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To date, the advanced synthetic approaches for palladium nanoparticle-based catalysts involve multistep, toxic, and high-cost fabrication routes with low catalytic and sensing performance. In this work, we introduce a new one-shot approach to produce highly sensitive Pd nanocomposites using a large-area polymer self-assembly strategy. This synthesis method allowed us to control the Pd nanoparticle shape and to tailor their plasmonic band positions in a wide light spectral range from ~350 to ~800 nm. We thus determined the critical synthesis conditions that give rise to a ringlike morphology in a reproducible manner. No need for a reducing agent and preliminary functionalization of the surface supporting the nanoparticles upon synthesis. To the best of our knowledge, few works have demonstrated the good performance of PdNPs in sensing. Here, we have demonstrated a robust SERS response for 4-mercaptopyridine with an enhancement factor of 4.2 × 105. We were able to exceed this high value, which matches the current maximum found in the literature, by decreasing the gap distances between Pd nanorings due to the high density of hotspots and the exacerbation of the coupling effect between PdNPs. These tailored products provide new insights for the use of Pd nanomaterials in photocatalysis applications, according to the well-established catalytic performance of Pd materials obtained in this work. [ABSTRACT FROM AUTHOR]

Multi-resonant plasmonic simple geometries like nanocylinders and nanorods are highly interesting for two-photon photoluminescence and second harmonic generation applications, due to their easy fabrication and reproducibility in comparison with complex multi-resonant systems like dimers or nanoclusters. We demonstrate experimentally that by using a simple gold nanocylinder we can achieve a double resonantly enhanced two-photon photoluminescence of quantum dots, by matching the excitation wavelength of the quantum dots with a dipolar plasmon mode, while the emission is coupled with a radiative quadrupolar mode. We establish a method to separate experimentally the enhancement factor at the excitation and at the emission wavelengths for this double resonant system. The sensitivity of the spectral positions of the dipolar and quadrupolar plasmon resonances to the ellipticity of the nanocylinders and its impact on the two-photon photoluminescence enhancement are discussed.

Phthalocyanines are frequently used as probing molecules in the field of single-molecule surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS). In this work, we systematically compare the SERS and TERS spectra from a thin cobalt phthalocyanine (CoPc) film that is deposited on a Au film. The contributions from electromagnetic (EM), resonance, and charge-transfer enhancements are discussed. Radially and azimuthally polarized vector beams are used to investigate the influences of molecular orientation and the localized surface plasmon resonance (SPR). Furthermore, two different excitation wavelengths (636 and 532 nm) are used to study the resonant excitation effect as well as the involvement of the charge-transfer processes between CoPc and the Au substrate. It is shown that the Raman peaks of CoPc are mostly enhanced by 636 nm excitation through a combination of resonant excitation, high EM enhancement, and chemical enhancement via charge transfer from the metal to the molecule. At 532 nm excitation, however, the SERS and TERS spectra are dominated by photoluminescence, which originates from a photo-induced charge-transfer process from the optically excited molecule to the metal. The contributions of the different enhancement mechanisms explain the optical contrasts seen in the TERS images of Au nanodisks covered by the CoPc film. The insight achieved in this work will help to understand the optical contrast in sub- or single-molecule TERS imaging and apply SERS or TERS in the field of photocatalysis.

Confocal optical microscopy and tip-enhanced optical microscopy are applied to characterize the defect distributions in chemical vapor deposition-grown WS2 monolayer triangles qualitatively and quantitatively. The presence of defects in individual monolayer WS2 triangles is revealed with diffraction-limited spatial resolution in their photoluminescence (PL) images, from which the inhomogeneous defect density distribution is calculated, showing an inverse relationship to the PL intensity. The defect-related surface-enhanced Raman spectroscopy (SERS) effect is investigated by depositing a thin copper phthalocyanine layer (5 nm) as the probe molecule on the monolayer WS2 triangles surface. Higher SERS enhancement effects are observed at the defect-rich areas. Furthermore, tip-enhanced optical measurements are performed, which can reveal morphologically defected areas invisible in the confocal optical measurements. Furthermore, the area with high defect density appears brighter than the low-defected area in the tip-enhanced optical measurements, which are different from the observation in the confocal optical measurements. The underlying reasons are attributed to the near-field enhancement of the defect exciton emission induced by the optically excited tip and to an improved coupling efficiency between the tip-generated near-field with the altered dipole moment orientation at the local defect. [ABSTRACT FROM AUTHOR]

Hypericin tautomerization that involves the migration of the labile protons is believed to be the primary photophysical process relevant to its light-activated antiviral activity. Despite the difficulty in isolating individual tautomers, it can be directly observed in single-molecule experiments. We show that the tautomerization of single hypericin molecules in free space is observed as an abrupt flipping of the image pattern accompanied with fluorescence intensity fluctuations, which are not correlated with lifetime changes. Moreover, the study can be extended to a λ/2 Fabry–Pérot microcavity. The modification of the local photonic environment by a microcavity is well simulated with a theoretical model that shows good agreement with the experimental data. Inside a microcavity, the excited state lifetime and fluorescence intensity of single hypericin molecules are correlated, and a distinct jump of the lifetime and fluorescence intensity reveals the temporal behavior of the tautomerization with high sensitivity and high temporal resolution. The observed changes are also consistent with time-dependent density functional theory calculations. Our approach paves the way to monitor and even control reactions for a wider range of molecules at the single molecule level. [ABSTRACT FROM AUTHOR]

The regular arrangement of metal nanoparticles influences their plasmonic behavior. It has been previously demonstrated that the coupling between diffracted waves and plasmon modes can give rise to extremely narrow plasmon resonances. This is the case when the single-particle localized surface plasmon resonance (λLSP) is very close in value to the Rayleigh anomaly wavelength (λRA) of the nanoparticles array. In this paper, we performed angle-resolved extinction measurements on a 2D array of gold nano-cylinders designed to fulfil the condition λRA

Avalanche multiphoton photoluminescence (AMPL) is observed from coupled Au–Al nanoantennas under intense laser pumping, which shows more than one order of magnitude emission intensity enhancement and distinct spectral features compared with ordinary metallic photoluminescence. The experiments are conducted by altering the incident laser intensity and polarization using a home-built scanning confocal optical microscope. The results show that AMPL originates from the recombination of avalanche hot carriers that are seeded by multiphoton ionization. Notably, at the excitation stage, multiphoton ionization is shown to be assisted by the local electromagnetic field enhancement produced by coupled plasmonic modes. At the emission step, the giant AMPL intensity can be evaluated as a function of the local field environment and the thermal factor for hot carriers, in accordance with a linear relationship between the power law exponent coefficient and the emitted photon energy. The dramatic change in the spectral profile is explained by spectral linewidth broadening mechanisms. This study offers nanospectroscopic evidence of both the potential optical damages for plasmonic nanostructures and the underlying physical nature of light–matter interactions under a strong laser field; it illustrates the significance of the emerging topics of plasmonic-enhanced spectroscopy and laser-induced breakdown spectroscopy. [ABSTRACT FROM AUTHOR]

Plasmonic film-nanoparticles coupled systems have had a renewed interest for the past 5 years both for the richness of the provided plasmonic modes and for their high technological potential. Many groups started to investigate the optical properties of film-nanoparticles coupled systems, as to whether the spacer layer thickness is tens of nanometers thick or goes down to a few nanometers or angstroms, even reaching contact. This article reviews the recent breakthroughs in the physical understanding of such coupled systems and the different systems where nanoparticles on top of the spacer layer are either isolated/random or form regular arrays. The potential for applications, especially as perfect absorbers or transmitters is also put into evidence.