ORCID Profile
0000-0002-4524-3423
Current Organisation
Ludwig-Maximilians-Universität München
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Publisher: American Chemical Society (ACS)
Date: 02-09-2022
Publisher: American Chemical Society (ACS)
Date: 20-08-2019
DOI: 10.1021/ACS.ACCOUNTS.9B00234
Abstract: In recent years, the possibility to induce chemical transformations by using tunable plasmonic modes has opened the question of whether we can control or create chemical hot spots in these systems. This can be rationalized as the reactive analogue of the well-established concept of optical hot spots, which have drawn a great deal of attention to plasmonic nanostructures for their ability to circumvent the far-field diffraction limit of conventional optical elements. Although optical hot spots can be mainly defined by the geometry and permittivity of the nanostructures, the degrees of freedom influencing their photocatalytic properties appear to be much more numerous. In fact, the reactivity of plasmonic systems are deeply influenced by the dynamics and interplay of photons, plasmon-polaritons, carriers, phonons, and molecular states. These degrees of freedom can affect the reaction rates, the product selectivity, or the spatial localization of a chemical reaction. In this Account, we discuss the oportunities to control chemical hot spots by tuning the cascade of events that follows the excitation and decay of plasmonic modes in nanostructures. We discuss a series of techniques to spatially map and image plasmonic nanoscale reactivity at the single photocatalyst level. We show how to optimize the reactivity of carriers by manipulating their excitation and decay mechanisms in plasmonic nanoparticles. In addition, the tailored generation of non-thermal phonons in metallic nanostructures and their dissipation is shown as a promise to understand and exploit thermal photocatalysis at the nanoscale. Understanding and controlling these processes is essential for the rational design of solar nanometric photocatalysts. Nevertheless, the ultimate capability of a plasmonic photocatalyst to trigger a chemical reaction is correlated to its ability to navigate through, or even modify, the potential energy surface of a given chemical reaction. Here we reunite both worlds, the plasmonic photocatalysts and the molecular ones, identifying different energy transfer pathways and their influence on selectivity and efficiency of chemical reactions. We foresee that the migration from optical to chemical hot spots will greatly assist the understanding of ongoing plasmonic chemistry.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9FD90011J
Publisher: IEEE
Date: 06-2019
Publisher: Optica Publishing Group
Date: 11-03-2021
DOI: 10.1364/OME.419398
Abstract: Three-dimensional laser nanoprinting represents a unique approach for implementing on-chip hollow-core waveguides. Here we discuss the fabrication characteristics of the light cage geometry arising from the used two-photon polymerization lithography. We reveal the current limits of achievable waveguide length (3 cm), single strand aspect ratio (8200) and modal attenuation. Very high reproducibility for light cages on the same chip is found, while different conditions in fabrication cycles impose chip-to-chip variations. We also highlight the relevance of including reinforcement rings to prevent structural collapse. The results presented uncover key issues that result from nanoprinting light cages and can be transferred to other nanoprinted waveguides.
Publisher: American Chemical Society (ACS)
Date: 17-08-2017
DOI: 10.1021/ACS.NANOLETT.7B02713
Abstract: Optical printing holds great potential to enable the use of the vast variety of colloidal nanoparticles (NPs) in nano- and microdevices and circuits. By means of optical forces, it enables the direct assembly of NPs, one by one, onto specific positions of solid surfaces with great flexibility of pattern design and no need of previous surface patterning. However, for unclear causes it was not possible to print identical NPs closer to each other than 300 nm. Here, we show that the repulsion restricting the optical printing of close by NPs arises from light absorption by the printed NPs and subsequent local heating. By optimizing heat dissipation, it is possible to reduce the minimum separation between NPs. Using a reduced graphene oxide layer on a sapphire substrate, we demonstrate for the first time the optical printing of Au-Au NP dimers. Modeling the experiments considering optical, thermophoretic, and thermo-osmotic forces we obtain a detailed understanding and a clear pathway for the optical printing fabrication of complex nano structures and circuits based on connected colloidal NPs.
