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The spectral relaxation of photogenerated excitations and the stimulated emission is studied in an alpha-sexithienyl single crystal using femtosecond differential transmission spectroscopy and time-resolved photoluminescence measurements at low temperature. Stimulated emission with amplification of the probe light which results in a positive differential transmission signal is found at two spectral positions for polarization parallel to the molecular c-axis.

The influence of the charge-transfer state on the photogeneration of free charges in alpha-sexithienyl is reassessed. The femtosecond differential transmission spectroscopy on an alpha-sexithienyl film at low temperature is performed by covering a broad range of excitation energies.

The creation and manipulation of optical vortices, both in free space and in two-dimensional systems such as surface plasmon polaritons (SPPs), has attracted widespread attention in nano-optics due to their robust topological structure. Coupled with strong spatial confinement in the case of SPPs, these plasmonic vortices and their underlying orbital angular momentum (OAM) have promise in novel light-matter interactions on the nanoscale with applications ranging from on-chip particle manipulation to tailored control of plasmonic quasiparticles. Until now, predominantly integer OAM values have been investigated. Here, we measure and analyze the time evolution of fractional OAM SPPs using time-resolved two-photon photoemission electron microscopy and near-field optical microscopy. We experimentally show the field's complex rotational dynamics and observe the beating of integer OAM eigenmodes at fractional OAM excitations. With our ability to access the ultrafast time dynamics of the electric field, we can follow the buildup of the plasmonic fractional OAM during the interference of the converging surface plasmons. By adiabatically increasing the phase discontinuity at the excitation boundary, we track the total OAM, leading to plateaus around integer OAM values that arise from the interplay between intrinsic and extrinsic OAM., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Nonlinear optical plasmonics investigates the emission of plasmonic nanoantennas with the aid of nonlinear spectroscopy. Here we introduce nonlinear spatially resolved spectroscopy (NSRS) which is capable of imaging the k-space as well as spatially resolving the THG signal of gold nanoantennas and investigating the emission of individual antennas by wide-field illumination of entire arrays. Hand in hand with theoretical simulations, we demonstrate our ability of imaging various oscillation modes inside the nanostructures and therefore spatial emission hotspots. Upon increasing intensity of the femtosecond excitation, an individual destruction threshold can be observed. We find certain antennas becoming exceptionally bright. By investigating those samples taking structural SEM images of the nanoantenna arrays afterward, our spatially resolved nonlinear image can be correlated with this data proving that antennas had deformed into a peanut-like shape. Thus, our NSRS setup enables the investigation of a nonlinear self-enhancement process of nanoantennas under critical laser excitation.

Structural colors of plasmonic metasurfaces have been promised to a strong technological impact thanks to their high brightness, durability, and dichroic properties. However, fabricating metasurfaces whose spatial distribution must be customized at each implementation and over large areas is still a challenge. Since the demonstration of printed image multiplexing on quasi-random plasmonic metasurfaces, laser processing appears as a promising technology to reach the right level of accuracy and versatility. The main limit comes from the absence of physical models to predict the optical properties that can emerge from the laser processing of metasurfaces in which random metallic nanostructures are characterized by their statistical properties. Here, we demonstrate that deep neural networks trained from experimental data can predict the spectra and colors of laser-induced plasmonic metasurfaces in various observation modes. With thousands of experimental data, produced in a rapid and efficient way, the training accuracy is better than the perceptual just noticeable change. This accuracy enables the use of the predicted continuous color charts to find solutions for printing multiplexed images. Our deep learning approach is validated by an experimental demonstration of laser-induced two-image multiplexing. This approach greatly improves the performance of the laser-processing technology for both printing color images and finding optimized parameters for multiplexing. The article also provides a simple mining algorithm for implementing multiplexing with multiple observation modes and colors from any printing technology. This study can improve the optimization of laser processes for high-end applications in security, entertainment, or data storage.

Nanophotonic chiral sensing has recently attracted a lot of attention. The idea is to exploit the strong light-matter interaction in nanophotonic resonators to determine the concentration of chiral molecules at ultralow thresholds, which is highly attractive for numerous applications in life science and chemistry. However, a thorough understanding of the underlying interactions is still missing. The theoretical description relies on either simple approximations or on purely numerical approaches. We close this gap and present a general theory of chiral light-matter interactions in arbitrary resonators. Our theory describes the chiral interaction as a perturbation of the resonator modes, also known as resonant states or quasi-normal modes. We observe two dominant contributions: A chirality-induced resonance shift and changes in the modes' excitation and emission efficiencies. Our theory brings deep insights for tailoring and enhancing chiral light-matter interactions. Furthermore, it allows us to predict spectra much more efficiently in comparison to conventional approaches. This is particularly true, as chiral interactions are inherently weak and therefore perturbation theory fits extremely well for this problem.

A high-quality plasmon-fiber cavity in a doubly resonant configuration can exhibit second-harmonic generation (SHG) with over 5 orders of magnitude enhancement compared to gold nanoparticles on a fused silica substrate. Through coupling to a fiber cavity with the proper diameter, a high-quality ( Q ≈ 160) resonance can be achieved in combination with a single gold nanoparticle. In a classical picture, where the incident electric field travels coherently Q times around the fiber during the nonlinear process, the high Q of the coupled mode aids in highly efficient SHG. We accomplish two feats: First, we analyze the Q factor dependence of the SHG efficiency, proving the expected Q 4 dependence and thus confirming coherent E-field amplification in the fiber cavity. Second, we carefully adjust the fiber size further and tune the plasmon response of a gold nanoparticle to a high- Q cavity mode. We make sure that the second harmonic wavelength is simultaneously in resonance with a higher order fiber cavity mode, fulfilling the doubly resonant condition. As a result, a giant SH response with conversion efficiency up to 1.6 × 10 -5 is detected upon a pump intensity of 5 × 10 8 W/cm 2 for 100 fs pump pulses around 840 nm incident wavelength. Additionally, the importance of the doubly resonant condition is proven by detuning the size of the fiber, which leads to a drastic drop in SHG efficiency. This disparity of the SHG efficiency can be observed even by eye, when monitoring the intensity changes of the visible SH light during detuning.

