In this work, we introduce and computationally investigate a new vibrational spectroscopy for electron microscopy, which we term “electron-and-light induced stimulated Raman” (ELISR) spectroscopy. ELISR combines an optical pump with an electron source, identifying the local chemical composition with nanometer-scale spatial resolution through electron-beam stimulated Raman scattering. To the best of our knowledge, this is the first proposal of this new imaging methodology which promises to overcome limitations of existing electron-beam vibrational spectroscopies. The implementation of ELISR will open new avenues for nanometer-scale chemical characterization of samples during electron imaging, ranging from van der Waals materials to polymer blends and biological cells and tissues.
Chirality in Nature can be found across all length scales, from the subatomic to the galactic. At the molecular scale, the spatial dissymmetry in the atomic arrangements of pairs of mirror-image molecules, known as enantiomers, gives rise to fascinating and often critical differences in chemical and physical properties. With increasing hierarchical complexity, protein function, cell communication, and organism health rely on enantioselective interactions between molecules with selective handedness. For example, neurodegenerative and neuropsychiatric disorders including Alzheimer’s and Parkinson’s diseases have been linked to distortion of chiral-molecular structure. Moreover, d-amino acids have become increasingly recognized as potential biomarkers, necessitating comprehensive analytical methods for diagnosis that are capable of distinguishing l- from d-forms and quantifying trace concentrations of d-amino acids. Correspondingly, many pharmaceuticals and agrochemicals consist of chiral molecules that target particular enantioselective pathways. Yet, despite the importance of molecular chirality, it remains challenging to sense and to separate chiral compounds. Chiral-optical spectroscopies are designed to analyze the purity of chiral samples, but they are often insensitive to the trace enantiomeric excess that might be present in a patient sample, such as blood, urine, or sputum, or pharmaceutical product. Similarly, existing separation schemes to enable enantiopure solutions of chiral products are inefficient or costly. Consequently, most pharmaceuticals or agrochemicals are sold as racemic mixtures, with reduced efficacy and potential deleterious impacts. Recent advances in nanophotonics lay the foundation toward highly sensitive and efficient chiral detection and separation methods. In this Account, we highlight our group’s effort to leverage nanoscale chiral light–matter interactions to detect, characterize, and separate enantiomers, potentially down to the single molecule level. Notably, certain resonant nanostructures can significantly enhance circular dichroism for improved chiral sensing and spectroscopy as well as high-yield enantioselective photochemistry. We first describe how achiral metallic and dielectric nanostructures can be utilized to increase the local optical chirality density by engineering the coupling between electric and magnetic optical resonances. While plasmonic nanoparticles locally enhance the optical chirality density, high-index dielectric nanoparticles can enable large-volume and uniform-sign enhancements in the optical chirality density. By overlapping these electric and magnetic resonances, local chiral fields can be enhanced by several orders of magnitude. We show how these design rules can enable high-yield enantioselective photochemistry and project a 2000-fold improvement in the yield of a photoionization reaction. Next, we discuss how optical forces can enable selective manipulation and separation of enantiomers. We describe the design of low-power enantioselective optical tweezers with the ability to trap sub-10 nm dielectric particles. We also characterize their chiral-optical forces with high spatial and force resolution using combined optical and atomic force microscopy. These optical tweezers exhibit an enantioselective optical force contrast exceeding 10 pN, enabling selective attraction or repulsion of enantiomers based on the illumination polarization. Finally, we discuss future challenges and opportunities spanning fundamental research to technology translation. Disease detection in the clinic as well as pharmaceutical and agrochemical industrial applications requiring large-scale, high-throughput production will gain particular benefit from the simplicity and relative low cost that nanophotonic platforms promise.
Chiral-optical spectroscopies, such as circular dichroism, are critical in the biomedical, pharmaceutical, and agrochemical industries for revealing structural information about molecules and determining the purity of chemical samples. Emerging nanophotonic platforms have been shown to increase the intrinsically weak interaction between circularly polarized light and chiral molecules through the concentration of the local density of optical chirality, C. However, enhancements in C have been limited to infrared and visible frequencies, while the chiral absorption features of most small molecules are in the ultraviolet. Furthermore, achievable C enhancements in nanophotonic systems remain relatively low, especially when averaged across the sample volume. Here, we use full-field simulations to design a high quality factor (high Q) diamond metasurface that enhances C by over 3 orders of magnitude in the ultraviolet regime. The diamond nanostructures enable ultraviolet Mie resonances while a biperiodic disk lattice activates high Q resonances that significantly increase the electromagnetic field intensities. When a high Q electric dipole and magnetic dipole mode are spatially and spectrally overlapped, a Kerker-like condition emerges that enables uniform sign C enhancements that are locally as high as 1130-fold. Even when averaged across the unit cell and 40 nm away from the surface, enhancements in C exceed 100-fold. We show how the quality factor and C can be further tuned by adjusting the structural asymmetry via the diameter offset in the biperiodic lattice. Our results pave the way for ultrasensitive chiral spectroscopy and efficient light-mediated enantiomer separation.
Raman optical spectroscopy promises label-free bacterial detection, identification, and antibiotic susceptibility testing in a single step. However, achieving clinically relevant speeds and accuracies remains challenging due to weak Raman signal from bacterial cells and numerous bacterial species and phenotypes. Here we generate an extensive dataset of bacterial Raman spectra and apply deep learning approaches to accurately identify 30 common bacterial pathogens. Even on low signal-to-noise spectra, we achieve average isolate-level accuracies exceeding 82% and antibiotic treatment identification accuracies of 97.0±0.3%. We also show that this approach distinguishes between methicillin-resistant and -susceptible isolates of Staphylococcus aureus (MRSA and MSSA) with 89±0.1% accuracy. We validate our results on clinical isolates from 50 patients. Using just 10 bacterial spectra from each patient isolate, we achieve treatment identification accuracies of 99.7%. Our approach has potential for culture-free pathogen identification and antibiotic susceptibility testing, and could be readily extended for diagnostics on blood, urine, and sputum.
