Time-Dependent Ultrafast Quadratic Nonlinearity in an Epsilon-Near-Zero Platform.

Ultrafast nonlinearity, which results in modulation of the linear optical response, is a basis for the development of time-varying media, in particular those operating in the epsilon-near-zero (ENZ) regime. Here, we demonstrate that the intraband excitation of hot electrons in the ENZ film results in a second-harmonic resonance shift of ∼10 THz (40 nm) and second-harmonic generation (SHG) intensity changes of >100% with only minor (<1%) changes in linear transmission. The modulation is 10-fold enhanced by a plasmonic metasurface coupled to a film, allowing for ultrafast modulation of circularly polarized SHG. The effect is described by the plasma frequency renormalization in the ENZ material and the modification of the electron damping, with a possible influence of the hot-electron dynamics on the quadratic susceptibility. The results elucidate the nature of the second-order nonlinearity in ENZ materials and pave the way to the rational engineering of active nonlinear metamaterials and metasurfaces for time-varying applications.

Molecular Plasmonics with Metamaterials.

Molecular plasmonics, the area which deals with the interactions between surface plasmons and molecules, has received enormous interest in fundamental research and found numerous technological applications. Plasmonic metamaterials, which offer rich opportunities to control the light intensity, field polarization, and local density of electromagnetic states on subwavelength scales, provide a versatile platform to enhance and tune light-molecule interactions. A variety of applications, including spontaneous emission enhancement, optical modulation, optical sensing, and photoactuated nanochemistry, have been reported by exploiting molecular interactions with plasmonic metamaterials. In this paper, we provide a comprehensive overview of the developments of molecular plasmonics with metamaterials. After a brief introduction to the optical properties of plasmonic metamaterials and relevant fabrication approaches, we discuss light-molecule interactions in plasmonic metamaterials in both weak and strong coupling regimes. We then highlight the exploitation of molecules in metamaterials for applications ranging from emission control and optical modulation to optical sensing. The role of hot carriers generated in metamaterials for nanochemistry is also discussed. Perspectives on the future development of molecular plasmonics with metamaterials conclude the review. The use of molecules in combination with designer metamaterials provides a rich playground both to actively control metamaterials using molecular interactions and, in turn, to use metamaterials to control molecular processes.

Transverse spin dynamics in structured electromagnetic guided waves.

Spin-momentum locking, a manifestation of topological properties that governs the behavior of surface states, was studied intensively in condensed-matter physics and optics, resulting in the discovery of topological insulators and related effects and their photonic counterparts. In addition to spin, optical waves may have complex structure of vector fields associated with orbital angular momentum or nonuniform intensity variations. Here, we derive a set of spin-momentum equations which describes the relationship between the spin and orbital properties of arbitrary complex electromagnetic guided modes. The predicted photonic spin dynamics is experimentally verified with four kinds of nondiffracting surface structured waves. In contrast to the one-dimensional uniform spin of a guided plane wave, a two-dimensional chiral spin swirl is observed for structured guided modes. The proposed framework opens up opportunities for designing the spin structure and topological properties of electromagnetic waves with practical importance in spin optics, topological photonics, metrology and quantum technologies and may be used to extend the spin-dynamics concepts to fluid, acoustic, and gravitational waves.

Broadband Transient Response and Wavelength-Tunable Photoacoustics in Plasmonic Hetero-nanoparticles.

The optically driven acoustic modes and nonlinear response of plasmonic nanoparticles are important in many applications, but are strongly resonant, which restricts their excitation to predefined wavelengths. Here, we demonstrate that multilayered spherical plasmonic hetero-nanoparticles, formed by alternating layers of gold and silica, provide a platform for a broadband nonlinear optical response from visible to near-infrared wavelengths. They also act as a tunable optomechanical system with mechanically decoupled layers in which different acoustic modes can be selectively switched on/off by tuning the excitation wavelength. These observations not only expand the knowledge about the internal structure of composite plasmonic nanoparticles but also allow for an additional degree of freedom for controlling their nonlinear optical and mechanical properties.

