Coupling of plasmon resonances in metallic gap antennas is of interest for a wide range of applications due to the highly localized strong electric fields supported by these structures, and their high sensitivity to alterations of their structure, geometry, and environment. Morphological alterations of asymmetric nanoparticle dimer antennas with (sub)-nanometer size gaps are assigned to changes of their optical response in correlative dark-field spectroscopy and high-resolution transmission electron microscopy (HR-TEM) investigations. This multimodal approach to investigate individual dimer structures clearly demonstrates that the coupling of the plasmon modes, in addition to well-known parameters such as the particle geometry and the gap size, is also affected by the relative alignment of both nanoparticles. The investigations corroborate that the alignment of the gap forming facets, and with that the gap area, is crucial for their scattering properties. The impact of a flat versus a rounded gap structure on the optical properties of equivalent dimers becomes stronger with decreasing gap size. These results hint at a higher confinement of the electric field in the gap and possibly a different onset of quantum transport effects for flat and rounded gap antennas in corresponding structures for very narrow gaps.
Gold-polymer hybrid nanoparticles attract wide interest as building blocks for the engineering of photonic materials and plasmonic (active) metamaterials with unique optical properties. In particular, the coupling of the localized surface plasmon resonances of individual metal nanostructures in the presence of nanometric gaps can generate highly enhanced and confined electromagnetic fields, which are frequently exploited for metal-enhanced light-matter interactions. The optical properties of plasmonic structures can be tuned over a wide range of properties by means of their geometry and the size of the inserted nanoparticles as well as by the degree of order upon assembly into 1D, 2D, or 3D structures. Here, the synthesis of silica-stabilized gold-poly(N-isopropylacrylamide) (SiO -Au-PNIPAM) core-satellite superclusters with a narrow size distribution and their incorporation into ordered self-organized 3D assemblies are reported. Significant alterations of the plasmon resonance are found for different assembled structures as well as strongly enhanced Raman signatures are observed. In a series of experiments, the origin of the highly enhanced signals can be assigned to the interlock areas of adjacent SiO -Au-PNIPAM core-satellite clusters and their application for highly sensitive nanoparticle-enhanced Raman spectroscopy is demonstrated.
Plasmonic nanoantennas have found broad applications in the fields of photovoltaics, electroluminescence, non-linear optics and for plasmon enhanced spectroscopy and microscopy. Of particular interest are fundamental limitations beyond the dipolar approximation limit. We introduce asymmetric gold nanoparticle antennas (AuNPs) with improved optical near-field properties based on the formation of sub-nanometer size gaps, which are suitable for studying matter with high-resolution and single molecule sensitivity. These dumbbell antennas are characterized in regard to their far-field and near-field properties and are compared to similar dimer and trimer antennas with larger gap sizes. The tailoring of the gap size down to sub-nanometer length scales is based on the integration of rigid macrocyclic cucurbituril molecules. Stable dimer antennas are formed with an improved ratio of the electromagnetic field enhancement and confinement. This ratio, taken as a measure of the performance of an antenna, can even exceed that exhibited by trimer AuNP antennas composed of comparable building blocks with larger gap sizes. Fluctuations in the far-field and near-field properties are observed, which are likely caused by distinct deviations of the gap geometry arising from the faceted structure of the applied colloidal AuNPs.
The ability of supramolecular transition metal coordination complexes to form stabilized, long-living, radiative charge-separated states has drawn interest to employ these triplet-state emitters for the design of photonic devices. Their applicability as photosensitizers of electron transfer in molecular photonic systems is directly coupled to fundamental studies of their rich and highly versatile photochemical and photophysical properties. Here, we demonstrate that the properties of individual dual-luminescent Ru2+-bis-terpyridine complexes can be addressed with excellent sensitivity in single-complex antenna-enhanced phosphorescence investigations. This sensitivity enables studying environmentally imposed alterations of their photophysical properties, e.g., in thin film applications. In contrast to ensemble averaging investigations in solution, single-complex antenna-enhanced phosphorescence investigations corroborate the existence of Ru2+-bis-terpyridine complexes with spectrally shifted emission peaks and diverging intrinsic quantum yields in the solid state. Across the sample of investigated individual complexes the observed emission spectra resemble the expected unique features of this specific Ru2+-bis-terpyridine complex. The origin of the shifted emission is discussed in terms of the existence of different molecular conformers of this specific Ru2+-bis-terpyridine complex facilitated by the embedment into a rigid solid matrix.
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