Upconverting nanoparticles provide valuable benefits as optical probes for bioimaging and Förster resonant energy transfer (FRET) due to their high signal-to-noise ratio, photostability, and biocompatibility; yet, making nanoparticles small yields a significant decay in brightness due to increased surface quenching. Approaches to improve the brightness of UCNPs exist but often require increased nanoparticle size. Here we present a unique core–shell–shell nanoparticle architecture for small (sub-20 nm), bright upconversion with several key features: (1) maximal sensitizer concentration in the core for high near-infrared absorption, (2) efficient energy transfer between core and interior shell for strong emission, and (3) emitter localization near the nanoparticle surface for efficient FRET. This architecture consists of β-NaYbF4 (core) @NaY0.8–xErxGd0.2F4 (interior shell) @NaY0.8Gd0.2F4 (exterior shell), where sensitizer and emitter ions are partitioned into core and interior shell, respectively. Emitter concentration is varied (x = 1, 2, 5, 10, 20, 50, and 80%) to investigate influence on single particle brightness, upconversion quantum yield, decay lifetimes, and FRET coupling. We compare these seven samples with the field-standard core–shell architecture of β-NaY0.58Gd0.2Yb0.2Er0.02F4 (core) @NaY0.8Gd0.2F4 (shell), with sensitizer and emitter ions codoped in the core. At a single particle level, the core–shell–shell design was up to 2-fold brighter than the standard core–shell design. Further, by coupling a fluorescent dye to the surface of the two different architectures, we demonstrated up to 8-fold improved emission enhancement with the core–shell–shell compared to the core–shell design. We show how, given proper consideration for emitter concentration, we can design a unique nanoparticle architecture to yield comparable or improved brightness and FRET coupling within a small volume.
Plasmon-coupled circular dichroism has emerged as a promising approach for ultrasensitive detection of biomolecular conformations through coupling between molecular chirality and surface plasmons. Chiral nanoparticle assemblies without chiral molecules present also have large optical activities. We apply single-particle circular differential scattering spectroscopy coupled with electron imaging and simulations to identify both structural chirality of plasmonic aggregates and plasmon-coupled circular dichroism induced by chiral proteins. We establish that both chiral aggregates and just a few proteins in interparticle gaps of achiral assemblies are responsible for the ensemble signal, but single nanoparticles do not contribute. We furthermore find that the protein plays two roles: It transfers chirality to both chiral and achiral plasmonic substrates, and it is also responsible for the chiral three-dimensional assembly of nanorods. Understanding these underlying factors paves the way toward sensing the chirality of single biomolecules.
The inherently weak nature of chiral light–matter interactions can be enhanced by orders of magnitude utilizing artificially-engineered nanophotonic structures. These structures enable high spatial concentration of electromagnetic fields with controlled helicity and chirality. However, the effective design and optimization of nanostructures requires defining physical observables which quantify the degree of electromagnetic helicity and chirality. In this perspective, we discuss optical helicity, optical chirality, and their related conservation laws, describing situations in which each provides the most meaningful physical information in free space and in the context of chiral light–matter interactions. First, an instructive comparison is drawn to the concepts of momentum, force, and energy in classical mechanics. In free space, optical helicity closely parallels momentum, whereas optical chirality parallels force. In the presence of macroscopic matter, the optical helicity finds its optimal physical application in the case of lossless, dual-symmetric media, while, in contrast, the optical chirality provides physically observable information in the presence of lossy, dispersive media. Finally, based on numerical simulations of a gold and silicon nanosphere, we discuss how metallic and dielectric nanostructures can generate chiral electromagnetic fields upon interaction with chiral light, offering guidelines for the rational design of nanostructure-enhanced electromagnetic chirality.
Time reversal symmetry stands as a fundamental restriction on the vast majority of optical systems and devices. The reciprocal nature of Maxwell’s equations in linear, time-invariant media adds complexity and scale to photonic diodes, isolators, circulators and also sets fundamental efficiency limits on optical energy conversion. Though many theoretical proposals and low frequency demonstrations of nonreciprocity exist, Faraday rotation remains the only known nonreciprocal mechanism that persists down to the atomic scale. Here, we present photon-spin-polarized stimulated Raman scattering as a new nonreciprocal optical phenomenon which has, in principle, no lower size limit. Exploiting this process, we numerically demonstrate nanoscale nonreciprocal transmission of free-space beams at near-infrared frequencies with a 250 nm thick silicon metasurface as well as a fully-subwavelength plasmonic gap nanoantenna. In revealing all-optical spin-splitting, our results provide a foundation for compact nonreciprocal communication and computing technologies, from nanoscale optical isolators and full-duplex nanoantennas to topologically-protected networks.
Plasmonic materials and metamaterials allow light to be controlled with nanoscale precision, enabling development of on-chip lasers, modulators, and detectors; novel medical therapeutics; efficient molecular sensors; sub-diffraction-limited optical microscopies; and improved photovoltaic and photocatalytic cells, among other extraordinary applications. However, a key challenge faced by the field is materials. Current plasmonic devices predominately employ noble metals, which exhibit high optical loss and limited tunability. Additionally, they pose challenges in standard semiconductor fabrication and integration, preventing full CMOS compatibility and wide-spread utilization. The goal of this special issue is to highlight novel materials that could replace traditional plasmonic metals. These materials not only address application-specific challenges but also reveal new physics and enable new functional devices that can readily integrated with existing technologies. The 28 papers of this feature issue focus on emerging materials and fabrication technologies for plasmonics, and encompass recent advances in both passive and active components as well as linear and nonlinear plasmonic devices.