Waveguide-Integrated Light-Emitting Metal-Insulator-Graphene Tunnel Junctions.

Ultrafast interfacing of electrical and optical signals at the nanoscale is highly desired for on-chip applications including optical interconnects and data processing devices. Here, we report electrically driven nanoscale optical sources based on metal-insulator-graphene tunnel junctions (MIG-TJs), featuring waveguided output with broadband spectral characteristics. Electrically driven inelastic tunneling in a MIG-TJ, realized by integrating a silver nanowire with graphene, provides broadband excitation of plasmonic modes in the junction with propagation lengths of several micrometers (∼10 times larger than that for metal-insulator-metal junctions), which therefore propagate toward the junction edge with low loss and couple to the nanowire waveguide with an efficiency of ∼70% (∼1000 times higher than that for metal-insulator-metal junctions). Alternatively, lateral coupling of the MIG-TJ to a semiconductor nanowire provides a platform for efficient outcoupling of electrically driven plasmonic signals to low-loss photonic waveguides, showing potential for applications at various integration levels.

Plasmonic Nanocavity Induced Coupling and Boost of Dark Excitons in Monolayer WSe2 at Room Temperature.

Spin-forbidden excitons in monolayer transition metal dichalcogenides are optically inactive at room temperature. Probing and manipulating these dark excitons are essential for understanding exciton spin relaxation and valley coherence of these 2D materials. Here, we show that the coupling of dark excitons to a metal nanoparticle-on-mirror cavity leads to plasmon-induced resonant emission with the intensity comparable to that of the spin-allowed bright excitons. A three-state quantum model combined with full-wave electrodynamic calculations reveals that the radiative decay rate of the dark excitons can be enhanced by nearly 6 orders of magnitude through the Purcell effect, therefore compensating its intrinsic nature of weak radiation. Our nanocavity approach provides a useful paradigm for understanding the room-temperature dynamics of dark excitons, potentially paving the road for employing dark exciton in quantum computing and nanoscale optoelectronics.

Atomically Smooth Single-Crystalline Platform for Low-Loss Plasmonic Nanocavities.

Nanoparticle-on-mirror plasmonic nanocavities, capable of extreme optical confinement and enhancement, have triggered state-of-the-art progress in nanophotonics and development of applications in enhanced spectroscopies. However, the optical quality factor and thus performance of these nanoconstructs are undermined by the granular polycrystalline metal films (especially when they are optically thin) used as a mirror. Here, we report an atomically smooth single-crystalline platform for low-loss nanocavities using chemically synthesized gold microflakes as a mirror. Nanocavities constructed using gold nanorods on such microflakes exhibit a rich structure of plasmonic modes, which are highly sensitive to the thickness of optically thin (down to ∼15 nm) microflakes. The microflakes endow nanocavities with significantly improved quality factor (∼2 times) and scattering intensity (∼3 times) compared with their counterparts based on deposited films. The developed low-loss nanocavities further allow for the integration with a mature platform of fiber optics, opening opportunities for realizing nanocavity-based miniaturized photonic devices for practical applications.

Angle-insensitive plasmonic nanorod metamaterial-based band-pass optical filters.

We demonstrate, experimentally and theoretically, a new class of angle-insensitive band-pass optical filters that utilize anisotropy of plasmonic nanorod metamaterials, in both ε ≃ -1 and epsilon-near-infinity regimes, to minimize dependence of optical path on the incident angle. The operating wavelength and bandwidth of the filter can be engineered by controlling the geometry of the metamaterial. Experimental results are in agreement with full wave numerical and analytical solutions of the Maxwell's equations. Theoretical simulations show that performance of the systems can be further improved by replacing metallic mirrors with dielectric stacks.