Chirality is found at all length scales in nature, and chiral metasurfaces have recently attracted attention due to their exceptional optical properties and their potential applications. Most of these metasurfaces are fabricated by top-down methods or bottom-up approaches that cannot be tuned in terms of structure and composition. By combining grazing incidence spraying of plasmonic nanowires and nanorods and Layer-by-Layer assembly, we show that nonchiral 1D nano-objects can be assembled into scalable chiral Bouligand nanostructures whose mesoscale anisotropy is controlled with simple macroscopic tools. Such multilayer helical assemblies of linearly oriented nanowires and nanorods display very high circular dichroism up to 13 000 mdeg and giant dissymmetry factors up to g ≈ 0.30 over the entire visible and near-infrared range. The chiroptical properties of the chiral multilayer stack are successfully modeled using a transfer matrix formalism based on the experimentally determined properties of each individual layer. The proposed approach can be extended to much more elaborate architectures and gives access to template-free and enantiomerically pure nanocomposites whose structure can be finely tuned through simple design principles.

A general and quantitative method to characterize molecular transport in polymers with good temporal and high spatial resolution, in complex environments, is an important need of the pharmaceutical, textile, and food and beverage packaging industries, and of general interest to the polymer science community. Here we show how the amplified infrared (IR) absorbance sensitivity provided by plasmonic nanoantenna-based surface enhanced infrared absorption (SEIRA) provides such a method. SEIRA enhances infrared (IR) absorbances primarily within 50 nm of the nanoantennas, enabling localized quantitative detection of even trace quantities of analytes and diffusion measurements in even thin polymer films. Relative to a commercial attenuated total internal reflection (ATR) system, the limit of detection is enhanced at least 13-fold, and as is important for measuring diffusion, the detection volume is about 15 times thinner. Via this approach, the diffusion coefficient and solubility of specific molecules, including l-ascorbic acid (vitamin C), ethanol, various sugars, and water, in both simple and complex mixtures (e.g., beer and a cola soda), were determined in poly(methyl methacrylate), high density polyethylene (HDPE)-based, and polypropylene-based polyolefin films as thin as 250 nm.

The optical properties of plasmonic nanoparticle ensembles are determined not only by the particle shape and size but also by the nanoantenna arrangement. To investigate the influence of the spatial ordering on the far-field optical properties of nanoparticle ensembles, we introduce a disorder model that encompasses both "frozen-phonon" and correlated disorder. We present experimental as well as computational approaches to gain a better understanding of the impact of disorder. A designated Fourier microscopy setup allows us to record the real- and Fourier-space images of plasmonic metasurfaces as either RGB images or fully wavelength-resolved data sets. Furthermore, by treating the nanoparticles as dipoles, we calculate the electric field based on dipole-dipole interaction, extract the far-field response, and convert it to RGB images. Our results reveal how the different disorder parameters shape the optical far field and thus define the optical appearance of a disordered metasurface and show that the relatively simple dipole approximation is able to reproduce the far-field behavior accurately. These insights can be used for engineering metasurfaces with tailored disorder to produce a desired bidirectional reflectance distribution function.

Here we directly probe the electronic properties of bilayer graphene using s-SNOM measurements with a broadly tunable laser source over the energy range from 0.3 to 0.54 eV. We tune an OPO/OPA system around the interband resonance of Bernal stacked bilayer graphene (BLG) and extract amplitude and phase of the scattered light. This enables us to retrieve and reconstruct the complex optical conductivity resonance in BLG around 0.39 eV with nanoscale resolution. Our technique opens the door toward nanoscopic noncontact measurements of the electronic properties in complex hybrid 2D and van der Waals material systems, where scanning tunneling spectroscopy cannot access the decisive layers., Competing Interests: The authors declare the following competing financial interest(s): H. Linnenbank, T. Steinle, and H. Giessen are co-founders of SI Stuttgart Instruments GmbH, a company producing the OPO/OPA laser system such as the one used in this study. The other authors declare no conflict of interests., (© 2021 American Chemical Society.)

To tackle climate change and reduce CO 2 emissions, it is important to measure CO 2 output precisely. Even though there are many different techniques, no simple and cheap optical method in the visible is available. This work studies plasmonically enhanced optical carbon dioxide sensors in the visible wavelength range. The sensor samples are based on an inert plasmonic perfect absorber, which can be easily and cheaply fabricated by colloidal etching lithography. A CO 2 -sensitive polyethylenimine (PEI) layer is then spin-coated on top to complete the samples. The samples are examined continuously by microspectroscopy during different CO 2 exposures to track spectral changes, particularly the position of the resonance centroid wavelength. The samples exhibit a resonance shift of up to 7 nm, depending on the CO 2 concentration and the temperature. The temperature influences the rise time as well as the sensitive concentration range. The concentration dependence of the resonance shift overall follows the shape of a Langmuir isotherm, which includes a nearly linear relation at lower concentrations and elevated temperatures and a saturating behavior at higher concentrations and lower temperatures. The results indicate that a sensitivity in the full range from 100 vol % to below 1 ppm can be achieved. The samples degenerate in a dry inert atmosphere in a matter of days but are useable over multiple weeks when exposed to humidity and CO 2 . The PEI reacts very selectively to CO 2 , showing no response to CO, NH 3 , NO 2 , CH 4 , H 2 , and only a very small response to O 2 . Overall, polyethylenimine is very promising as a CO 2 -sensitive material for many practical sensing applications over a wide range of concentrations. An adjustment of the temperature is mandatory to control the sensitivity and response time.

