Ultraviolet Resonant Nanogap Antennas with Rhodium Nanocube Dimers for Enhancing Protein Intrinsic Autofluorescence.

Plasmonic optical nanoantennas offer compelling solutions for enhancing light-matter interactions at the nanoscale. However, until now, their focus has been mainly limited to the visible and near-infrared regions, overlooking the immense potential of the ultraviolet (UV) range, where molecules exhibit their strongest absorption. Here, we present the realization of UV resonant nanogap antennas constructed from paired rhodium nanocubes. Rhodium emerges as a robust alternative to aluminum, offering enhanced stability in wet environments and ensuring reliable performance in the UV range. Our results showcase the nanoantenna's ability to enhance the UV autofluorescence of label-free streptavidin and hemoglobin proteins. We achieve significant enhancements of the autofluorescence brightness per protein by up to 120-fold and reach zeptoliter detection volumes, enabling UV autofluorescence correlation spectroscopy (UV-FCS) at high concentrations of several tens of micromolar. We investigate the modulation of fluorescence photokinetic rates and report excellent agreement between the experimental results and numerical simulations. This work expands the applicability of plasmonic nanoantennas to the deep UV range, unlocking the investigation of label-free proteins at physiological concentrations.

Self-assembled photonic structure: a Ga optical antenna on GaP nanowires.

Semiconductor nanowires are the perfect platform for nanophotonic applications owing to their resonant, waveguiding optical properties and technological capabilities providing control over their crystalline and chemical compositions. The vapor-liquid-solid growth mechanism allows the formation of hybrid metal-dielectric nanostructures promoting sub-wavelength light manipulation. In this work, we explore both experimentally and numerically the plasmonic effects promoted by a gallium (Ga) nanoparticle optical antenna decorating the facet of gallium phosphide (GaP) nanowires. Raman, photoluminescence and near-field mapping techniques are used to study the effects. We demonstrate several phenomena including field enhancement, antenna effect and increase in internal reflection. We show that the observed effects have to be considered when nanowires with a plasmonic particle are used in nanophotonic circuits and discuss the ways for utilization of these effects for efficient coupling of light into nanowire waveguide and field tailoring. The results open up promising pathways for the development of both passive and active nanophotonic elements, light harvesting and sensorics.

Ultraviolet Nanophotonics Enables Autofluorescence Correlation Spectroscopy on Label-Free Proteins with a Single Tryptophan.

Using the ultraviolet autofluorescence of tryptophan amino acids offers fascinating perspectives to study single proteins without the drawbacks of fluorescence labeling. However, the low autofluorescence signals have so far limited the UV detection to large proteins containing several tens of tryptophan residues. This limit is not compatible with the vast majority of proteins which contain only a few tryptophans. Here we push the sensitivity of label-free ultraviolet fluorescence correlation spectroscopy (UV-FCS) down to the single tryptophan level. Our results show how the combination of nanophotonic plasmonic antennas, antioxidants, and background reduction techniques can improve the signal-to-background ratio by over an order of magnitude and enable UV-FCS on thermonuclease proteins with a single tryptophan residue. This sensitivity breakthrough unlocks the applicability of UV-FCS technique to a broad library of label-free proteins.

Ultraviolet optical horn antennas for label-free detection of single proteins.

Single-molecule fluorescence techniques have revolutionized our ability to study proteins. However, the presence of a fluorescent label can alter the protein structure and/or modify its reaction with other species. To avoid the need for a fluorescent label, the intrinsic autofluorescence of proteins in the ultraviolet offers the benefits of fluorescence techniques without introducing the labelling drawbacks. Unfortunately, the low autofluorescence brightness of proteins has greatly challenged single molecule detection so far. Here we introduce optical horn antennas, a dedicated nanophotonic platform enabling the label-free detection of single proteins in the UV. This design combines fluorescence plasmonic enhancement, efficient collection up to 85° angle and background screening. We detect the UV autofluorescence from immobilized and diffusing single proteins, and monitor protein unfolding and dissociation upon denaturation. Optical horn antennas open up a unique and promising form of fluorescence spectroscopy to investigate single proteins in their native states in real time.

Anisotropic Radiation in Heterostructured "Emitter in a Cavity" Nanowire.

