5 times larger PL enhancement factor is observed. These results indicate the correlation between the surface plasmonic effective areas and enhancement ratio of PL, which can help identify a condition for the maximized enhancement of PL intensity for designing more efficient future bio-imaging devices.

Finite-size and quantum effects in plasmonics: manifestations and theoretical modelling [Invited

The tremendous growth of the field of plasmonics in the past twenty years owes much to the pre-existence of solid theoretical foundations. Rather than calling for the introduction of radically new theory and computational techniques, plasmonics required, to a large extent, application of some of the most fundamental laws in physics, namely Maxwell’s equations, albeit adjusted to the nanoscale. The success of this description, which was triggered by the rapid advances in nanofabrication, makes a striking example of new effects and novel applications emerging by applying known physics to a different context. Nevertheless, the prosperous recipe of treating nanostructures within the framework of classical electrodynamics and with use of macroscopic, bulk material response functions (known as the local-response approximation, LRA) has its own limitations, and inevitably fails once the relevant length scales approach the few- to sub-nm regime, dominated by characteristic length scales such as the electron mean free path and the Fermi wavelength. Here we provide a review of the main non-classical effects that emerge when crossing the border between the macroscopic and atomistic worlds. We study the physical mechanisms involved, highlight experimental manifestations thereof and focus on the theoretical efforts developed in the quest for models that implement atomistic descriptions into otherwise classical-electrodynamic calculations for mesoscopic plasmonic nanostructures.

Impacts of plasmonic nanoparticles incorporation and interface energy alignment for highly efficient carbon-based perovskite solar cells

This work utilizes a realistic electro-optical coupled simulation to study the (i) impact of mesoporous TiO2 removal; (ii) the embedding of Ag@SiO2 and SiO2@Ag@SiO2 plasmonic nanoparticles; (iii) utilization of solution-processed inorganic p-type copper(I) thiocyanate (CuSCN) layer at the perovskite/carbon interface; and (iv) the increase of the work function of carbon electrodes (via incorporation of suitable additives/binders to the carbon ink) on the performance of carbon-based PSCs. Removal of mesoporous TiO2 increased the power conversion efficiency (PCE) of the device from 14.83 to 16.50% due to the increase in exciton generation rate and charge carriers’ mobility in the vicinity of the perovskite-compact TiO2 interface. Subsequently, variable mass ratios of Ag@SiO2 and SiO2@Ag@SiO2 plasmonic nanoparticles are embedded in the vicinity of the perovskite-compact TiO2 interface. In the optimum cases, the PCE of the devices increased to 19.72% and 18.92%, respectively, due to light trapping, scattering, and strong plasmonic fields produced by the plasmonic nanoparticles. Furthermore, adding the CuSCN layer remarkably increased the PCE of the device with a 0.93% mass ratio of Ag@SiO2 nanoparticles from 19.72 to 26.58% by a significant improvement of Voc and FF, due to the proper interfacial energy band alignment and the reduction of the recombination current density. Similar results were obtained by increasing the carbon work function, and the cell PCE was enhanced up to 26% in the optimal scenario. Our results pave the way to achieve high efficiencies in remarkably stable printable carbon-based PSCs.

Orbital-resolved visualization of single-molecule photocurrent channels.

Given its central role in utilizing light energy, photoinduced electron transfer (PET) from an excited molecule has been widely studied1-6. However, even though microscopic photocurrent measurement methods7-11 have made it possible to correlate the efficiency of the process with local features, spatial resolution has been insufficient to resolve it at the molecular level. Recent work has, however, shown that single molecules can be efficiently excited and probed when combining a scanning tunnelling microscope (STM) with localized plasmon fields driven by a tunable laser12,13. Here we use that approach to directly visualize with atomic-scale resolution the photocurrent channels through the molecular orbitals of a single free-base phthalocyanine (FBPc) molecule, by detecting electrons from its first excited state tunnelling through the STM tip. We find that the direction and the spatial distribution of the photocurrent depend sensitively on the bias voltage, and detect counter-flowing photocurrent channels even at a voltage where the averaged photocurrent is near zero. Moreover, we see evidence of competition between PET and photoluminescence12, and find that we can control whether the excited molecule primarily relaxes through PET or photoluminescence by positioning the STM tip with three-dimensional, atomic precision. These observations suggest that specific photocurrent channels can be promoted or suppressed by tuning the coupling to excited-state molecular orbitals, and thus provide new perspectives for improving energy-conversion efficiencies by atomic-scale electronic and geometric engineering of molecular interfaces.