Planar electron-driven photon sources have been recently proposed as miniaturized light sources, with prospects for ultrafast conjugate electron-photon microscopy and spectral interferometry. Such sources usually follow the symmetry of the electron-induced polarization: transition-radiation-based sources, for example, only generate p-polarized light. Here we demonstrate that the polarization, the bandwidth, and the directionality of photons can be tailored by utilizing photon-sieve-based structures. We design, fabricate, and characterize self-complementary chiral structures made of holes in an Au film and generate light vortex beams with specified angular momentum orders. The incoming electron interacting with the structure generates chiral surface plasmon polaritons on the structured Au surface that scatter into the far field. The outcoupled radiation interferes with transition radiation creating TE- and TM-polarized Laguerre-Gauss light beams with a chiral intensity distribution. The generated vortex light and its unique spatiotemporal features can form the basis for the generation of structured-light electron-driven photon sources.

Excitons in monolayer transition-metal-dichalcogenides (TMDs) dominate their optical response and exhibit strong light-matter interactions with lifetime-limited emission. While various approaches have been applied to enhance light-exciton interactions in TMDs, the achieved strength have been far below unity, and a complete picture of its underlying physical mechanisms and fundamental limits has not been provided. Here, we introduce a TMD-based van der Waals heterostructure cavity that provides near-unity excitonic absorption, and emission of excitonic complexes that are observed at ultralow excitation powers. Our results are in full agreement with a quantum theoretical framework introduced to describe the light-exciton-cavity interaction. We find that the subtle interplay between the radiative, nonradiative and dephasing decay rates plays a crucial role, and unveil a universal absorption law for excitons in 2D systems. This enhanced light-exciton interaction provides a platform for studying excitonic phase-transitions and quantum nonlinearities and enables new possibilities for 2D semiconductor-based optoelectronic devices.

Palladium nanoparticles have proven to be exceptionally suitable materials for the optical detection of hydrogen gas due to the dielectric function that changes with the hydrogen concentration. The development of a reliable, low-cost, and widely applicable hydrogen detector requires a simple optical readout mechanism and an optimization of the lowest detectable hydrogen concentration. The so-called "perfect absorber"-type structures, consisting of a layer of plasmonic palladium nanoantennas suspended above a metallic mirror layer, are a promising approach to realizing such sensors. The absorption of hydrogen by palladium leads to a shift of the plasmon resonance and, thus, to a change in the far-field reflectance spectrum. The spectral change can be analyzed in detail using spectroscopic measurements, while the reflectance change at a specific wavelength can be detected with a simple photometric system of a photodiode and a monochromatic light source. Here, we systematically investigate the geometry of cavity-coupled palladium nanostructures as well as the optical system concept, which enables us to formulate a set of design rules for optimizing the hydrogen sensitivity. Employing these principles, we demonstrate the robust detection of hydrogen at concentrations down to 100 ppm. Our results are not limited to hydrogen sensing but can be applied to any type of plasmonic sensor.

Due to the changing global climate, the role of renewable energy sources is of increasing importance. Hydrogen can play an important role as an energy carrier in the transition from fossil fuels. However, to ensure safe operations, a highly reliable and sensitive hydrogen sensor is required for leakage detection. We present a sensor design with purely optical readout that reliably operates between 50 and 100,000 ppm. The building block of the sensor is a reactive sample that consists of a layered structure with palladium nanodisks as the top layer and changes its optical properties depending on the external hydrogen partial pressure. We use a fiber-coupled setup consisting of an LED, a sensor body containing the reactive sample, and a photodiode to probe and read out the reflectance of the sample. This allows separation of the explosive detection area from the operating electronics and thus comes with an inherent protection against hydrogen ignition by electronic malfunctions. Our results prove that this sensor design provides a large detection range, fast response times, and enhanced robustness against aging compared to conventional thin-film technologies. Especially, the simplicity, feasibility, and scalability of the presented approach yield a holistic approach for industrial hydrogen monitoring.

Wide-spread applications of nanoparticles require large-scale fabrication techniques. Being intrinsically scalable, bottom-up nanoparticle synthesis shows an ever-growing control over particle morphology, enabling even chirally selective shapes. Significant efforts have been undertaken to refine the synthesis in order to decrease the structural spread of the particles and to purify and maximize the resulting handedness. So far, imaging technologies such as electron microscopy are mostly used to investigate the quality of the synthesis. However, for nanophotonic and plasmonic applications, the optical properties are, in fact, key. In this work, we show that single particle chiral scatterometry holds great potential as a feedback to characterize the (chir-)optical quality of chemically synthesized nanoparticles. The spectra of single helicoid nanoparticles reveal a diverse set of chiroptical responses with hugely varying absolute chiral asymmetry in spite of the well-controlled morphology of the particles. Averaging over the single nanoparticles reproduces the solution ensemble measurement remarkably well. This demonstrates that the single particles, despite their morphological and consequently chiroptical differences, exhibit a clearly pronounced chiral spectral and structural feature. We find that the  g -factor, that is, the degree of asymmetry of chiral light scattering of single nanoparticles can be up to 4 times larger than that for the ensemble. This proves that chiral scatterometry can be a highly important optical feedback for bottom-up nanoparticle synthesis as it reveals that the asymmetry of the ensemble solution can be further increased and maximized by appropriate refinement methods or by postfabrication purification.