Photonic Spin Lattices: Symmetry Constraints for Skyrmion and Meron Topologies.

Symmetry and topology govern many electronic, magnetic, and photonic phenomena in condensed matter physics and optics, resulting in counterintuitive skyrmion, meron, and other phenomena important for modern technologies. Here we demonstrate photonic spin lattices as a new topological construct governed by the spin-orbit coupling in an optical field. The symmetry of the electromagnetic field in the presence of the spin-orbit interaction may result in only two types of photonic spin lattices: either hexagonal spin-skyrmion or square spin-meron lattices. We show that these spin structures correspond to the lowest energy of the electromagnetic field configuration, therefore, energetically stable. We further show that in the absence of spin-orbit coupling these spin topologies are degenerated in dynamic field skyrmions, unifying the description of electromagnetic field topologies. The results provide a new understanding of electromagnetic field topology and its transformations as well as new opportunities for applications in quantum technologies, spin optics, and topological photonics.

3D Full-Color Image Projection Based on Reflective Metasurfaces under Incoherent Illumination.

Metasurfaces provide an efficient approach to control light wavefronts and have emerged at the forefront of digital holography. Nevertheless, full-color image projection remains challenging. Using a combination of specular and diffuse reflections from a metasurface, in analogy to the normal mapping technique, we designed a reflective metasurface performing in the whole visible spectral range to demonstrate 2D images with shading effects of 3D objects. The noninterleaved metasurface is based on aluminum nanostructures with high and relatively uniform efficiency across the visible spectrum. It operates under incoherent illumination and does not require polarizing optics to observe images. The integration of the metasurface behind pre-existing transparent color images is also demonstrated for introduction of 3D effects. Emulating color 3D images with flat metasurfaces can be useful for security applications and decorative purposes. The design of broadband metasurface diffusers is also interesting for flat optical diffusing elements with engineered properties and display technology.

Giant Enhancement of Second-Order Nonlinearity of Epsilon-near- Zero Medium by a Plasmonic Metasurface.

Nonlinear frequency conversion at the nanoscale is important for many applications in free space and integrated photonics. In epsilon-near-zero (ENZ) materials, second-harmonic generation (SHG) is significantly enhanced but the oblique incidence is required to address nonlinearity. To circumvent this constraint, we design a hybrid metasurface consisting of plasmonic nanostructures on an ENZ nanofilm generating strongly enhanced SHG at normal incidence in transmission. We show that the Au meta-atoms on an indium-tin-oxide (ITO) layer provide an approximately 104-fold experimentally measured SHG enhancement at normal incidence at the fundamental wavelength near the ENZ condition of ITO. This giant enhancement stems from reshaping the vectorial properties of the incident light near the Au nanostructures and its increased coupling to the ENZ film. The proposed hybrid ENZ metasurface offers a promising platform for developing ultracompact and efficient nonlinear optical sources at the nanoscale.

Optoelectronic Synapses Based on Hot-Electron-Induced Chemical Processes.

Highly efficient information processing in the brain is based on processing and memory components called synapses, whose output is dependent on the history of the signals passed through them. Here, we have developed an artificial synapse with both electrical and optical memory effects using chemical transformations in plasmonic tunnel junctions. In an electronic implementation, the electrons tunneled into plasmonic nanorods under a low bias voltage are harvested to write information into the tunnel junctions via hot-electron-mediated chemical reactions with the environment. In an optical realization, the information can be written by an external light illumination to excite hot electrons in the plasmonic nanorods. The stored information is nonvolatile and can be read either electrically or optically by measuring the resistance or inelastic-tunneling-induced light emission, respectively. The described architecture provides a high density (∼1010 cm-2) of memristive optoelectronic devices which can be used as multilevel nonvolatile memory, logic units, or artificial synapses in future electronic, optoelectronic, and artificial neural networks.

Plasmonic Metamaterials for Nanochemistry and Sensing.

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.