Broadly tunable photonic crystals in the near- to mid-infrared region could find use in spectroscopy, non-invasive medical diagnosis, chemical and biological sensing, and military applications, but so far have not been widely realized. We report the fabrication and characterization of three-dimensional tunable photonic crystals composed of polymer nanolattices with an octahedron unit-cell geometry. These photonic crystals exhibit a strong peak in reflection in the mid-infrared that shifts substantially and reversibly with application of compressive uniaxial strain. A strain of ~40% results in a 2.2um wavelength shift in the pseudo-stop band, from 7.3um for the as-fabricated nanolattice to 5.1um when strained. We found a linear relationship between the overall compressive strain in the photonic crystal and the resulting stopband shift, with a ~50nm blueshift in the reflection peak position per percent increase in strain. These results suggest that architected nanolattices can serve as efficient three-dimensional mechanically tunable photonic crystals, providing a foundation for new opto-mechanical components and devices across infrared and possibly visible frequencies.
We investigate the effect of parity-time (PT) symmetric optical potentials on the radiation of achiral and chiral dipole sources. Two properties unique to PT-symmetric potentials are observed. First, the dipole can be tuned to behave as a strong optical emitter or absorber based on the non-Hermiticity parameter and the dipole location. Second, exceptional points give rise to new system resonances that lead to orders-of-magnitude enhancements in the dipolar emitted or absorbed power. Utilizing these properties, we show that enantiomers of chiral molecules near PT-symmetric metamaterials exhibit a 4.5-fold difference in their emitted power and decay rate. The results of this work could enable new atom-cavity interactions for quantum optics, as well as all-optical enantioselective separation.
Tomography has enabled the characterization of the Earth's interior, visualization of the inner workings of the human brain, and three-dimensional reconstruction of matter at the atomic scale. However, tomographic techniques that rely on optical excitation or detection are generally limited in their resolution by diffraction. Here, we introduce a tomographic technique - cathodoluminescence spectroscopic tomography - to probe optical properties in three dimensions with nanometre-scale spatial and spectral resolution. We first obtain two-dimensional cathodoluminescence maps of a three-dimensional nanostructure at various orientations. We then use the method of filtered back-projection to reconstruct the cathodoluminescence intensity at each wavelength. The resulting tomograms allow us to locate regions of efficient cathodoluminescence in three dimensions across visible and near-infrared wavelengths, with contributions from material luminescence and radiative decay of electromagnetic eigenmodes. The experimental signal can be further correlated with the radiative local density of optical states in particular regions of the reconstruction. We demonstrate how cathodoluminescence tomography can be used to achieve nanoscale three-dimensional visualization of light-matter interactions by reconstructing a three-dimensional metal-dielectric nanoresonator.
NaYF4:Yb3+,Er3+ nanoparticle upconverters are hindered by low quantum efficiencies arising in large part from the parity-forbidden nature of their optical transitions and the nonoptimal spatial separations between lanthanide ions. Here, we use pressure-induced lattice distortion to systematically modify both parameters. Although hexagonal-phase nanoparticles exhibit a monotonic decrease in upconversion emission, cubic-phase particles experience a nearly 2-fold increase in efficiency. In-situ X-ray diffraction indicates that these emission changes require only a 1% reduction in lattice constant. Our work highlights the intricate relationship between upconversion efficiency and lattice geometry and provides a promising approach to modifying the quantum efficiency of any lanthanide upconverter.
Non-Hermitian parity-time (PT)-symmetric optical potentials have led to a new class of unidirectional photonic components based on the spatially symmetric and balanced inclusion of loss and gain. While most proposed and implemented PT-symmetric optical devices have wavelength-scale dimensions, no physical constraints preclude development of subwavelength PT-symmetric components. We theoretically demonstrate a nanoscale PT-symmetric, all-optical plasmonic modulator capable of phase-controlled amplification and directional absorption. The modulator consists of two deeply subwavelength channels composed of either gain or loss dielectric material, embedded in a metallic cladding. When illuminating on-resonance by two counter-propagating plane waves, the aperture's total output can be modulated by changing the phase offset between the two waves. Modulation depths are greater than 10?dB, with output power varying from less than one half of the incident power to more than six times amplification. Off-resonance, the aperture possesses strong phase-controlled directionality with the output from one side varying from perfect absorption to strong scattering and transmission. The device design provides a platform for nanoscale all-optical modulators with gain while potentially enabling coherent perfect absorption and lasing in a single, compact structure.
The field of plasmonics has revolutionized the ability to control nanoscale light-matter interactions with applications ranging from high-efficiency photovoltaic modules to ultrasensitive biodetectors, electromagnetic cloaks, and subwavelength integrated photonic circuits. This article summarizes my group?s efforts to contribute to this burgeoning field, with emphasis on our research in quantum plasmonics and optical-frequency magnetism. First, we explore the plasmon resonances of individual nanoparticles as they transition from a classical to a quantum-influenced regime. We then utilize these results to directly monitor hydrogen absorption and desorption in individual palladium nanocrystals. Subsequently, using real-time manipulation of plasmonic particles, we investigate plasmonic coupling between pairs of particles separated by nanometer- and angstrom-scale gaps. For sufficiently small separations, we observe the effects of quantum tunneling between particles on their plasmonic resonances. Finally, using the properties of coupled metallic nanoparticles, we demonstrate the colloidal synthesis of an isotropic metafluid or "metamaterial paint" that exhibits a strong optical-frequency magnetic response and the potential for negative permeabilities and negative refractive indices.
The sun is the most abundant source of carbon-free sustainable energy, but current solar cells can only capture energy from a limited portion of the solar spectrum?specifically those photons with energies above the solar cell bandgap. Here, we explore a promising approach to reduce such transmission losses: placing an upconverter behind the solar cell. Upconverting materials can absorb low-energy photons and emit higher-energy photons back toward the solar cell, thereby improving the cell?s photocurrent. An ideal upconverter can increase the efficiency of an ideal solar cell from 30% to 44%. Existing upconverting materials offer much smaller improvements, though a boost in their upconverter efficiency could yield an absolute increase in solar cell efficiency of over 2% . We discuss several schemes to improve upconverter efficiency, focusing on use of nanophotonic and plasmonic antennas to increase the absorption and emission of upconverters. These schemes can in theory enable orders-of-magnitude improvement in upconverter efficiency, positioning the technology for significant commercial applications.