Monosaccharides, which include the simple sugars such as glucose and fructose, are among the most important carbohydrates in the human diet. Certain chronic diseases, e.g., diabetes mellitus, are associated with anomalous glucose blood levels. Detecting and measuring the levels of monosaccharides in vivo or in aqueous solutions is thus of the utmost importance in life science, health, and point-of-care applications. Noninvasive sensing would avoid problems such as pain and potential infection hazards. Here, with the help of surface enhanced infrared absorption (SEIRA) spectroscopy, we demonstrate the reliable optical detection in the mid-infrared spectral range of pure glucose and fructose solutions as well as mixtures of both in aqueous solution. We utilize a reflection flow cell geometry with physiologically relevant concentrations as small as 10 g/L. As significant improvement over the standard baseline correction employed in SEIRA applications, we utilize principal component analysis (PCA) as machine learning algorithm, which is ideally suited for the extraction of vibrational data. We anticipate our results as important step in biosensing applications that will stimulate efforts to further improve the employed SEIRA substrates, the noise level of the spectroscopic light source, as well as the flow cell environment en route to significantly higher sensitivities and quantitative analysis, even in tear drops.

Proteins perform a variety of essential functions in living cells and thus are of critical interest for drug delivery as well as disease biomarkers. The different functions are derived from a hugely diverse set of structures, fueling interest in their conformational states. Surface-enhanced infrared absorption spectroscopy has been utilized to detect and discriminate protein monomers. As an important step forward, we are investigating collagen peptides consisting of  a  triple helix. While they constitute the main structural building blocks in many complex proteins, they are also a perfect model system for the complex proteins relevant in biological systems. Their complex spectroscopic information as well as the overall small size present a significant challenge for their detection and discrimination. Using resonant plasmonic nanoslits, which are known to show larger specificity compared to nanoantennas, we overcome this challenge. We perform in vitro surface-enhanced absorption spectroscopy studies and track the conformational changes of these collagen peptides under two different external stimuli, which are temperature and chemical surroundings. Modeling the coupling between the amide I vibrational modes and the plasmonic resonance, we can extract the conformational state of the collages and thus monitor the folding and unfolding dynamics of even a single monolayer. This leads to new prospects in studies of single layers of proteins and their folding behavior in minute amounts in a living environment.

Proteins and peptides play a predominant role in biochemical reactions of living cells. In these complex environments, not only the constitution of the molecules but also their three-dimensional configuration defines their functionality. This so-called secondary structure of proteins is crucial for understanding their function in living matter. Misfolding, for example, is suspected as the cause of neurodegenerative diseases such as Alzheimer's and Parkinson's disease. Ultimately, it is necessary to study a single protein and its folding dynamics. Here, we report a first step in this direction, namely ultrasensitive detection and discrimination of in vitro polypeptide folding and unfolding processes using resonant plasmonic nanoantennas for surface-enhanced vibrational spectroscopy. We utilize poly-l-lysine as a model system which has been functionalized on the gold surface. By in vitro infrared spectroscopy of a single molecular monolayer at the amide I vibrations we directly monitor the reversible conformational changes between α-helix and β-sheet states induced by controlled external chemical stimuli. Our scheme in combination with advanced positioning of the peptides and proteins and more brilliant light sources is highly promising for ultrasensitive in vitro studies down to the single protein level.

We demonstrate second-harmonic generation with ultranarrow resonances in hybrid plasmon-fiber cavities, formed by depositing single-crystalline gold nanorods onto the surface of tapered microfibers with diameters in the range of 1.7-1.8 μm. The localized surface plasmon mode of the single gold nanorod efficiently couples with a whispering gallery mode of the fiber, resulting in a very narrow hybrid plasmon-fiber resonance with a high quality factor Q of up to 250. When illuminated with a tunable 100 fs laser, a sharp SHG peak narrower than half of the spectral width of the impinging laser emerges, superimposed on a broad multiphoton photoluminescence background. The enhancement of the SHG peak of the hybrid system is typically 1000-fold when compared to that of a single gold nanorod alone. Tuning the laser over the hybrid resonance enables second-harmonic spectroscopy and yields an ultranarrow line width as small as 6.4 nm. We determine the second-harmonic signal to rise with the square of the laser power, while the multiphoton photoluminescence background rises with powers between 4 and 6, indicating a very efficient higher-order process. A coupled anharmonic oscillator model is able to describe the linear as well as second-harmonic resonances very well. Our work will open the door to the simultaneous utilization of narrow whispering gallery resonances together with high plasmonic near-field enhancement and should allow for nonlinear sensing and extremely efficient nonlinear light generation from ultrasmall volumes.

Active plasmonics is enabling novel devices such as switchable metasurfaces for active beam steering or dynamic holography. Magnesium with its particle plasmon resonances in the visible spectral range is an ideal material for this technology. Upon hydrogenation, metallic magnesium switches reversibly into dielectric magnesium hydride (MgH 2 ), turning the plasmonic resonances off and on. However, up until now, it has been unknown how exactly the hydrogenation process progresses in the individual plasmonic nanoparticles. Here, we introduce a new method, namely nanoscale hydrogenography, that combines near-field scattering microscopy, atomic force microscopy, and single-particle far-field spectroscopy to visualize the hydrogen absorption process in single Mg nanodisks. Using this method, we reveal that hydrogen progresses along individual single-crystalline nanocrystallites within the nanostructure. We are able to monitor the spatially resolved forward and backward switching of the phase transitions of several individual nanoparticles, demonstrating differences and similarities of that process. Our method lays the foundations for gaining a better understanding of hydrogen diffusion in metal nanoparticles and for improving future active nano-optical switching devices.