Publisher: American Chemical Society (ACS)
Date: 19-10-2022
DOI: 10.1021/ACSSENSORS.2C00988
Abstract: Nanoparticle tracking analysis (NTA) is a widely used methodology to investigate nanoscale systems at the single species level. Here, we introduce the locally structured on-chip optofluidic hollow-core light cage, as a novel platform for waveguide-assisted NTA. This hollow waveguide guides light by the antiresonant effect in a sparse array of dielectric strands and includes a local modification to realize aberration-free tracking of in idual nano-objects, defining a novel on-chip solution with properties specifically tailored for NTA. The key features of our system are (i) well-controlled nano-object illumination through the waveguide mode, (ii) diffraction-limited and aberration-free imaging at the observation site, and (iii) a high level of integration, achieved by on-chip interfacing to fibers. The present study covers all aspects relevant for NTA including design, simulation, implementation via 3D nanoprinting, and optical characterization. The capabilities of the approach to precisely characterize practically relevant nanosystems have been demonstrated by measuring the solvency-induced collapse of a nanoparticle system which includes polymer brush-based shells that react to changes in the liquid environment. Our study unlocks the advantages of the light cage approach in the context of NTA, suggesting its application in various areas such as bioanalytics, life science, environmental science, or nanoscale material science in general.
Publisher: American Chemical Society (ACS)
Date: 07-03-2019
Publisher: AIP Publishing
Date: 06-2021
DOI: 10.1063/5.0048501
Abstract: Interfacing integrated on-chip waveguides with spectroscopic approaches represents one research direction within current photonics aiming at reducing geometric footprints and increasing device densities. Particularly relevant is to connect chip-integrated waveguides with established fiber-based circuitry, opening up the possibility for a new class of devices within the field of integrated photonics. Here, one attractive waveguide is the on-chip light cage, confining and guiding light in a low-index core through the anti-resonance effect. This waveguide, implemented via 3D nanoprinting and reaching nearly 100% overlap of mode and material of interest, uniquely provides side-wise access to the core region through the open spaces between the cage strands, drastically reducing gas diffusion times. Here, we extend the capabilities of the light cage concept by interfacing light cages and optical fibers, reaching a fully fiber-integrated on-chip waveguide arrangement with its spectroscopic capabilities demonstrated here on the ex le of tunable diode laser absorption spectroscopy of ammonia. Controlling and optimizing the fiber circuitry integration have been achieved via automatic alignment in etched v-grooves on silicon chips. This successful device integration via 3D nanoprinting highlights the fiber-interfaced light cage to be an attractive waveguide platform for a multitude of spectroscopy-related fields, including bio-analytics, lab-on-chip photonic sensing, chemistry, and quantum metrology.
Publisher: Springer Science and Business Media LLC
Date: 31-05-2021
DOI: 10.1038/S41377-021-00556-Z
Abstract: Controlling coherent interaction between optical fields and quantum systems in scalable, integrated platforms is essential for quantum technologies. Miniaturised, warm alkali-vapour cells integrated with on-chip photonic devices represent an attractive system, in particular for delay or storage of a single-photon quantum state. Hollow-core fibres or planar waveguides are widely used to confine light over long distances enhancing light-matter interaction in atomic-vapour cells. However, they suffer from inefficient filling times, enhanced dephasing for atoms near the surfaces, and limited light-matter overlap. We report here on the observation of modified electromagnetically induced transparency for a non-diffractive beam of light in an on-chip, laterally-accessible hollow-core light cage. Atomic layer deposition of an alumina nanofilm onto the light-cage structure was utilised to precisely tune the high-transmission spectral region of the light-cage mode to the operation wavelength of the atomic transition, while additionally protecting the polymer against the corrosive alkali vapour. The experiments show strong, coherent light-matter coupling over lengths substantially exceeding the Rayleigh range. Additionally, the stable non-degrading performance and extreme versatility of the light cage provide an excellent basis for a manifold of quantum-storage and quantum-nonlinear applications, highlighting it as a compelling candidate for all-on-chip, integrable, low-cost, vapour-based photon delay.