Upconversion, the conversion of photons from lower to higher energies, is a process that promises applications ranging from high-efficiency photovoltaic and photocatalytic cells to background-free bioimaging and therapeutic probes. Existing upconverting materials, however, remain too inefficient for viable implementation. In this Perspective, we describe the significant improvements in upconversion efficiency that can be achieved using plasmon resonances. As collective oscillations of free electrons, plasmon resonances can be used to enhance both the incident electromagnetic field intensity and the radiative emission rates. To date, this approach has shown upconversion enhancements up to 450x. We discuss both theoretical underpinnings and experimental demonstrations of plasmon-enhanced upconversion, examining the roles of upconverter quantum yield, plasmonic geometry, and plasmon spectral overlap. We also discuss nonoptical consequences of including metal nanostructures near upconverting emitters. The rapidly expanding field of plasmon-enhanced upconversion provides novel fundamental insight into nanoscale light?matter interactions while improving prospects for technological relevance.
Many energy- and information-storage processes rely on phase changes of nanomaterials in reactive environments. Compared to their bulk counterparts, nanostructured materials seem to exhibit faster charging and discharging kinetics, extended life cycles, and size-tunable thermodynamics. However, in ensemble studies of these materials, it is often difficult to discriminate between intrinsic size-dependent properties and effects due to sample size and shape dispersity. Here, we detect the phase transitions of individual palladium nanocrystals during hydrogen absorption and desorption, using in situ electron energy-loss spectroscopy in an environmental transmission electron microscope. In contrast to ensemble measurements, we find that palladium nanocrystals undergo sharp transitions between the alpha and beta phases, and that surface effects dictate the size dependence of the hydrogen absorption pressures. Our results provide a general framework for monitoring phase transitions in individual nanocrystals in a reactive environment and highlight the importance of single-particle approaches for the characterization of nanostructured materials.
We theoretically investigate the optical properties of parity-time (PT) symmetric three-dimensional metamaterials composed of strongly-coupled planar plasmonic waveguides. By tuning the loss-gain balance, we show how the initially isotropic material becomes both asymmetric and unidirectional. Investigation of the band structure near the material's exceptional point reveals several intriguing optical properties, including double negative refraction, Bloch power oscillations, unidirectional invisibility, and reflection and transmission coefficients that are simultaneously equal to or greater than unity. The highly tunable optical dispersion of PT-symmetric metamaterials provides a foundation for designing an entirely new class of three-dimensional bulk synthetic media, with applications ranging from lossless sub-diffraction-limited optical lenses to non-reciprocal nanophotonic devices.
Non-Hermitian Hamiltonians arising from parity-time PT-symmetric potentials have been extensively explored in optical systems, owing to their ability to generate asymmetric and even non-reciprocal light propagation. In this paper, we investigate such PT-potentials in plasmonic systems, demonstrating asymmetric optical propagation in deeply subwavelength waveguides. In particular, we investigate a five layer plasmonic waveguide composed of metallic layers separated by dielectric media containing either loss or gain in equal quantities. Through an analytic solution of Maxwell's equations, we identify the four lowest order modes of the waveguide, including two positive index modes and two negative index modes, and investigate their evolution with increasing but balanced gain and loss, K. Both the exact analytic approach and an approximate one based on Rayleigh-Schrodinger perturbation theory demonstrate eigenvalue merging and state coalescence with increasing K, unlike the familiar energy-level splitting observed in conventional coupled systems. The state coalescence always occurs between modes of opposite parity. Also, by changing the coupling between the waveguide layers, state coalescence can occur between modes with opposite refractive indices, resulting in the merging of a positive index mode with a negative index mode at the exceptional point. We use dispersion diagrams and field profiles to illustrate the asymmetric plasmon propagation properties with increasing K. We also show that at the system's exceptional point, the modal power varies quadratically along the waveguide. To our knowledge, this study represents the first spectral analysis of deeply sub wavelength PT-symmetric plasmonic and multi-modal photonic waveguides, and provides a foundation for designing novel asymmetric and unidirectional nanophotonic devices.
Advances in the field of metamaterials have enabled unprecedented control of lightmatter interactions. Metamaterial constituents support high-frequency electric and magnetic dipoles, which can be used as building blocks for new materials capable of negative refraction, electromagnetic cloaking, strong visible-frequency circular dichroism, and enhancing magnetic or chiral transitions in ions and molecules. While all metamaterials to date have existed in the solid-state, considerable interest has emerged in designing a colloidal metamaterial or ‘metafluid.’ Such metafluids would combine the advantages of solution-based processing with facile integration into conventional optical components. Here we demonstrate the colloidal synthesis of an isotropic metafluid that exhibits a strong magnetic response at visible frequencies. Protein-antibody interactions are used to direct the solution-phase self-assembly of discrete metamolecules comprised of silver nanoparticles tightly packed around a single dielectric core. The electric and magnetic response of individual metamolecules and the bulk metamaterial solution are directly probed with optical scattering and spectroscopy. This colloidal metafluid can be synthesized in large-quantity and high-quality, and may accelerate development of advanced nanophotonic and metamaterial devices.
We theoretically investigate light matter interactions for chiral molecules in the presence of non-chiral nanoantennas. Isotropic nanostructures supporting optical-frequency electric or magnetic dipoles are sufficient to locally enhance the excitation of a molecule's chiral polarizability and thus its circular dichroism spectrum. However, simultaneous electric and magnetic dipoles are necessary to achieve a net, spatially-averaged enhancement. Our contribution provides a theoretical framework to understand chiral light-matter interactions at the nanoscale and sets the necessary and sufficient conditions to enhance circular dichroism spectroscopy in the presence of nanoantennas. The results may lead to new, field-enhanced, chiral spectroscopic techniques.