We analyze and optimize the performance of coupled plasmonic nanoantennas for refractive index sensing. The investigated structure supports a sub- and super-radiant mode that originates from the weak coupling of a dipolar and quadrupolar mode, resulting in a Fano-type spectral line shape. In our study, we vary the near-field coupling of the two modes and particularly examine the influence of the spectral detuning between them on the sensing performance. Surprisingly, the case of matched resonance frequencies does not provide the best sensor. Instead, we find that the right amount of coupling strength and spectral detuning allows for achieving the ideal combination of narrow line width and sufficient excitation strength of the subradiant mode, and therefore results in optimized sensor performance. Our findings are confirmed by experimental results and first-order perturbation theory. The latter is based on the resonant state expansion and provides direct access to resonance frequency shifts and line width changes as well as the excitation strength of the modes. Based on these parameters, we define a figure of merit that can be easily calculated for different sensing geometries and agrees well with the numerical and experimental results.

We use subcycle time-resolved photoemission microscopy to unambiguously distinguish optically triggered electron emission (photoemission) from effects caused purely by the plasmonic field (termed "plasmoemission"). We find from time-resolved imaging that nonlinear plasmoemission is dominated by the transverse plasmon field component by utilizing a transient standing wave from two counter-propagating plasmon pulses of opposite transverse spin. From plasmonic foci on flat metal surfaces, we observe highly nonlinear plasmoemission up to the fifth power of intensity and quantized energy transfer, which reflects the quantum-mechanical nature of surface plasmons. Our work constitutes the basis for novel plasmonic devices such as nanometer-confined ultrafast electron sources as well as applications in time-resolved electron microscopy.

Refractory plasmonics deals with metallic nanostructures that can withstand high temperatures and intense laser pulses. The common belief was that refractory materials such as TiN are necessary for this purpose. Here we show that refractory plasmonics is possible without refractory materials. We demonstrate that gold nanostructures which are overcoated with 4 and 40 nm Al 2 O 3 (alumina) by an atomic layer deposition process or by thick IC1-200 resist can withstand temperatures of over 800 °C at ambient atmospheric conditions. Furthermore, the alumina-coated structures can withstand intense laser radiation of over 10 GW/cm 2 at ambient conditions without damage. Thus, it is possible to combine the excellent linear and nonlinear plasmonic properties of gold with material properties that were believed to be only possible with the lossier and less nonlinear refractory materials.

Integrated single-photon sources with high photon-extraction efficiency are key building blocks for applications in the field of quantum communications. We report on a bright single-photon source realized by on-chip integration of a deterministic quantum dot microlens with a 3D-printed multilens micro-objective. The device concept benefits from a sophisticated combination of in situ 3D electron-beam lithography to realize the quantum dot microlens and 3D femtosecond direct laser writing for creation of the micro-objective. In this way, we obtain a high-quality quantum device with broadband photon-extraction efficiency of (40 ± 4)% and high suppression of multiphoton emission events with g (2) (τ = 0) < 0.02. Our results highlight the opportunities that arise from tailoring the optical properties of quantum emitters using integrated optics with high potential for the further development of plug-and-play fiber-coupled single-photon sources.

Resonantly excited plasmonic gold nanoantennas are strong sources of third-harmonic (TH) radiation. It has been shown that the response originates from large microscopic nonlinearity of the gold itself, which is enhanced by the near-field of the plasmonic nanoantenna. To further enhance this response, one can incorporate nonlinear media into the near-fields of the nanoantenna, as an additional TH source. To obtain a significant contribution from the added medium, its nonlinear susceptibility should be comparable to that of the antenna material. Many organic materials offer the necessary nonlinear susceptibility and their incorporation is possible with simple spin-coating. Furthermore, organic materials are often susceptible to photodegradation. This degradation can be used to investigate the influence of organic materials on the hybrid system. Our investigated hybrid organic plasmonic nanoantenna system consists of a gold nanorod array and poly(methyl methacrylate) as the nonlinear dielectric medium. The experiments clearly reveal two contributions to the generated TH radiation, one from the nanoantenna itself and one from the polymer. The nonlinear response of the hybrid material exceeds the response of both individual constituents and opens the path to more efficient nanoscale nonlinear light generation., Competing Interests: The authors declare no competing financial interest.

Spectroscopic infrared chemical imaging is ideally suited for label-free and spatially resolved characterization of molecular species, but often suffers from low infrared absorption cross sections. Here, we overcome this limitation by utilizing confined electromagnetic near-fields of resonantly excited plasmonic nanoantennas, which enhance the molecular absorption by orders of magnitude. In the experiments, we evaporate microstructured chemical patterns of C 60 and pentacene with nanometer thickness on top of homogeneous arrays of tailored nanoantennas. Broadband mid-infrared spectra containing plasmonic and vibrational information were acquired with diffraction-limited resolution using a two-dimensional focal plane array detector. Evaluating the enhanced infrared absorption at the respective frequencies, spatially resolved chemical images were obtained. In these chemical images, the microstructured chemical patterns are only visible if nanoantennas are used. This confirms the superior performance of our approach over conventional spectroscopic infrared imaging. In addition to the improved sensitivity, our technique provides chemical selectivity, which would not be available with plasmonic imaging that is based on refractive index sensing. To extend the accessible spectral bandwidth of nanoantenna-enhanced spectroscopic imaging, we employed nanostructures with dual-band resonances, providing broadband plasmonic enhancement and sensitivity. Our results demonstrate the potential of nanoantenna-enhanced spectroscopic infrared chemical imaging for spatially resolved characterization of organic layers with thicknesses of several nanometers. This is of potential interest for medical applications which are currently hampered by state-of-art infrared techniques, e.g., for distinguishing cancerous from healthy tissues.