Publisher: SPIE
Date: 24-02-2020
DOI: 10.1117/12.2539265
Publisher: Wiley
Date: 14-09-2023
Publisher: American Chemical Society (ACS)
Date: 09-12-2020
Publisher: Optica Publishing Group
Date: 24-12-2019
DOI: 10.1364/OL.45.000196
Abstract: Here, we show that the optical properties of direct-laser-written on-chip hollow-core waveguides—so-called light cages—can be controlled to a very high degree by dielectric nanofilms. Using low-temperature atomic layer deposition (ALD), alumina nanofilms are concentrically deposited on the high-aspect strands that surround the central air core and confine the light via the anti-resonant effect. In accordance with modal cutoff simulations without any free parameters, a linear spectral shift of the resonances with increasing film thickness is experimentally observed. The phenomenon is explained by a shift in the dispersions of cladding supermodes. As neither cage geometry nor polymer is affected by the film deposition, our results suggest ALD to be an essential tool for fine-tuning the properties of hollow-core light cages and to protect them from aggressive substances, being relevant for, e.g., bioanalytics or quantum technology.
Publisher: Optica Publishing Group
Date: 11-01-2023
DOI: 10.1364/OE.475794
Abstract: Here, we unlock the properties of the recently introduced on-chip hollow-core microgap waveguide in the context of optofluidics which allows for intense light-water interaction over long lengths with fast response times. The nanoprinted waveguide operates by the anti-resonance effect in the visible and near-infrared domain and includes a hollow core with defined gaps every 176 µm. The spectroscopic capabilities are demonstrated by various absorption-related experiments, showing that the Beer-Lambert law can be applied without any modification. In addition to revealing key performance parameters, time-resolved experiments showed a decisive improvement in diffusion times resulting from the lateral access provided by the microgaps. Overall, the microgap waveguide represents a pathway for on-chip spectroscopy in aqueous environments.
Publisher: The Optical Society
Date: 09-08-2019
DOI: 10.1364/OL.44.004016
Publisher: OSA
Date: 2019
Publisher: American Chemical Society (ACS)
Date: 31-12-2018
Publisher: American Chemical Society (ACS)
Date: 21-02-2019
DOI: 10.1021/ACS.NANOLETT.8B04950
Abstract: Plasmonic hot carriers have been recently identified as key elements for photocatalysis at visible wavelengths. The possibility to transfer energy between metal plasmonic nanoparticles and nearby molecules depends not only on carrier generation and collection efficiencies but also on their energy at the metal-molecule interface. Here an energy screening study was performed by monitoring the aniline electro-polymerization reaction via an illuminated 80 nm gold nanoparticle. Our results show that plasmon excitation reduces the energy required to start the polymerization reaction as much as 0.24 eV. Three possible photocatalytic mechanisms were explored: the enhanced near field of the illuminated particle, the temperature increase at the metal-liquid interface, and the excited electron-hole pairs. This last phenomenon is found to be the one contributing most prominently to the observed energy reduction.
Publisher: Springer Science and Business Media LLC
Date: 07-2021
Publisher: Research Square Platform LLC
Date: 13-12-2022
DOI: 10.21203/RS.3.RS-2233698/V1
Abstract: Localized surface plasmons are lossy and generate heat. However, accurate measurement of the temperature of metallic nanoparticles under illumination remains an open challenge, creating difficulties in the interpretation of results across plasmonic applications. Particularly, there is a quest for understanding the role of temperature in plasmon-assisted catalysis. Bimetallic nanoparticles combining plasmonic with catalytic metals are raising increasing interest in artificial photosynthesis and the production of solar fuels. Here, we perform single-particle nanothermometry measurements to investigate the link between morphology and thermal performance of colloidal Au/Pd nanoparticles with two different configurations: Au core – Pd shell and Au core- Pd satellites. It is observed that the inclusion of Pd as a shell strongly reduces the photothermal response in comparison to the bare cores, while the inclusion of Pd as satellites keeps photothermal properties almost unaffected. These results contribute to a better understanding of energy conversion processes in plasmon-assisted catalysis.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8FD00138C
Abstract: Nanoscopic inspection of reactivity in single plasmonic photocatalysts.
No related grants have been discovered for Julian Gargiulo.