A broadband metamaterial presenting negative indices across hundreds of nanometers in the visible and near-infrared spectral regimes is demonstrated theoretically, using transformation optics to design the metamaterial constituents. The approach begins with an infinite plasmonic waveguide that supports a broadband but dark (i.e, not easily optically accessed) negative index mode. Conformal mapping of this waveguide to a finite split-ring-resonator-type structure transforms this mode into a bright (i.e, efficiently excited) resonance composed of degenerate electric and magnetic dipoles. A periodic array of such resonators exhibits negative refractive indices at optical frequencies in multiple regions exceeding 200 nm in bandwidth. The metamaterial response is confirmed through simulations of plane-wave refraction through a metamaterial prism. These results illustrate the power of transformation optics for new metamaterial designs and provide a foundation for future broadband metamaterial devices.
Upconversion of sub-bandgap photons is a promising approach to exceed the Shockley-Queisser limit in solar technologies. Calculations have indicated that ideal, upconverter-enhanced cell efficiencies can exceed 44% for non-concentrated sunlight, but such improvements have yet to be observed experimentally. To explain this discrepancy, we develop a thermodynamic model of an upconverter-cell considering a highly realistic narrow-band, non-unity-quantum-yield upconverter. As expected, solar cell efficiencies increase with increasing upconverter bandwidth and quantum yield, with maximum efficiency enhancements found for near-infrared upconverter absorption bands. Our model indicates that existing bimolecular and lanthanide-based upconverters will not improve cell efficiencies more than 1%, consistent with recent experiments. However, our calculations show that these upconverters can significantly increase cell efficiencies from 28% to over 34% with improved quantum yield, despite their narrow bandwidths. Our results highlight the interplay of absorption and quantum-yield in upconversion, and provide a platform for optimizing future solar upconverter designs.
This News and Views describes results from the article "Tailoring and imaging the plasmonic local density of states in crystalline nanoprisms," by Sviatlana Viarbitskaya, Alexandre Teulle, Renaud Marty, Jadab Sharma, Christian Girard, Arnaud Arbouet, and Erik Dujardin, Nature Materials (2013). Their results describe how two-photon luminescence in metallic nanostructures provides a unique signature of the number of plasmonic modes per unit energy and volume, paving the way for more efficient plasmonic sources, detectors and sensors.
The plasmon resonances of two closely spaced metallic particles have enabled applica- tions including single-molecule sensing and spectroscopy, novel nanoantennas, molecular rulers, and nonlinear optical devices. In a classical electrodynamic context, the strength of such dimer plasmon resonances increases monotonically as the particle gap size de- creases. In contrast, a quantum mechanical framework predicts that electron tunneling will strongly diminish the dimer plasmon strength for sub-nanometer-scale separations. Here, we directly observe the plasmon resonances of coupled metallic nanoparticles as their gap size is reduced to atomic dimensions. Using the electron beam of a scanning transmis- sion electron microscope (STEM), we dynamically manipulate pairs of 10-nm-diameter spherical silver nanoparticles on a substrate, controlling their convergence and eventual coalescence into a single nanosphere. We simultaneously employ electron energy-loss spectroscopy (EELS) to observe the dynamic plasmonic properties of these dimers before and after particle contact. As separations are reduced from 7 nm, the dominant dipolar peak exhibits a redshift consistent with classical calculations. However, gaps smaller than 0.5 nm cause this mode to exhibit a reduced intensity consistent with quantum theories that incorporate electron tunneling. As the particles overlap, the bonding dipolar mode disappears and is replaced by a dipolar charge transfer mode. Our dynamic imaging, manipulation, and spectroscopy of nanostructures enables therst full spectral mapping of dimer plasmon evolution, and may provide new avenues for in-situ nanoassembly and analysis in the quantum regime.
Optical trapping using focused laser beams has emerged as a powerful tool in the biological and physical sciences. However, scaling this technique to nanosized objects remains challenging due to the diffraction limit of light and the high power levels required for nanoscale trapping. In this paper, we propose plasmonic coaxial apertures as low-power optical traps for nanosized specimens. The illumination of a coaxial aperture with a linearly polarized plane wave generates a dual optical trapping potential well. We theoretically show that this potential can stably trap dielectric particles smaller than 10 nm in diameter while keeping the trapping power level below 20 mW. By tapering the thickness of the coaxial dielectric channel, trapping can be extended to sub-2-nm particles. The proposed structures may enable optical trapping and manipulation of dielectric particles ranging from single proteins to small molecules with sizes previously inaccessible.
Electrons and photons can coexist as a single entity called a surface plasmon — an elementary excitation found at the interface between a conductor and an insulator. Because of their hybrid electric and photonic nature, plasmons allow photons to be precisely controlled on the nanoscale. Plasmons are evident in the vivid hues of rose windows, which derive their color from small metallic nanoparticles embedded in the glass. They also provide the basis for color-changing biosensors (such as home pregnancy tests), photothermal cancer treatments, improved photovoltaic cell efficiencies, and nanoscale lasers. While surface plasmons were first identified nearly 55 years ago, many of their exciting applications are yet to come. This issue of MRS Bulletin reviews the progress and promise of plasmonics—from the characterization tools that have allowed nanometer-scale probing of plasmons to the new materials that may enable low-loss, active, and quantum plasmonics. Within reach are applications ranging from integrated plasmonic circuits for nanophotonic computation to plasmonic optical tweezers for manipulation of nano-sized particles and proteins.