Recent advances in ultrafast plasmonics: from strong field physics to ultraprecision spectroscopy

Abstract Surface plasmons, the collective oscillation of electrons, enable the manipulation of optical fields with unprecedented spatial and time resolutions. They are the workhorse of a large set of applications, such as chemical/biological sensors or Raman scattering spectroscopy, to name only a few. In particular, the ultrafast optical response configures one of the most fundamental characteristics of surface plasmons. Thus, the rich physics about photon–electron interactions could be retrieved and studied in detail. The associated plasmon-enhanced electric fields, generated by focusing the surface plasmons far beyond the diffraction limit, allow reaching the strong field regime with relatively low input laser intensities. This is in clear contrast to conventional optical methods, where their intrinsic limitations demand the use of large and costly laser amplifiers, to attain high electric fields, able to manipulate the electron dynamics in the non-linear regime. Moreover, the coherent plasmonic field excited by the optical field inherits an ultrahigh precision that could be properly exploited in, for instance, ultraprecision spectroscopy. In this review, we summarize the research achievements and developments in ultrafast plasmonics over the last decade. We particularly emphasize the strong-field physics aspects and the ultraprecision spectroscopy using optical frequency combs.

Resolved terahertz spectroscopy of tiny molecules employing tunable spoof plasmons in an otto prism configuration

Sensitive detection of terahertz fingerprint absorption spectrum for tiny molecules is essential for bioanalysis. However, it is extremely challenging for traditional terahertz spectroscopy measurement because of the weak spectral response caused by the large mismatch between terahertz wavelengths and biomolecular dimensions. Here, we proposed a wideband-tunable metal plasmonic terahertz biosensor to detect tiny biomolecules, employing attenuated total reflection in an Otto prism configuration and tightly confined spoof surface plasmons on the grooved metal surface. Benefitting from the plasmonic electric field enhancement, such a biosensor is able to identify the molecular terahertz fingerprints. As a proof of concept, a hypothetical molecule modeled by the Lorentz model with two vibrational modes is used as the sensing analytes. Simulation results show that the absorption of two vibrational modes of analytes can be selectively enhanced up to ten times by plasmonic resonance, and their fingerprints can be resolved by sweeping incident angle in a wide waveband. Our work provides an effective approach for the highly sensitive identification of molecular fingerprints in fields of biochemical sensing for tiny analytes.

Understanding Quantum Plasmonic Enhancement in Nanorod Dimers from Time-Dependent Orbital-Free Density Functional Theory

Localized surface plasmon resonances could yield extreme enhancement of local electric fields at surfaces of plasmonic nanostructures. Herein, we have performed quantum mechanical simulations to systematically study plasmonic resonances in sodium (Na) nanorod dimers based on time-dependent orbital-free density functional theory. Several representative geometries, including end-to-end, side-to-side, and right-angle T- and L-shaped dimer arrangements are explored in detail. The optical spectra, tunneling electric current, and electric field enhancement (hot spots) are examined as a function of the size of the nanorods, their relative arrangement, and their gap distance (≤2 nm). Two plasmon resonant modes are identified to be responsible for the observed electric field enhancement. One of them is of quantum nature, arising from quantum tunneling across the gap of the two nanorods. The other mode is of electrostatic nature, originating from the dipolar interaction between the plasmonic oscillations of each nanorod. Among the examined geometries, the end-to-end dimer exhibits the strongest field enhancement, which increases with the aspect ratio and the gap distance. The interplay between electron tunneling across the gap and the spill-out of electrons at the nanorod surfaces is revealed to dominate the modulation of plasmonic resonances and field enhancement in the nanorod dimers.