Infrared spectroscopy is a powerful tool widely used in research and industry for a label-free and unambiguous identification of molecular species. Inconveniently, its application to spectroscopic analysis of minute amounts of materials, for example, in sensing applications, is hampered by the low infrared absorption cross-sections. Surface-enhanced infrared spectroscopy using resonant metal nanoantennas, or short "resonant SEIRA", overcomes this limitation. Resonantly excited, such metal nanostructures feature collective oscillations of electrons (plasmons), providing huge electromagnetic fields on the nanometer scale. Infrared vibrations of molecules located in these fields are enhanced by orders of magnitude enabling a spectroscopic characterization with unprecedented sensitivity. In this Review, we introduce the concept of resonant SEIRA and discuss the underlying physics, particularly, the resonant coupling between molecular and antenna excitations as well as the spatial extent of the enhancement and its scaling with frequency. On the basis of these fundamentals, different routes to maximize the SEIRA enhancement are reviewed including the choice of nanostructures geometries, arrangements, and materials. Furthermore, first applications such as the detection of proteins, the monitoring of dynamic processes, and hyperspectral infrared chemical imaging are discussed, demonstrating the sensitivity and broad applicability of resonant SEIRA.

We introduce a new concept that enables subwavelength polarization-resolved probing of the second-harmonic near-field distribution of plasmonic nanostructures. As a local sensor, this method utilizes aluminum nanoantennas, which are resonant to the second-harmonic wavelength and which allow to efficiently scatter the local second-harmonic light to the far-field. We place these sensors into the second-harmonic near-field generated by plasmonic nanostructures and carefully vary their position and orientation. Observing the second-harmonic light resonantly scattered by the aluminum nanoantennas provides polarization-resolved information about the local second-harmonic near-field distribution. We then investigate the polarization-resolved second-harmonic near-field of inversion symmetric gold dipole nanoantennas. Interestingly, we find strong evidence that the second-harmonic dipole is predominantly oriented perpendicular to the gold nanoantenna long axis, although the excitation laser is polarized parallel to the nanoantennas. We believe that our investigations will help to disentangle the highly debated origin of the second-harmonic response of inversion symmetric plasmonic structures. Furthermore, we believe that our new method, which enables the measurement of local nonlinear electric fields, will find widespread implementation and applications in nonlinear near-field optical microscopy.

We present an analytic derivation for the enhancement of local optical chirality in the near field of plasmonic nanostructures by tuning the far-field polarization of external light. We illustrate the results by means of simulations with an achiral and a chiral nanostructure assembly and demonstrate that local optical chirality is significantly enhanced with respect to circular polarization in free space. The optimal external far-field polarizations are different from both circular and linear. Symmetry properties of the nanostructure can be exploited to determine whether the optimal far-field polarization is circular. Furthermore, the optimal far-field polarization depends on the frequency, which results in complex-shaped laser pulses for broadband optimization.

Titanium nitride (TiN) is a novel refractory plasmonic material which can sustain high temperatures and exhibits large optical nonlinearities, potentially opening the door for high-power nonlinear plasmonic applications. We fabricate TiN nanoantenna arrays with plasmonic resonances tunable in the range of about 950-1050 nm by changing the antenna length. We present second-harmonic (SH) spectroscopy of TiN nanoantenna arrays, which is analyzed using a nonlinear oscillator model with a wavelength-dependent second-order response from the material itself. Furthermore, characterization of the robustness upon strong laser illumination confirms that the TiN antennas are able to endure laser irradiation with high peak intensity up to 15 GW/cm(2) without changing their optical properties and their physical appearance. They outperform gold antennas by one order of magnitude regarding laser power sustainability. Thus, TiN nanoantennas could serve as promising candidates for high-power/high-temperature applications such as coherent nonlinear converters and local heat sources on the nanoscale.

We introduce the concept of nonlinear plasmonic sensing, relying on third harmonic generation from simple plasmonic nanoantennas. Because of the nonlinear conversion process we observe a larger sensitivity to a local change in the refractive index as compared to the commonly used linear localized surface plasmon resonance sensing. Refractive index changes as small as 10(-3) can be detected. In order to determine the spectral position of highest sensitivity, we perform linear and third harmonic spectroscopy on plasmonic nanoantenna arrays, which are the fundamental building blocks of our sensor. Furthermore, simultaneous detection of linear and nonlinear signals allows quantitative comparison of both methods, providing further insight into the working principle of our sensor. While the signal-to-noise ratio is comparable, nonlinear sensing gives about seven times higher relative signal changes.

Chirality is a highly important topic in modern chemistry, given the dramatically different pharmacological effects that enantiomers can have on the body. Chirality of natural molecules can be controlled by reconfiguration of molecular structures through external stimuli. Despite the rapid progress in plasmonics, active regulation of plasmonic chirality, particularly in the visible spectral range, still faces significant challenges. In this Letter, we demonstrate a new class of hybrid plasmonic metamolecules composed of magnesium and gold nanoparticles. The plasmonic chirality from such plasmonic metamolecules can be dynamically controlled by hydrogen in real time without introducing macroscopic structural reconfiguration. We experimentally investigate the switching dynamics of the hydrogen-regulated chiroptical response in the visible spectral range using circular dichroism spectroscopy. In addition, energy dispersive X-ray spectroscopy is used to examine the morphology changes of the magnesium particles through hydrogenation and dehydrogenation processes. Our study can enable plasmonic chiral platforms for a variety of gas detection schemes by exploiting the high sensitivity of circular dichroism spectroscopy.

Investigating new materials plays an important role for advancing the field of nanoplasmonics. In this work, we fabricate nanodisks from magnesium and demonstrate tuning of their plasmon resonance throughout the whole visible wavelength range by changing the disk diameter. Furthermore, we employ a catalytic palladium cap layer to transform the metallic Mg particles into dielectric MgH2 particles when exposed to hydrogen gas. We prove that this transition can be reversed in the presence of oxygen. This yields plasmonic nanostructures with an extinction spectrum that can be repeatedly switched on or off or kept at any intermediate state, offering new perspectives for active plasmonic metamaterials.

