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. The parameters that determine the reactivity of plasmonic systems are deeply influenced by the dynamics and interplay of photons, plasmon-polaritons, carriers, phonons and molecular states. 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. These degrees of freedom can affect the reaction rates, the product selectivity or the spatial localization of a chemical reaction. In this Account, we show how the control of chemical hot spots can be achieved by carefully tuning the parameters that influence the cascade of events following the optical excitation of plasmonic modes in nanostructures. We discuss here a series of single photocatalyst techniques and ideas of how plasmonic nanoscale reactivity can be spatially mapped and imaged, and how the lifetime of hot and thermalized carriers can be altered by trap states on semiconductors and by metal-semiconductor interfaces. 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. Surpassing or enhancing each of these energy channels should enable to engineer 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.

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.

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.

The successful development of artificial photosynthesis requires finding new materials able to efficiently harvest sunlight and catalyze hydrogen generation and carbon dioxide reduction reactions. Plasmonic nanoparticles are promising candidates for these tasks, due to their ability to confine solar energy into molecular regions. Here, we review recent developments in hybrid plasmonic photocatalysis, including the combination of plasmonic nanomaterials with catalytic metals, semiconductors, perovskites, 2D materials, metal–organic frameworks, and electrochemical cells. We perform a quantitative comparison of the demonstrated activity and selectivity of these materials for solar fuel generation in the liquid phase. In this way, we critically assess the state-of-the-art of hybrid plasmonic photocatalysts for solar fuel production, allowing its benchmarking against other existing heterogeneous catalysts. Our analysis allows the identification of the best performing plasmonic systems, useful to design a new generation of plasmonic catalysts.

Optical printing is a simple and flexible method to bring colloidal nanoparticles from suspension to specific locations of a substrate. However, its application has been limited to the fabrication of arrays of isolated nanoparticles because, until now, it was never possible to bring nanoparticles closer together than approximately 300 nm. Here, we propose this limitation is due to thermophoretic repulsive forces generated by plasmonic heating of the NPs. We show how to overcome this obstacle and demonstrate the optical printing of connected nanoparticles with well-defined orientation. These experiments constitute a key step toward the fabrication by optical printing of functional nanostructures and microcircuits based on colloidal nanoparticles.

Optical printing is a powerful all-optical method that allows the incorporation of colloidal nanoparticles (NPs) onto substrates with nanometric precision. Here, we present a systematic study of the accuracy of optical printing of Au and Ag NPs, using different laser powers and wavelengths. When using light of wavelength tuned to the localized surface plasmon resonance (LSPR) of the NPs, the accuracy improves as the laser power is reduced, whereas for wavelengths off the LSPR, the accuracy is independent of the laser power. Complementary studies of the printing times of the NPs reveal the roles of Brownian and deterministic motion. Calculated trajectories of the NPs, taking into account the interplay between optical forces, electrostatic forces, and Brownian motion, allowed us to rationalize the experimental results and gain a detailed insight into the mechanism of the printing process. A clear framework is laid out for future optimizations of optical printing and optical manipulation of NPs near substrates.

Several fields of applications require a reliable characterization of the photothermal response and heat dissipation of nanoscopic systems, which remains a challenging task for both modeling and experimental measurements. Here, we present an implementation of anti-Stokes thermometry that enables the in situ photothermal characterization of individual nanoparticles (NPs) from a single hyperspectral photoluminescence confocal image. The method is label-free, potentially applicable to any NP with detectable anti-Stokes emission, and does not require any prior information about the NP itself or the surrounding media. With it, we first studied the photothermal response of spherical gold NPs of different sizes on glass substrates, immersed in water, and found that heat dissipation is mainly dominated by the water for NPs larger than 50 nm. Then, the role of the substrate was studied by comparing the photothermal response of 80 nm gold NPs on glass with sapphire and graphene, two materials with high thermal conductivity. For a given irradiance level, the NPs reach temperatures 18% lower on sapphire and 24% higher on graphene than on bare glass. The fact that the presence of a highly conductive material such as graphene leads to a poorer thermal dissipation demonstrates that interfacial thermal resistances play a very significant role in nanoscopic systems and emphasize the need for in situ experimental thermometry techniques. The developed method will allow addressing several open questions about the role of temperature in plasmon-assisted applications, especially ones where NPs of arbitrary shapes are present in complex matrixes and environments.

Optical waveguides represent the key element of integrated planar photonic circuitry having revolutionized many fields of photonics ranging from telecommunications, medicine, environmental science and light generation. However, the use of solid cores imposes limitations on applications demanding strong light-matter interaction within low permittivity media such as gases or liquids, which has gas triggered substantial interest towards hollow core waveguides. Here, we introduce the concept of an on-chip hollow core light cage that consists of free standing arrays of cylindrical dielectric strands around a central hollow core implemented using 3D nanoprinting. The cage operates by an anti-resonant guidance effect and exhibits extraordinary properties such as (1) diffractionless propagation in "quasi-air" over more than one centimetre distance within the ultraviolet, visible and near-infrared spectral domains, (2) unique side-wise direct access to the hollow core via open spaces between the strands speeding up gas diffusion times by at least a factor of 10 4 , and (3) an extraordinary high fraction of modal fields in the hollow section (> 99.9%). With these properties, the light cage can overcome the limitations of current planar hollow core waveguide technology, allowing unprecedented future on-chip applications within quantum technology, ultrafast spectroscopy, bioanalytics, acousto-optics, optofluidics and nonlinear optics. MotivationOne of the key objectives in current photonics research is to reduce the geometric footprint of bulky optical components by replacing them with their compact on-chip integrated counterparts in a costefficient way. Remarkable progress has been made in the development of planar waveguides, which constitute the principle element of integrated photonic devices, with applications in quantum technology [1], nonlinear physics [2] [3] and biophotonics [4]. However, most waveguides rely on solid cores, limiting the design flexibility of photonic sensors that require intense light-analyte interaction in medium with a lower dielectric permittivity as gases and liquids. The sensitivity of waveguides to detect refractive index (RI) changes of analytes is correlated to the fraction of electromagnetic power in the sensing medium and thus efforts are concentrated on finding guidance schemes which allow an enhanced concentration of light in the low index medium.One widely used sensing approach relies on evanescent waves. Integrated waveguides with exposed cores can provide access to the evanescent fields and found applications in areas such as spectroscopy and biosensing [5] [6] but can demand excessively long waveguide lengths to