Recent advances on improved optical, thermal, and radiative characteristics of plasmonic nanofluids: Academic insights and perspectives

To enhance the assimilation of light in the solar thermal area, we need to focus beyond the thermo-physical properties of the nanoparticles, i.e., optical properties of the nanoparticles (NPs) augment the optical characteristics of the solar spectrum; therefore, the concept of plasmonic nanofluids has been introduced. The plasmonic nanoparticles (mainly work on scattering and absorption mechanisms) suspended in a base fluid are known to enhance the thermal and photon efficiency of the volumetric solar thermal collectors compared to the conventional ones. Further, this study aims to review the most recently published works on plasmonic nanofluids that exclusively present its preparation methods, thermophysical properties, and applications in solar collectors. Following, an overview of the potential features of plasmonic nanofluids and their preparation methods are presented. Afterward, the stability and thermophysical properties of such nanofluids are discussed. Then, the application in solar energy collectors, automotive cooling, as well as biomedical applications are overviewed. Finally, some future directions for further research in this field of study are suggested. In this work, we reviewed the work done in the plasmonic field in the last decade, and we have tried to summarize the results based on published data and future outlooks. This work can benefit researchers in this field as there is no comprehensive review of plasmonic nanofluids available. This work is believed to help the researchers to modernize the latest trends and understand the potential research gap in the optical properties of nanofluids to enhance the performance of solar collectors further and reduce thermal losses.

Ultrafast microscopy of a twisted plasmonic spin skyrmion

We report a transient plasmonic spin skyrmion topological quasiparticle within surface plasmon polariton vortices, which is described by analytical modeling and imaging of its formation by ultrafast interferometric time-resolved photoemission electron microscopy. Our model finds a twisted skyrmion spin texture on the vacuum side of a metal/vacuum interface and its integral opposite counterpart in the metal side. The skyrmion pair forming a hedgehog texture is associated with co-gyrating anti-parallel electric and magnetic fields, which form intense pseudoscalar E·B focus that breaks the local time-reversal symmetry and can drive magnetoelectric responses of interest to the axion physics. Through nonlinear two-photon photoemission, we record attosecond precision images of the plasmonic vectorial vortex field evolution with nanometer spatial and femtosecond temporal (nanofemto) resolution, from which we derive the twisted plasmonic spin skyrmion topological textures, their boundary, and topological charges; the modeling and experimental measurements establish a quantized integer photonic topological charge that is stable over the optical generation pulse envelope.

Nanoscale-Femtosecond Imaging of Evanescent Surface Plasmons on Silver Film by Photon-Induced Near-Field Electron Microscopy.

Surface plasmons on silver nanostructures have a broad range of tunable resonance properties in visible and near-infrared regimes, which possess wide applications in nanophotonics and optoelectronics. Here we use a femtosecond laser to excite surface plasmons on a silver film and trace the subsequent transient dynamics via photon-induced near-field electron microscopy (PINEM). A polarization experiment of PINEM demonstrates a conspicuous polarization dependence of the transient surface plasmon field on the silver film; however, unlike silver nanowires and nanorods, there is no polarization dependence for the PINEM intensity. This compelling finding suggests a thin film platform can be more easily used to identify the temporal and spatial overlaps between the pump laser and probe electron pulses in 4D ultrafast electron microscopy (UEM). Our work illustrates the femtosecond excitation and transient behavior of the surface plasmons on silver film and paves a universal, simple way for identifying the time zero in 4D UEM.

Research Progress of Plasmonic Nanostructure-Enhanced Photovoltaic Solar Cells.