We propose and demonstrate a novel type of coupling between polarons in a conjugated polymer and localized surface plasmons in infrared (IR) nanoantennas. The near-field interaction between plasmons and polarons is revealed by polarized photoinduced absorption measurements, probing mid-IR polaron transitions, and infrared-active vibrational modes of the polymer, which directly gauge the density of photogenerated charge carriers. This work proves the possibility of tuning the polaronic properties of organic semiconductors with plasmonic nanostructures.

Active control over the handedness of a chiral metamaterial has the potential to serve as key element for highly integrated polarization engineering approaches, polarization sensitive imaging devices, and stereo display technologies. However, this is hard to achieve as it seemingly involves the reconfiguration of the metamolecule from a left-handed into a right-handed enantiomer and vice versa. This type of mechanical actuation is intricate and usually neither monolithically realizable nor viable for high-speed applications. Here, enabled by the phase change material Ge3Sb2Te6 (GST-326), we demonstrate a tunable and switchable mid-infrared plasmonic chiral metamaterial in a proof-of-concept experiment. A large tunability range of the circular dichroism response from λ = 4.15 to 4.90 μm is achieved, and we experimentally demonstrate that the combination of a passive bias-type chiral layer with the active chiral metamaterial allows for switchable chirality, that is, the reversal of the circular dichroism sign, in a fully planar, layered design without the need for geometrical reconfiguration. Because phase change materials can be electrically and optically switched, our designs may open up a path for highly integrated mid-IR polarization engineering devices that can be modulated on ultrafast time scales.

We perform second harmonic spectroscopy of aluminum nanoantenna arrays that exhibit plasmonic resonances at the second harmonic wavelength between 450 and 570 nm by focusing sub-30 fs laser pulses tunable from 900 to 1140 nm onto the nanoantenna arrays. We find that a plasmonic resonance at the second harmonic wavelength boosts the overall nonlinear process by more than an order of magnitude. In particular, in the measurement the resonant second harmonic polarization component is a factor of about 70 stronger when compared to the perpendicular off-resonant second harmonic polarization. Furthermore, the maximum of the second harmonic conversion efficiency is found to be slightly blue-shifted with respect to the peak of the linear optical far-field spectrum. This fact can be understood from a simple model that accounts for the almost off-resonant absorption at the fundamental wavelength and the resonant emission process at the second harmonic.

We derive a closed-form expression that accurately predicts the peak frequency shift and broadening induced by tiny perturbations of plasmonic nanoresonators without critically relying on repeated electrodynamic simulations of the spectral response of nanoresonator for various locations, sizes, or shapes of the perturbing objects. In comparison with other approaches of the same kind, the force of the present approach is that the derivation is supported by a mathematical formalism based on a rigorous normalization of the resonance modes of nanoresonators consisting of lossy and dispersive materials. Accordingly, accurate predictions are obtained for a large range of nanoparticle shapes and sizes used in various plasmonic nanosensors even beyond the quasistatic limit. The expression gives quantitative insight and, combined with an open-source code, provides accurate and fast predictions that are ideally suited for preliminary designs or for interpretation of experimental data. It is also valid for photonic resonators with large mode volumes.

Plasmonic devices with absorbance close to unity have emerged as essential building blocks for a multitude of technological applications ranging from trace gas detection to infrared imaging. A crucial requirement for such elements is the angle independence of the absorptive performance. In this work, we develop theoretically and verify experimentally a quantitative model for the angular behavior of plasmonic perfect absorber structures based on an optical impedance matching picture. To achieve this, we utilize a simple and elegant k-space measurement technique to record quantitative angle-resolved reflectance measurements on various perfect absorber structures. Particularly, this method allows quantitative reflectance measurements on samples where only small areas have been nanostructured, for example, by electron-beam lithography. Combining these results with extensive numerical modeling, we find that matching of both the real and imaginary parts of the optical impedance is crucial to obtain perfect absorption over a large angular range. Furthermore, we successfully apply our model to the angular dispersion of perfect absorber geometries with disordered plasmonic elements as a favorable alternative to current array-based designs.

Infrared vibrations of molecular species can be enhanced by several orders of magnitude with plasmonic nanoantennas. Based on the confined electromagnetic near-fields of resonantly excited metal nanoparticles, this antenna-assisted surface-enhanced infrared spectroscopy enables the detection of minute amounts of analytes localized in the nanometer-scale vicinity of the structure. Among other important parameters, the distance of the vibrational oscillator of the analyte to the nanoantenna surface determines the signal enhancement. For sensing applications, this is a particularly important issue since the vibrating dipoles of interest may be located far away from the antenna surface because of functional layers and the large size of biomolecules, proteins, or bacteria. The relation between distance and signal enhancement is thus of paramount importance and measured here with in situ infrared spectroscopy during the growth of a probe layer. Our results indicate a diminishing signal enhancement and the effective saturation of the plasmonic resonance shift beyond 100 nm. The experiments carried out under ultra-high-vacuum conditions are supported by numerical calculations.

We perform third harmonic spectroscopy of dolmen-type nanostructures, which exhibit plasmonic Fano resonances in the near-infrared. Strong third harmonic emission is predominantly radiated close to the low energy peak of the Fano resonance. Furthermore, we find that the third harmonic polarization of the subradiant mode interferes destructively and diminishes the nonlinear signal in the far-field. By comparing the experimental third harmonic spectra with finite element simulations and an anharmonic oscillator model, we find strong indications that the source of the third harmonic is the optical nonlinearity of the bare gold enhanced by the resonant plasmonic polarization.

