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Temperature measurements at the nanoscale are vital for the application of plasmonic structures in medical photothermal therapy and materials science but very challenging to realize in practice. In this work, we exploit a combination of surface-enhanced Raman spectroscopy together with the characteristic temperature dependence of the Raman peak maxima observed in β-phase copper phthalocyanine (β-CuPc) to measure the surface temperature of plasmonic gold nanoparticles under laser irradiation. We begin by measuring the temperature-dependent Raman shifts of the three most prominent modes of β-CuPc films coated on an array of Au nanodisks over a temperature range of 100-500 K. We then use these calibration curves to determine the temperature of an array of Au nanodisks irradiated with varying laser powers. The extracted temperatures agree quantitatively with the ones obtained via numerical modeling of electromagnetic and thermodynamic properties of the irradiated array. Thin films of β-CuPc display low extinction coefficients in the blue-green region of the visible spectrum as well as exceptional thermal stability, allowing a wide temperature range of operation of our Raman thermometer, with minimal optical distortion of the underlying structures. Thanks to the strong thermal response of the Raman shifts in β-CuPc, our work opens the opportunity to investigate photothermal effects at the nanoscale in real time.

Light absorption and scattering by metal nanoparticles can drive catalytic reactions at their surface via the generation of hot charge carriers, elevated temperatures, and focused electromagnetic fields. These photoinduced processes can substantially alter the shape, surface structure, and oxidation state of surface atoms of the nanoparticles and therefore significantly modify their catalytic properties. Information on such local structural and chemical change in plasmonic nanoparticles is however blurred in ensemble experiments, due to the typical large heterogeneity in sample size and shape distributions. Here, we use single-particle dark-field and Raman scattering spectroscopy to elucidate the reshaping and surface restructuring of individual silver nanodisks under plasmon excitation and during photocatalytic CO2 hydrogenation. We show that silver nanoparticles reshape significantly in inert N2 atmosphere, due to photothermal effects. Furthermore, by collecting the inelastic scattering during laser irradiation in a reducing gas environment, we observe intermittent light emission from silver clusters transiently formed at the nanoparticle surface. These clusters are likely to modify the photocatalytic activity of silver nanodisks and to enable detection of reaction products by enhancing their Raman signal. Our results highlight the dynamic nature of the catalytic surface of plasmonic silver nanoparticles and demonstrate the power of single-particle spectroscopic techniques to unveil their structure-activity relationship both in situ and in real time.

Localized surface plasmon resonances (LSPRs) in metal nanoparticles can drive chemical reactions at their surface, but it is often challenging to disentangle the exact activation mechanism. The decay of LSPRs can lead to photothermal heating, electromagnetic hot spots, and the ejection of nonthermalized charge carriers, but all of these processes typically occur simultaneously and on ultrafast time scales. Here, we develop a plasmon-assisted Au@Ag core@shell nanorod synthesis in which each plasmon-decay mechanism can be independently assessed. Using different illumination wavelengths combined with extinction spectroscopy, transmission electron microscopy, thermal characterization, and finite-difference time-domain simulations, we unequivocally identify the transfer of interband holes to ascorbic acid as the rate-limiting step in the silver shell growth reaction. Our conclusion is corroborated by single-particle studies of gold nanospheres that display isotropic reactivity, consistent with interband hole-driven nanoparticle syntheses. Our strategy for distinguishing among plasmon-activation mechanisms can be extended to a variety of light-driven processes, including photocatalysis, nanoparticle syntheses, and drug delivery.

Plasmonic particle arrays have remarkable optical properties originating from their collective behavior, which results in resonances with narrow line widths and enhanced electric fields extending far into the surrounding medium. Such resonances can be exploited for applications in strong light-matter coupling, sensing, light harvesting, nonlinear nanophotonics, lasing, and solid-state lighting. However, as the lattice constants associated with plasmonic particle arrays are on the order of their resonance wavelengths, mapping the interaction between point dipoles and plasmonic particle arrays cannot be done with diffraction-limited methods. Here, we map the enhanced emission of single fluorescent molecules coupled to a plasmonic particle array with ∼20 nm in-plane resolution by using stochastic super-resolution microscopy. We find that extended lattice resonances have minimal influence on the spontaneous decay rate of an emitter but instead can be exploited to enhance the outcoupling and directivity of the emission. Our results can guide the rational design of future optical devices based on plasmonic particle arrays.