Enhancement of the electromagnetic properties of metallic nanostructures constitute an extensive research field related to plasmonics. The latter term is derived from plasmons, which are quanta corresponding to longitudinal waves that are propagating in matter by the collective motion of electrons. Plasmonics are increasingly finding wide application in sensing, microscopy, optical communications, biophotonics, and light trapping enhancement for solar energy conversion. Although the plasmonics field has relatively a short history of development, it has led to substantial advancement in enhancing the absorption of the solar spectrum and charge carrier separation efficiency. Recently, huge developments have been made in understanding the basic parameters and mechanisms governing the application of plasmonics, including the effects of nanoparticles’ size, arrangement, and geometry and how all these factors impact the dielectric field in the surrounding medium of the plasmons. This review article emphasizes recent developments, fundamentals, and fabrication techniques for plasmonic nanostructures while investigating their thermal effects and detailing light-trapping enhancement mechanisms. The mismatch effect of the front and back light grating for optimum light trapping is also discussed. Different arrangements of plasmonic nanostructures in photovoltaics for efficiency enhancement, plasmonics’ limitations, and modeling performance are also deeply explored.

Unique Electronic Excitations at Highly Localized Plasmonic Field.

ConspectusUnder visible light illuminations, noble metal nanostructures can condense photon energy into the nanoscale region. By precisely tuning the metal nanostructures, the ultimate confinement of photoenergy at the molecular scale can be obtained. At such a confined photon energy field, various unique photoresponses of molecules, such as efficient visible light energy conversion processes or efficient multielectron transfer reactions, can be observed. Light-matter interactions also increase with the condensation of photons with nanoscale regions, leading to efficient light energy utilizations. Moreover, the strong field confinement can often modulate electronic excitations beyond normal selection rules. Such unique electronic excitations could realize innovative photoenergy conversion systems. On the other hand, such interactions lead to changes in the optical absorption property of the system via the formation of hybridized electronic energy states. This hybridized state is expected to have the potential to modulate the chemical reaction pathways. Taking these facts into consideration, a probe for the molecular absorption process with high sensitivity allows us to find novel ways for further precise tuning of light-matter interactions. In this Account, we review phenomena of unique electronic excitations from the perspective of our previous investigations using surface-enhanced Raman scattering (SERS) spectroscopy at electrified interfaces. Because the enhancement mechanism of Raman scattering at interfaces is deeply correlated with the photon absorption process accompanied by the electronic excitations between molecules and electrode surfaces, the detailed SERS investigations of the well-defined system can provide information on the electronic excitation processes. Through SERS observations of single-molecule junctions at electrodes or well-defined low-dimensional carbon materials, we have observed the characteristic Raman bands containing additional polarization tensors, indicating the occurrence of electronic polarization induced by electronic excitations based on a distinct selection rule. The origins for the observed facts were attributed to the highly condensed electric field producing the huge intensity gradient at the nano scale. The electrochemical potential control of the system would be valuable for the control of the excitation process. Additionally, from Raman spectra of dye molecules coupled to the plasmonic field, the changes in the Raman scattering intensity depending on the strength of interactions suggested the modulation of the absorption characteristics of the system. In addition, we have proved that the electrochemical potential control method can be a powerful tool for the active tuning of the light-matter interaction, leading to the change in the light absorption property. The molecular behaviors of dyes in the strong-coupling regime were reversibly tuned to show intense SERS. The current descriptions provide novel insights for these unique electronic excitations, realized by the plasmon excitation, that lead to advanced photoenergy conversions beyond the limits of present systems.