Tailorable synthesis of axially heterostructured epitaxial nanowires (NWs) with a proper choice of materials allows for the fabrication of novel photonic devices, such as a nanoemitter in the resonant cavity. An example of the structure is a GaP nanowire with ternary GaPAs insertions in the form of nano-sized discs studied in this work. With the use of the micro-photoluminescence technique and numerical calculations, we experimentally and theoretically study photoluminescence emission in individual heterostructured NWs. Due to the high refractive index and near-zero absorption through the emission band, the photoluminescence signal tends to couple into the nanowire cavity acting as a Fabry-Perot resonator, while weak radiation propagating perpendicular to the nanowire axis is registered in the vicinity of each nano-sized disc. Thus, within the heterostructured nanowire, both amplitude and spectrally anisotropic photoluminescent signals can be achieved. Numerical modeling of the nanowire with insertions emitting in infrared demonstrates a decay in the emission directivity and simultaneous rise of the emitters coupling with an increase in the wavelength. The emergence of modulated and non-modulated radiation is discussed, and possible nanophotonic applications are considered.

Numerical Study of GaP Nanowires: Individual and Coupled Optical Waveguides and Resonant Phenomena.

The development of novel nanophotonic devices and circuits necessitates studies of optical phenomena in nanoscale structures. Catalyzed semiconductor nanowires are known for their unique properties including high crystallinity and silicon compatibility making them the perfect platform for optoelectronics and nanophotonics. In this work, we explore numerically optical properties of gallium phosphide nanowires governed by their dimensions and study waveguiding, coupling between the two wires and resonant field confinement to unveil nanoscale phenomena paving the way for the fabrication of the integrated optical circuits. Photonic coupling between the two adjacent nanowires is studied in detail to demonstrate good tolerance of the coupling to the distance between the two aligned wires providing losses not exceeding 30% for the gap of 100 nm. The dependence of this coupling is investigated with the wires placed nearby varying their relative position. It is found that due to the resonant properties of a nanowire acting as a Fabry-Perot cavity, two coupled wires represent an attractive system for control over the optical signal processing governed by the signal interference. We explore size-dependent plasmonic behaviors of the metallic Ga nanoparticle enabling GaP nanowire as an antenna-waveguide hybrid system. We demonstrate numerically that variation of the structure dimensions allows the nearfield tailoring. As such, we explore GaP NWs as a versatile platform for integrated photonic circuits.

Single Photon Source from a Nanoantenna-Trapped Single Quantum Dot.

Single photon sources with high brightness and subnanosecond lifetimes are key components for quantum technologies. Optical nanoantennas can enhance the emission properties of single quantum emitters, but this approach requires accurate nanoscale positioning of the source at the plasmonic hotspot. Here, we use plasmonic nanoantennas to simultaneously trap single colloidal quantum dots and enhance their photoluminescence. The nano-optical trapping automatically locates the quantum emitter at the nanoantenna hotspot without further processing. Our dedicated nanoantenna design achieves a high trap stiffness of 0.6 (fN/nm)/mW for quantum dot trapping, together with a relatively low trapping power of 2 mW/µm2. The emission from the nanoantenna-trapped single quantum dot shows 7× increased brightness, 50× reduced blinking, 2× shortened lifetime, and a clear antibunching below 0.5 demonstrating true single photon emission. Combining nano-optical tweezers with plasmonic enhancement is a promising route for quantum technologies and spectroscopy of single nano-objects.

Zero-mode waveguides can be made better: fluorescence enhancement with rectangular aluminum nanoapertures from the visible to the deep ultraviolet.

Nanoapertures milled in metallic films called zero-mode waveguides (ZMWs) overcome the limitations of classical confocal microscopes by enabling single molecule analysis at micromolar concentrations with improved fluorescence brightness. While the ZMWs have found many applications in single molecule fluorescence studies, their shape has been mainly limited to be circular. Owing to the large parameter space to explore and the lack of guidelines, earlier attempts using more elaborate shapes have led to unclear conclusions whether or not the performance was improved as compared to a circular ZMW. Here, we comparatively analyze the performance of rectangular-shaped nanoapertures milled in aluminum to enhance the fluorescence emission rate of single molecules from the near infrared to the deep ultraviolet. Our new design is based on rational principles taking maximum advantage of the laser linear polarization. While the long edge of the nanorectangle is set to meet the cut-off size for the propagation of light into the nanoaperture, the short edge is reduced to 30 nm to accelerate the photodynamics while maintaining bright fluorescence rates. Our results show that both in the red and in the ultraviolet, the nanorectangles provide 50% brighter photon count rates as compared to the best performing circular ZMWs and achieve fluorescence lifetimes shorter than 300 ps. These findings can be readily used to improve the performance of ZMWs, especially for fast biomolecular dynamics, bright single-photon sources, and ultraviolet plasmonics.