Hexagonal Plasmonic Arrays for High-Throughput Multicolor Single-Molecule Studies.

Nanophotonic biosensors offer exceptional sensitivity in the presence of strong background signals by enhancing and confining light in subwavelength volumes. In the field of nanophotonic biosensors, antenna-in-box (AiB) designs consisting of a nanoantenna within a nanoaperture have demonstrated remarkable single-molecule fluorescence detection sensitivities under physiologically relevant conditions. However, their full potential has not yet been exploited as current designs prohibit insightful correlative multicolor single-molecule studies and are limited in terms of throughput. Here, we overcome these constraints by introducing aluminum-based hexagonal close-packed AiB (HCP-AiB) arrays. Our approach enables the parallel readout of over 1000 HCP-AiBs with multicolor single-molecule sensitivity up to micromolar concentrations using an alternating three-color excitation scheme and epi-fluorescence detection. Notably, the high-density HCP-AiB arrays not only enable high-throughput studies at micromolar concentrations but also offer high single-molecule detection probabilities in the nanomolar range. We demonstrate that robust and alignment-free correlative multicolor studies are possible using optical fiducial markers even when imaging in the low millisecond range. These advancements pave the way for the use of HCP-AiB arrays as biosensor architectures for high-throughput multicolor studies on single-molecule dynamics.

Hybrid Plasmonic Nanostructures for Enhanced Single-Molecule Detection Sensitivity.

Biosensing applications based on fluorescence detection often require single-molecule sensitivity in the presence of strong background signals. Plasmonic nanoantennas are particularly suitable for these tasks, as they can confine and enhance light in volumes far below the diffraction limit. The recently introduced antenna-in-box (AiB) platforms achieved high single-molecule detection sensitivity at high fluorophore concentrations by placing gold nanoantennas in a gold aperture. However, hybrid AiB platforms with alternative aperture materials such as aluminum promise superior performance by providing better background screening. Here, we report on the fabrication and optical characterization of hybrid AiBs made of gold and aluminum for enhanced single-molecule detection sensitivity. We computationally optimize the optical properties of AiBs by controlling their geometry and materials and find that hybrid nanostructures not only improve signal-to-background ratios but also provide additional excitation intensity and fluorescence enhancements. We further establish a two-step electron beam lithography process to fabricate hybrid material AiB arrays with high reproducibility and experimentally validate the higher excitation and emission enhancements of the hybrid nanostructures as compared to their gold counterpart. We foresee that biosensors based on hybrid AiBs will provide improved sensitivity beyond the capabilities of current nanophotonic sensors for a plethora of biosensing applications ranging from multicolor fluorescence detection to label-free vibrational spectroscopy.

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.

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.