Fabrication of TiO2 nanodot films using simple solution dipping method and block copolymer template

Block copolymer (BCP) self-assembled nanostructures as a template in conjunction with a low-cost inorganic material deposition method can be a practical solution for many applications in the fields of microelectronics, optoelectronics, and plasmonics. Here, we demonstrate the fabrication of TiO2 nanodot films using polystyrene-b-polymethylmethacrylate (PS-b-PMMA) BCP as a template and a simple solution dipping process for TiO2 deposition. For this purpose, we prepared BCP templates using two different methods, namely, the selective deposition method and the masked deposition method. In the selective deposition method, as-grown self-assembled cylinder forming PS-b-PMMA was used as a template and in the masked deposition method, PMMA was etched out selectively from PS-b-PMMA nanostructured films. The scanning electron microscopy results show the average diameter of TiO2 nanodots grown by the selective deposition method is smaller compared to the masked deposition method, whereas the inter-nanodot distance is similar for both deposition methods. X-ray diffraction and photoluminescence confirm the formation of TiO2 in samples deposited by these two methods. The smaller nanodot size for the selective deposition method can be attributed to the limited interaction of the Ti precursor used here with the PMMA copolymer active functional groups. Therefore, in addition to being advantageous due to less processing steps, the selective deposition method can be used for the fabrication of lower dimensional nanostructures by identifying proper precursors and polymers and by controlling the interaction parameters. Our results will be useful for exploring interactions of other polymers with inorganic material precursors and thereby fabricating different nanostructures with desired morphologies using a simple and cost-effective dipping method.

Comparing the nature of quantum plasmonic excitations for closely spaced silver and gold dimers.

In the new field of quantum plasmonics, plasmonic excitations of silver and gold nanoparticles are utilized to manipulate and control light-matter interactions at the nanoscale. While quantum plasmons can be described with atomistic detail using Time-Dependent Density Functional Theory (DFT), such studies are computationally challenging due to the size of the nanoparticles. An efficient alternative is to employ DFT without approximations only for the relatively fast ground state calculations and use tight-binding approximations in the demanding linear response calculations. In this work, we use this approach to investigate the nature of plasmonic excitations under the variation of the separation distance between two nanoparticles. We thereby provide complementary characterizations of these excitations in terms of Kohn-Sham single-orbital transitions, intrinsic localized molecular fragment orbitals, scaling of the electron-electron interactions, and probability of electron tunneling between monomers.

Far-field position-tunable trapping of dielectric particles using a graphene-based plasmonic lens.

In this report, a graphene-based plasmonic lens is designed for far-field position-tunable trapping of dielectric particles at a wavelength of 1550 nm, in which target particles can be floated at a variable z-position, using a variable gate voltage applied to the graphene ribbons. Preventing proximity of the trapped particle and the metallic lens structure, we can diminish general thermal issues in plasmonic tweezers, while realizing higher degrees of freedom in studying target characteristics of the particles by achieving position-tunable 3D trapping. These advantageous aspects are impossible in conventional plasmonic tweezers, because of the highly evanescent nature of the plasmonic field at the metal interface. The proposed structure is comprised of two concentric circular slit-sets (S1, S2), each capable of sending a directive beam, which can lead to a constructive interference, and forming a subwavelength focal spot in the far-field. Taking advantage of the epsilon-near-zero (ENZ) behavior of graphene, each of the radiating slit-sets can be switched ON/OFF, with a radiation switching ratio of about 49, by applying a small electric pulse of 80 meV to change the Fermi energy of the corresponding graphene ribbon from 0.535 eV to 0.615 eV. Hence, inverting the radiation state of the designed lens, from (S1:ON, S2:OFF) to (S1:OFF, S2:ON), we can change the z-position of the focal trapping site from 5000 nm to 9800 nm. This configuration can be proposed as a new generation of long-range, electrostatically tunable 3D plasmonic tweezing, without the need for any external bulky optomechanical equipment.

Control of plasmonic field enhancement by mode-mixing

We demonstrate experimentally that nanoscale control of plasmonic field enhancement becomes available by changing the polarization state of light. This is revealed by photoelectron emission from plasmonic nanorods illuminated with linearly and circularly polarized femtosecond laser pulses. Simulations show that the tunability of the field enhancement originates from the mode-mixing property of circularly polarized illumination, meaning simultaneous excitation of multiple plasmon modes of the nanostructures. Performing trajectory calculations of the photoemitted electrons, we prove that the kinetic energy scaling law remains the same irrespective to the polarization state.