Nanocrystal superlattices have emerged as a new platform for bottom-up metamaterial design, but their optical properties are largely unknown. Here, we investigate their emergent optical properties using a generalized semi-analytic, full-field solver based on rigorous coupled wave analysis. Attention is given to superlattices composed of noble metal and dielectric nanoparticles in unary and binary arrays. By varying the nanoparticle size, shape, separation, and lattice geometry, we demonstrate the broad tunability of superlattice optical properties. Superlattices composed of spherical or octahedral nanoparticles in cubic and AB2 arrays exhibit magnetic permeabilities tunable between 0.2 and 1.7, despite having non-magnetic constituents. The retrieved optical parameters are nearly polarization and angle-independent over a broad range of incident angles. Accordingly, nanocrystal superlattices behave as isotropic bulk metamaterials. Their tunable permittivities, permeabilities, and emergent magnetism may enable new, bottom-up metamaterials and negative index materials at visible frequencies.
Collective electron excitations in metals, called plasmons, can play an important role in second harmonic generation of light. This Viewpoint describes results from the article "Nonlinear plasmon-photon interaction resolved by k-space spectroscopy," by Nicolai B. Grosse, Jan Heckmann, and Ulrike Woggonthe, Physical Review Letters (2012)
The plasmon resonances of metallic nanoparticles have received considerable attention for their applications in nanophotonics, biology, sensing, spectroscopy and solar energy harvesting. Although thoroughly characterized for spheres larger than ten nanometres in diameter, the plasmonic properties of particles in the quantum size regime have been historically difficult to describe owing to weak optical scattering, metal–ligand interactions, and inhomogeneity in ensemble measurements. Such difficulties have precluded probing and controlling the plasmonic properties of quantum-sized particles in many natural and engineered processes, notably catalysis. Here we investigate the plasmon resonances of individual ligand-free silver nanoparticles using aberration-corrected transmission electron microscope (TEM) imaging and monochromated scanning TEM electron energy-loss spectroscopy (EELS). This technique allows direct correlation between a particle’s geometry and its plasmon resonance. As the nanoparticle diameter decreases from 20 nanometres to less than two nanometres, the plasmon resonance shifts to higher energy by 0.5 electronvolts, a substantial deviation from classical predictions. We present an analytical quantum mechanical model that describes this shift due to a change in particle permittivity. Our results highlight the quantum plasmonic properties of small metallic nanospheres, with direct application to understanding and exploiting catalytically active and biologically relevant nanoparticles.
Reducing reflection and transmission losses in photovoltaic devices is essential for realizing highly efficient power conversion. Here, we theoretically investigate arrays of radial junction silicon wires to determine the optimal geometry for maximized light absorption. Using a generalized rigorous coupled wave analysis, we calculate the scattering spectra of arrays of varying wire radii, length, and lattice filling factors. Near unity absorption, far exceeding that of conventional thin film devices, is calculated for a square array of 20 µm long wires with radii of 200 nm and a filling fraction of 30%. These results suggest a potentially cost-effective route toward high efficiency solar cells.
Upconversion of sub-bandgap photons can increase the maximum efficiency of a single-junction solar cell from 30% to over 44%. However, upconverting materials often have small absorption cross-sections and poor radiative recombination efficiencies that limit their utility in solar applications. Here, we show that the efficiency of upconversion can be substantially enhanced with a suitably designed plasmonic nanostructure. The structure consists of a spherical nanocrescent composed of an upconverter-doped dielectric core and a crescent-shaped metallic shell. Using numerical techniques, we calculate a greater than 10-fold absorption enhancement for a broad range of sub-bandgap wavelengths throughout the entire upconverting core. Further, this nanocrescent enables a 100-fold increase in above-bandgap power emission toward the solar cell. Our results provide a framework for achieving low-power solar upconversion, potentially enabling a single-junction solar cell with an efficiency exceeding the Shockley–Queisser limit.
Loss is one of the most substantial impediments to integrated plasmonics. In this paper, we present a theoretical analysis of active cylindrical plasmon slot waveguides, including their modal characteristics, gain spectra, and lasing threshold. Particular attention is given to two classes of waveguide geometries composed of various core/channel/cladding materials: a dielectric/dielectric/metal (DDM) waveguide and a metal/dielectric/metal (MDM) waveguide. Using empirically determined optical constants, we systematically study the dispersion, propagation length, threshold gain, modal gain, and confinement factor of these slot structures. For DDM waveguides, we show that introducing the gain in the channel rather than the core is of paramount importance for reduced threshold gain and increased modal gain. Confinement factor enhancement is even more pronounced in MDM waveguides, where modal gain can exceed threshold gain by 10× to 100× across visible and near-infrared frequencies. By carefully tuning the core/channel relative dimensions along with the lasing frequency, we show that threshold gain as low as 500 inverse cm is achievable in cylindrical plasmonic devices with overall diameters less than 200 nm. Our results indicate the promise of plasmonic slot structures for low-loss optical networking, and provide a roadmap for the design of optimized nanoscale plasmonic laser cavities.
Assemblies of strongly coupled plasmonic nanoparticles can support highly tunable electric and magnetic resonances in the visible spectrum. In this letter, we theoretically demonstrate Fano-like interference effects between the fields radiated by the electric and magnetic modes of symmetric nanoparticle trimers. Breaking the symmetry of the trimer system leads to a strong interaction between the modes. The near and far field electromagnetic properties of the broken symmetry trimer are tunable across a large spectral range. We exploit this Fano-like effect to demonstrate spatial and temporal control of the localized electromagnetic hotspots in the plasmonic trimer.
Upconverting materials can be used to increase the energy conversion efﬁciency of a solar cell. Such materials convert low-energy transmitted photons to higher-energy photons that can be absorbed by the cell, substantially reducing the spectral mismatch between the cell and the solar spectrum. Previously, the performance enhancements achievable with an ideal upconverter-solar cell system were theoretically investigated. Here, we perform a comprehensive analysis to determine the effects of non-ideal cell and upconverter systems, accounting for non-ideal absorption and radiative recombination. We also allow for realistic nonradiative relaxation within the upconverter. The system is modeled using a detailed balance approach, with the upconverter treated as a series connection of two small-bandgap solar cells and a large-bandgap light emitting diode. We demonstrate that signiﬁcant improvements in efﬁciency are possible even for nonconcentrated light, as long as the upconverter includes a small nonradiative relaxation pathway. Furthermore, we show that the existence of a nonradiative relaxation event in the upconverter is necessary for improved power conversion when cell absorption efﬁciency is low. Our results indicate that the efﬁciencies of both conventional-Si and thin ﬁlm photovoltaic cells can be substantially improved with upconverting materials, even including non-idealities.
