Spatially Resolved Nonlinear Plasmonics.

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.

Dielectric Mie voids: confining light in air.

Manipulating light on the nanoscale has become a central challenge in metadevices, resonant surfaces, nanoscale optical sensors, and many more, and it is largely based on resonant light confinement in dispersive and lossy metals and dielectrics. Here, we experimentally implement a novel strategy for dielectric nanophotonics: Resonant subwavelength localized confinement of light in air. We demonstrate that voids created in high-index dielectric host materials support localized resonant modes with exceptional optical properties. Due to the confinement in air, the modes do not suffer from the loss and dispersion of the dielectric host medium. We experimentally realize these resonant Mie voids by focused ion beam milling into bulk silicon wafers and experimentally demonstrate resonant light confinement down to the UV spectral range at 265 nm (4.68 eV). Furthermore, we utilize the bright, intense, and naturalistic colours for nanoscale colour printing. Mie voids will thus push the operation of functional high-index metasurfaces into the blue and UV spectral range. The combination of resonant dielectric Mie voids with dielectric nanoparticles will more than double the parameter space for the future design of metasurfaces and other micro- and nanoscale optical elements. In particular, this extension will enable novel antenna and structure designs which benefit from the full access to the modal field inside the void as well as the nearly free choice of the high-index material for novel sensing and active manipulation strategies.

Predicting Laser-Induced Colors of Random Plasmonic Metasurfaces and Optimizing Image Multiplexing Using Deep Learning.

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: How Does It Actually Work?

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.

Giant Second Harmonic Generation Enhancement in a High-Q Doubly Resonant Hybrid Plasmon-Fiber Cavity System.

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 Q4 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 × 108 W/cm2 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.

Shaping the Color and Angular Appearance of Plasmonic Metasurfaces with Tailored Disorder.

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.

3D printed hybrid refractive/diffractive achromat and apochromat for the visible wavelength range.

Three-dimensional (3D) direct laser writing is a powerful technology to create nano- and microscopic optical devices. While the design freedom of this technology offers the possibility to reduce different monochromatic aberrations, reducing chromatic aberrations is often neglected. In this Letter, we successfully demonstrate the combination of refractive and diffractive surfaces to create a refractive/diffractive achromat and show, to the best of our knowledge, the first refractive/diffractive apochromat by using DOEs and simultaneously combining two different photoresists, namely IP-S and IP-n162. These combinations drastically reduce chromatic aberrations in 3D printed micro-optics for the visible wavelength range. The optical properties, as well as the substantial reduction of chromatic aberrations, are characterized, and we outline the benefits of 3D direct laser written achromats and apochromats for micro-optics.

Optical Carbon Dioxide Detection in the Visible Down to the Single Digit ppm Range Using Plasmonic Perfect Absorbers.

To tackle climate change and reduce CO2 emissions, it is important to measure CO2 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 CO2-sensitive polyethylenimine (PEI) layer is then spin-coated on top to complete the samples. The samples are examined continuously by microspectroscopy during different CO2 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 CO2 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 CO2. The PEI reacts very selectively to CO2, showing no response to CO, NH3, NO2, CH4, H2, and only a very small response to O2. Overall, polyethylenimine is very promising as a CO2-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.

Watching in situ the hydrogen diffusion dynamics in magnesium on the nanoscale.

Active plasmonic and nanophotonic systems require switchable materials with extreme material contrast, short switching times, and negligible degradation. On the quest for these supreme properties, an in-depth understanding of the nanoscopic processes is essential. Here, we unravel the nanoscopic details of the phase transition dynamics of metallic magnesium (Mg) to dielectric magnesium hydride (MgH2) using free-standing films for in situ nanoimaging. A characteristic MgH2 phonon resonance is used to achieve unprecedented chemical specificity between the material states. Our results reveal that the hydride phase nucleates at grain boundaries, from where the hydrogenation progresses into the adjoining nanocrystallites. We measure a much faster nanoscopic hydride phase propagation in comparison to the macroscopic propagation dynamics. Our innovative method offers an engineering strategy to overcome the hitherto limited diffusion coefficients and has substantial impact on the further design, development, and analysis of switchable phase transition as well as hydrogen storage and generation materials.

Low-Cost Hydrogen Sensor in the ppm Range with Purely Optical Readout.

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.

Design Principles for Sensitivity Optimization in Plasmonic Hydrogen Sensors.

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.

Nanoscale Hydrogenography on Single Magnesium Nanoparticles.

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 (MgH2), 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.

Hydrogen-Regulated Chiral Nanoplasmonics.

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.

Magnesium as Novel Material for Active Plasmonics in the Visible Wavelength Range.

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.