Optimizing hot carrier effects in Pt-decorated plasmonic heterostructures.

Hot carrier generation by light in various semiconductors and metallic nanostructures is important for many photocatalytic and photochemical processes, including water and hydrogen splitting. Here, we report on investigations of hot electron generation and extraction from Pt decorated SiO2-Au nanoparticles using the degradation of methylene blue dye as a test-bed. Enhanced catalytic activity was found with an increase of Pt loading on the surface of the heterostructures. The small size of the Au nanoparticles (∼12 nm) decorating the silica nanoparticles reduces hot electron collisions and related thermalization processes, since charge carriers have short paths to the surface where reactions take place and where Pt is situated. The heterostructures exhibit a broad plasmonic resonance in the visible wavelength range from 500 to 700 nm and hot carrier generation predominately takes place under resonant excitation. Electron-microscopy characterization and numerical modelling have allowed the optimization of Pt coverage for hot-electron transfer, consisting of a thin Pt shell covering the Au nanoparticle with Pt nanoparticles additionally placed on top. This geometry provides an increased number of active sites for methylene blue degradation and promotes separation of charge carriers generated by plasmonic excitations in Au. Such SiO2-Au-Pt nanoparticles are attractive for hot-electron production due to the tunability of their plasmonic resonance and enhanced catalytic activity.

Nanocone-based plasmonic metamaterials.

Metamaterials and metasurfaces provide unprecedented opportunities for designing light-matter interactions. Optical properties of hyperbolic metamaterials with meta-atoms based on plasmonic nanorods, important in nonlinear optics, sensing and spontaneous emission control, can be tuned by varying geometrical sizes and arrangement of the meta-atoms. At the same time the role of the shape of the meta-atoms forming the array has not been studied. We present the fabrication and optical characterization of metamaterials based on arrays of plasmonic nanocones closely packed at the subwavelength scale. The plasmonic mode structure of the individual nanocones and pronounced coupling effects between them provide multiple degrees of freedom to engineer both the field enhancement and the optical properties of the resulting metamaterials. The metamaterials are fabricated using a scalable manufacturing procedure, allowing mass-production at the centimeter scale. The ultra-sharp cone apex ([Formula: see text]2 nm) and the associated field enhancement provide an extremely high density of electromagnetic hot-spots (∼1010 cm-2). These properties of nanocone-based metamaterials are important for the development of gradient-index metamaterials and in numerous applications in fluorescence enhancement, surface enhanced Raman spectroscopy as well as hot-carrier plasmonics and photocatalysis.

Nonlinearity-Induced Multiplexed Optical Trapping and Manipulation with Femtosecond Vector Beams.

Optical trapping and manipulation of atoms, nanoparticles, and biological entities are widely employed in quantum technology, biophysics, and sensing. Single traps are typically achieved with linearly polarized light, while vortex beams form rotationally unstable symmetric traps. Here we demonstrate multiplexed optical traps reconfigurable with intensity and polarization of the trapping beam using intensity-dependent polarizability of nanoparticles. Nonlinearity combined with a longitudinal field of focused femtosecond vortex beams results in a stable optical force potential with multiple traps, in striking contrast to a linear trapping regime. The number of traps and their orientation can be controlled by the cylindrical vector beam order, polarization, and intensity. The nonlinear trapping demonstrated here on the example of plasmonic nanoparticles opens up opportunities for deterministic trapping and polarization-controlled manipulation of multiple dielectric and semiconductor particles, atoms, and biological objects since most of them exhibit a required intensity-dependent refractive index.

DNA-Assembled Plasmonic Waveguides for Nanoscale Light Propagation to a Fluorescent Nanodiamond.