In this work, H2 absorption and desorption in faceted, crystalline Au/Pd core/shell nanocrystals and their interaction with a SiOx/Si support were studied at the single-particle level. Dark-field microscopy was used to monitor the changing optical properties of these Au/Pd nanoparticles (NPs) upon exposure to H2 as reversible H2 uptake from the Pd shell proceeded. Analysis of the heterogeneous ensemble of NPs revealed the H2 uptake trajectory of each nanocrystal to be shape-dependent. Differences in particle uptake trajectories were observed for individual particles with different shapes, faceting, and Pd shell thickness. In addition to palladium hydride formation, the single-particle trajectories were able to decipher specific instances where palladium silicide formation and Au/Pd interdiffusion occurred and helped us determine that this was more frequently seen in those particles within an ensemble having thicker Pd shells. This noninvasive, plasmonic-based direct sensing technique shows the importance of single-particle experiments in catalytically active systems and provides a foundation for studying more complex catalytic processes in inhomogeneous NP systems.
Silicon-based photonic devices dissipate substantially less power and provide a significantly greater information bandwidth than electronic components. Unfortunately, large-scale integration of photonic devices has been limited by their large, wavelength-scale size and the weak optical response of Si. Surface plasmons may overcome these two limitations. Combining the high localization of electronic waves with the propagation properties of optical waves, plasmons can achieve extremely small mode wavelengths and large local electromagnetic field intensities. Si-based plasmonics has the potential to not only reduce the size of photonic components to deeply-subwavelength scales, but also to enhance the emission, detection, and manipulation of optical signals in Si. In this article, we discuss recent advances in Si-based plasmonics, including subwavelength interconnects, modulators, and emission sources. From scales spanning slab waveguides to single nanocrystals, we show that Si-based plasmonics can enable optical functionality competitive in size and speed with contemporary electronic components.
We report a method for filtering white light into individual colors using metal−insulator−metal resonators. The resonators are designed to support photonic modes at visible frequencies, and dispersion relations are developed for realistic experimental configurations. Experimental results indicate that passive Ag/Si3N4/Au resonators exhibit color filtering across the entire visible spectrum. Full field electromagnetic simulations were performed on active resonators for which the resonator length was varied from 1−3 μm and the output slit depth was systematically varied throughout the thickness of the dielectric layer. These resonators are shown to filter colors based on interference between the optical modes within the dielectric layer. By careful design of the output coupling, the resonator can selectively couple to intensity maxima of different photonic modes and, as a result, preferentially select any of the primary colors. We also illustrate how refractive index modulation in metal−insulator−metal resonators can yield actively tunable color filters. Simulations using lithium niobate as the dielectric layer and the top and bottom Ag layers as electrodes indicate that the output color can be tuned over the visible spectrum with an applied field.
Realization of chip-based all-optical and optoelectronic computational networks will require ultracompact Si-compatible modulators, ideally comprising dimensions, materials, and functionality similar to electronic complementary metal−oxide−semiconductor (CMOS) components. Here we demonstrate such a modulator, based on field-effect modulation of plasmon waveguide modes in a MOS geometry. Near-infrared transmission between an optical source and drain is controlled by a gate voltage that drives the MOS into accumulation. Using the gate oxide as an optical channel, electro-optic modulation is achieved in device volumes of half of a cubic wavelength with femtojoule switching energies and the potential for gigahertz modulation frequencies.
We present a theoretical analysis of planar plasmonic waveguides that support propagation of positive and negative index modes. Particular attention is given to the modes sustained by metal-insulator-metal (MIM), insulator-metal-insulator (IMI), and insulator-insulator-metal (IIM) geometries at visible and near-infrared frequencies. We find that all three plasmonic structures are characterized by negative indices over a finite range of visible frequencies, with figures of merit approaching 20. Moreover, using finite-difference time-domain simulations, we demonstrate that visible-wavelength light propagating from free space into these waveguides can exhibit negative refraction. Refractive index and figure-of-merit calculations are presented for Ag/GaP and Ag/Si3N4 - based structures with waveguide core dimensions ranging from 5 to 50 nm and excitation wavelengths ranging from 350 nm to 850 nm. Our results provide the design criteria for realization of broadband, visible-frequency negative index materials and transformation-based optical elements for two-dimensional guided waves. These geometries can serve as basic elements of three-dimensional negative-index metamaterials.
A diffusion bonding method has been developed that enables layer transfer of single crystal lithium niobate thin films to silicon substrates. A silver film was deposited onto both the silicon and lithium niobate surfaces prior to bonding, and upon heating, a diffusion bond was formed. Transmission electron microscopy confirms the interface evolution via diffusion bonding which combines interfacial diffusion, power law creep, and growth of (111) silver grains to replace the as-bonded interface by a single polycrystalline silver film. The transferred film composition was the same as bulk lithium niobate.
A nanoscale gap between two metal surfaces can confine propagating surface plasmon polaritons (SPPs) to very small dimensions, but this geometry makes it inherently difficult to image SPP propagation at high resolution. We demonstrate the near-field probing of these SPPs, propagating within a 50 nm thick Si3N4 waveguide with Ag cladding layers for frequencies ranging from the blue to the near-infrared. Using near-field SPP interferometry, we determine the wave vector, showing that the wavelength is shortened to values as small as 156 nm for a free-space wavelength of 532 nm.