We present a comprehensive experimental and theoretical study on the near- and far-field properties of plasmonic oligomers using radially and azimuthally polarized excitation. These unconventional polarization states are perfectly matched to the high spatial symmetry of the oligomers and thus allow for the excitation of some of the highly symmetric eigenmodes of the structures, which cannot be excited by linearly polarized light. In particular, we study hexamer and heptamer structures and strikingly find very similar optical responses, as well as the absence of a Fano resonance. Furthermore, we investigate the near-field distributions of the oligomers using near-field scanning optical microscopy (NSOM). We observe significantly enhanced near-fields, which arise from efficient excitation of the highly symmetric eigenmodes by the radially and azimuthally polarized light fields. Our study opens up possibilities for tailored light-matter interaction, combining the design freedom of complex plasmonic structures with the remarkable properties of radially and azimuthally polarized light fields.

We incorporate dielectric indium tin oxide nanocrystals into the hot-spot of gold nanogap-antennas and perform third harmonic spectroscopy on these hybrid nanostructure arrays. The combined system shows a 2-fold increase of the radiated third harmonic intensity when compared to bare gold antennas. In order to identify the origin of the enhanced nonlinear response we perform finite element simulations of the nanostructures, which are in excellent agreement with our measurements. We find that the third harmonic signal enhancement is mainly related to changes in the linear optical properties of the plasmonic antenna resonances when the ITO nanocrystals are incorporated. Furthermore, the dominant source of the third harmonic is found to be located in the gold volume of the plasmonic antennas.

A key challenge for the development of active plasmonic nanodevices is the lack of materials with fully controllable plasmonic properties. In this work, we demonstrate that a plasmonic resonance in top-down nanofabricated yttrium antennas can be completely and reversibly turned on and off using hydrogen exposure. We fabricate arrays of yttrium nanorods and optically observe, in extinction spectra, the hydrogen-induced phase transition between the metallic yttrium dihydride and the insulating trihydride. Whereas the yttrium dihydride nanostructures exhibit a pronounced particle plasmon resonance, the transition to yttrium trihydride leads to a complete vanishing of the resonant behavior. The plasmonic resonance in the dihydride state can be tuned over a wide wavelength range by simply varying the size of the nanostructures. Furthermore, we develop an analytical diffusion model to explain the temporal behavior of the hydrogen loading and unloading trajectories observed in our experiments and gain information about the thermodynamics of our device. Thus, our nanorod system serves as a versatile basic building block for active plasmonic devices ranging from switchable perfect absorbers to active local heating control elements.

Plasmonics offers the opportunity of tailoring the interaction of light with single quantum emitters. However, the strong field localization of plasmons requires spatial fabrication accuracy far beyond what is required for other nanophotonic technologies. Furthermore, this accuracy has to be achieved across different fabrication processes to combine quantum emitters and plasmonics. We demonstrate a solution to this critical problem by controlled positioning of plasmonic nanoantennas with an accuracy of 11 nm next to single self-assembled GaAs semiconductor quantum dots, whose position can be determined with nanometer precision. These dots do not suffer from blinking or bleaching or from random orientation of the transition dipole moment as colloidal nanocrystals do. Our method introduces flexible fabrication of arbitrary nanostructures coupled to single-photon sources in a controllable and scalable fashion.

We study the coupling between the plasmonic resonances of solid and inverse metallic nanostructures. While the coupling between solid-solid and inverse-inverse plasmonic structures is well-understood, mixed solid-inverse systems have not yet been studied in detail. In particular, it remains unclear whether or not an efficient coupling is even possible and which prerequisites have to be met. We find that an efficient coupling between inverse and solid resonances is indeed possible, identify the necessary geometrical prerequisites, and demonstrate a novel solid-inverse plasmonic electromagnetically induced transparency (EIT) structure as well as a mixed chiral system. We furthermore show that for the coupling of asymmetric rod-shaped inverse and solid structures symmetry breaking is crucial. In contrast, highly symmetric structures such as nanodisks and nanoholes are straightforward to couple. Our results constitute a significant extension of the plasmonic coupling toolkit, and we thus envision the emergence of a large number of intriguing novel plasmonic coupling phenomena in mixed solid-inverse structures.

We introduce a new optical near-field mapping method, namely utilizing the plasmon-mediated luminescence from the apex of a sharp gold nanotip. The tip acts as a quasi-point light source which does not suffer from bleaching and gives a spatial resolution of ≤25 nm. We demonstrate our method by imaging the near field of azimuthally and radially polarized plasmonic modes of nonluminescent aluminum oligomers.

We manufacture large-area plasmonic structures featuring 3-dimensional chirality by colloidal nanohole lithography. By varying the polar rotating speed of the samples during gold evaporation, we can fabricate spiral-type ramp nanostructures. The optical properties show chiroptical resonances in the 100 to 400 THz frequency region (750 to 3000 nm), with circular dichroism values of up to 13%. Our method offers a simple low-cost manufacturing method of cm(2)-sized chiral plasmonic templates for chiroptical applications such as stereochemical enantiomer sensors.

We measure for the first time transient absorption spectra of individual CdSe nanowires with about 10 nm diameter. Confinement of the carrier wave functions leads to discrete states which can be described by a six-band effective mass model. Combining transient absorption and luminescence spectroscopy allows us to track the excitation dynamics in the visible and near-infrared spectral range. About 10% of all absorbed photons lead to an excitation of the lowest energy state. Of these excitations, less than 1% lead to a photon in the optical far-field. Almost all emission is reabsorbed by other parts of the nanowire. These findings might explain the low overall quantum efficiency of CdSe nanowires.