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Dumbbell gold nanoparticle dimer antennas with advanced optical properties

2018, Herrmann, Janning F., Höppener, Christiane

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.

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Multimodal Characterization of Resin Embedded and Sliced Polymer Nanoparticles by Means of Tip-Enhanced Raman Spectroscopy and Force-Distance Curve Based Atomic Force Microscopy

2020, Höppener, Christiane, Schacher, Felix H., Deckert, Volker

Understanding the property-function relation of nanoparticles in various application fields involves determining their physicochemical properties, which is still a remaining challenge to date. While a multitude of different characterization tools can be applied, these methods by themselves can only provide an incomplete picture. Therefore, novel analytical techniques are required, which can address both chemical functionality and provide structural information at the same time with high spatial resolution. This is possible by using tip-enhanced Raman spectroscopy (TERS), but due to its limited depth information, TERS is usually restricted to investigations of the nanoparticle surface. Here, TERS experiments are established on polystyrene nanoparticles (PS NPs) after resin embedding and microtome slicing. With that, unique access to their internal morphological features is gained, and thus, enables differentiation between information obtained for core- and shell-regions. Complementary information is obtained by means of transmission electron microscopy (TEM) and from force-distance curve based atomic force microscopy (FD-AFM). This multimodal approach achieves a high degree of discrimination between the resin and the polymers used for nanoparticle formulation. The high potential of TERS combined with advanced AFM spectroscopy tools to probe the mechanical properties is applied for quality control of the resin embedding procedure.

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Microwave-Assisted Synthesis of Core–Shell Nanoparticles—Insights into the Growth of Different Geometries

2020, Womiloju, Aisha A., Höppener, Christiane, Schubert, Ulrich S., Hoeppener, Stephanie

Microwave irradiation is utilized for the rapid synthesis of gold–silver core–shell bimetallic nanoparticles (NPs) in a two-step process. A strategy of establishing a bilayer organic barrier around the core using citrate and ascorbic acid as capping agents, providing a means to achieve a well-defined boundary layer between the core and the shell material, is reported. These boundary layers are essential for synthesizing different core–shell morphologies and the approach results in tunable bimetallic NPs with defined core–shell structures, both for spherical as well as for triangular seed cores. In addition, theoretical calculations of the plasmonic characteristics based on the boundary element method of different classes of NPs are conducted. These investigations enable conclusions to be drawn on the influence of the core morphology on the tunability of their localized surface plasmon resonances. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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On the stability of microwave-fabricated SERS substrates - chemical and morphological considerations

2021, Wang, Limin, Womiloju, Aisha Adebola, Höppener, Christiane, Schubert, Ulrich Sigmar, Hoeppener, Stephanie

The stability of surface-enhanced Raman spectroscopy (SERS) substrates in different organic solvents and different buffer solutions was investigated. SERS substrates were fabricated by a microwave-assisted synthesis approach and the morphological as well as chemical changes of the SERS substrates were studied. It was demonstrated that the SERS substrates treated with methanol, ethanol, or N,N-dimethylformamide (DMF) were comparable and showed overall good stability and did not show severe morphological changes or a strong decrease in their Raman activity. Toluene treatment resulted in a strong decrease in the Raman activity whereas dimethyl sulfoxide (DMSO) treatment completely preserved or even slightly improved the Raman enhancement capabilities. SERS substrates immersed into phosphate-buffered saline (PBS) solutions were observed to be rather instable in low and neutral pH buffer solutions. Other buffer systems showed less severe influences on the SERS activity of the substrates and a carbonate buffer at pH 10 was found to even improve SERS performance. This study represents a guideline on the stability of microwave-fabricated SERS substrates or other SERS substrates consisting of non-stabilized silver nanoparticles for the application of different organic solvents and buffer solutions.