Nanofabricated photonic materials offer opportunities for crafting the propagation and dispersion of light in matter. We demonstrate an experimental realization of a two-dimensional negative-index material in the blue-green region of the visible spectrum, substantiated by direct geometric visualization of negative refraction. Negative indices were achieved with the use of an ultrathin Au-Si3N4-Ag waveguide sustaining a surface plasmon polariton mode with antiparallel group and phase velocities. All-angle negative refraction was observed at the interface between this bimetal waveguide and a conventional Ag-Si3N4-Ag slot waveguide. The results may enable the development of practical negative-index optical designs in the visible regime.
We report experimental realization of subwavelength slot waveguides that exhibit both micrometer-range propagation and high spatial confinement of light. Attention is given to rectangular waveguides with a Si3N4 core and Ag cladding; core thicknesses of 50−100 nm and widths of 250 nm − 10 μm are explored. Propagation lengths of 5λ are achieved with light confined to lateral and transverse dimensions of λ/5 and λ/2, respectively. This unique combination of light localization and propagation is achieved via interacting surface plasmons, which produce short modal wavelengths and strong field confinement at each metal/dielectric interface.
We present a numerical analysis of surface plasmon waveguides exhibiting both long-range propagation and spatial confinement of light with lateral dimensions of less than 10% of the free-space wavelength. Attention is given to characterizing the dispersion relations, wavelength-dependent propagation, and energy density decay in two-dimensional Ag∕SiO2∕Ag structures with waveguide thicknesses ranging from 12 nm to 250 nm. As in conventional planar insulator-metal-insulator (IMI) surface plasmon waveguides, analytic dispersion results indicate a splitting of plasmon modes—corresponding to symmetric and antisymmetric electric field distributions—as SiO2 core thickness is decreased below 100 nm. However, unlike IMI structures, surface plasmon momentum of the symmetric mode does not always exceed photon momentum, with thicker films (d∼50 nm) achieving effective indices as low as n=0.15. In addition, antisymmetric mode dispersion exhibits a cutoff for films thinner than d=20 nm, terminating at least 0.25 eV below resonance. From visible to near infrared wavelengths, plasmon propagation exceeds tens of microns with fields confined to within 20 nm of the structure. As the SiO2 core thickness is increased, propagation distances also increase with localization remaining constant. Conventional waveguiding modes of the structure are not observed until the core thickness approaches 100 nm. At such thicknesses, both transverse magnetic and transverse electric modes can be observed. Interestingly, for nonpropagating modes (i.e., modes where propagation does not exceed the micron scale), considerable field enhancement in the waveguide core is observed, rivaling the intensities reported in resonantly excited metallic nanoparticle waveguides.
A numerical analysis of surface plasmon dispersion, propagation, and localization on smooth lossy films is presented. Particular attention is given to determining wavelength-dependent behavior of thin Ag slab waveguides embedded in a symmetric SiO2 environment. Rather than considering Ag as a damped free electron gas, the metal is defined by the experimentally determined optical constants of Johnson and Christy and Palik. As in free electron gas models, analytic dispersion results indicate a splitting of plasmon modes—corresponding to symmetric and antisymmetric field distributions—as film thickness is decreased below 50 nm. However, unlike free electron gas models, the surface plasmon wave vector remains finite at resonance with the antisymmetric-field plasmon converging to a pure photon mode for very thin films. In addition, allowed excitation modes are found to exist between the bound and radiative branches of the dispersion curve. The propagation characteristics of all modes are determined, and for thin films (depending upon electric field symmetry), propagation distances range from microns to centimeters in the near infrared. Propagation distances are correlated with both the field decay (skin depth) and energy density distribution in the metal and surrounding dielectric. While the energy density of most long-range surface plasmons exhibits a broad spatial extent with limited confinement in the waveguide, it is found that high-field confinement does not necessarily limit propagation. In fact, enhanced propagation is observed for silver films at ultraviolet wavelengths despite strong field localization in the metal. The surface plasmon characteristics described in this paper provide a numerical springboard for engineering nanoscale metal plasmon waveguides, and the results may provide a new avenue for integrated optoelectronic applications.
Since the development of the light microscope in the 16th century, optical device sizeand performance have been limited by diffraction.Optoelectronic devices of today aremuch bigger than the smallest electronic devices for this reason.Achieving control oflight–material interactions for photonic device applications at the nanoscale requiresstructures that guide electromagnetic energy with subwavelength-scale modeconfinement.By converting the optical mode into nonradiating surface plasmons,electromagnetic energy can be guided in structures with lateral dimensions of less than10% of the free-space wavelength.A variety of methods—including electron-beamlithography and self-assembly—have been used to construct both particle and planarplasmon waveguides.Recent experimental studies have confirmed the strongly coupledcollective plasmonic modes of metallic nanostructures.In plasmon waveguidesconsisting of closely spaced silver rods, electromagnetic energy transport over distancesof 0.5m has been observed.Moreover, numerical simulations suggest the possibility ofmulti-centimeter plasmon propagation in thin metallic stripes.Thus, there appears to beno fundamental scaling limit to the size and density of photonic devices, and ongoingwork is aimed at identifying important device performance criteria in the subwavelengthsize regime.Ultimately, it may be possible to design an entire class of subwavelength-scale optoelectronic components (waveguides, sources, detectors, modulators) thatcould form the building blocks of an optical device technology—a technology scalable to molecular dimensions, with potential imaging, spectroscopy, and interconnectionapplications in computing, communications, and chemical/biological detection.
By the mid-17th century, numerous scientists—notably including Hooke and Gallileo—had developed transparent ground lenses and applied them in the construction of compound optical microscopes. This development revolutionized the contemporary understanding of the natural world by, for example, enabling the imaging of blood cells and microbes. Ever since this now bygone era of fantastic development of optics principles and instrumentation, the size and performance of photonic devices has been largely limited by diffraction. Photonic devices of today are generally composed of dielectric materials with modest dielectric constants, and are much bigger than the smallest electronic devices (e.g., transistors in silicon integrated circuits) for this reason.