Plasmonic waveguides consisting of metal nanoparticle chains can localize and guide light well below the diffraction limit, but high propagation losses due to lithography-limited large interparticle spacing have impeded practical applications. Here, we demonstrate that DNA-origami-based self-assembly of monocrystalline gold nanoparticles allows the interparticle spacing to be decreased to ∼2 nm, thus reducing propagation losses to 0.8 dB per 50 nm at a deep subwavelength confinement of 62 nm (∼λ/10). We characterize the individual waveguides with nanometer-scale resolution by electron energy-loss spectroscopy. Light propagation toward a fluorescent nanodiamond is directly visualized by cathodoluminescence imaging spectroscopy on a single-device level, thereby realizing nanoscale light manipulation and energy conversion. Simulations suggest that longitudinal plasmon modes arising from the narrow gaps are responsible for the efficient waveguiding. With this scalable DNA origami approach, micrometer-long propagation lengths could be achieved, enabling applications in information technology, sensing, and quantum optics.

Temperature stability of thin film refractory plasmonic materials.

Materials such as W, TiN, and SrRuO3 (SRO) have been suggested as promising alternatives to Au and Ag in plasmonic applications owing to their stability at high operational temperatures. However, investigation of the reproducibility of the optical properties after thermal cycling between room and elevated temperatures is so far lacking. Here, thin films of W, Mo, Ti, TiN, TiON, Ag, Au, SrRuO3 and SrNbO3 are investigated to assess their viability for robust refractory plasmonic applications. These results are further compared to the performance of SrMoO3 reported in literature. Films ranging in thickness from 50 to 105 nm are deposited on MgO, SrTiO3 and Si substrates by e-beam evaporation, RF magnetron sputtering and pulsed laser deposition, prior to characterisation by means of AFM, XRD, spectroscopic ellipsometry, and DC resistivity. Measurements are conducted before and after annealing in air at temperatures ranging from 300 to 1000° C for one hour, to establish the maximum cycling temperature and potential longevity at elevated temperatures for each material. It is found that SrRuO3 retains metallic behaviour after annealing at 800° C, while SrNbO3 undergoes a phase transition resulting in a loss of metallic behaviour after annealing at 400° C. Importantly, the optical properties of TiN and TiON are degraded as a result of oxidation and show a loss of metallic behaviour after annealing at 500° C, while the same is not observed in Au until annealing at 600° C. Nevertheless, both TiN and TiON may be better suited than Au or SRO for high temperature applications operating under vacuum conditions.

Directional scattering from particles under evanescent wave illumination: the role of reactive power.

Study of photonic spin-orbital interactions, which involves control of the propagation and spatial distributions of light via its polarization, is not only important at the fundamental level but also has significant implications for functional photonic applications that require active tuning of directional light propagation. Many of the experimental demonstrations have been attributed to the spin-momentum locking characteristic of evanescent waves. In this Letter, we show another property of evanescent waves: the polarization-dependent direction of the imaginary part of the Poynting vector, i.e., reactive power. Based on this property, we propose a simple and robust way to tune the directional far-field scattering from nanoparticles near a surface under evanescent wave illumination by controlling its polarization and direction of the incident light.

Interferometric Evanescent Wave Excitation of a Nanoantenna for Ultrasensitive Displacement and Phase Metrology.

We propose a method for ultrasensitive displacement and phase measurements based on a nanoantenna illuminated with interfering evanescent waves. We show that with a proper nanoantenna design, tiny displacements and relative phase variations can be converted into changes of the scattering direction in the Fourier space. These sensitive changes stem from the strong position dependence of the orientation of the purely imaginary Poynting vector produced in the interference pattern of evanescent waves. Using strongly confined evanescent standing waves, high sensitivity is demonstrated on the nanoantenna's zero-scattering direction, which varies linearly with displacement over a wide range. With weakly confined evanescent wave interference, even higher sensitivity to tiny displacement or phase changes can be reached near a particular location. The high sensitivity of the proposed method can form the basis for many metrology applications. Furthermore, this concept demonstrates the importance of the imaginary part of the Poynting vector, a property that is related to reactive power and is often ignored in photonics.