We report on the recent scientific research contribution of non-linear optics based on Sum-Frequency Generation (SFG) spectroscopy as a surface probe of the plasmonic properties of materials. In this review, we present a general introduction to the fundamentals of SFG spectroscopy, a well-established optical surface probe used in various domains of physical chemistry, when applied to plasmonic materials. The interest of using SFG spectroscopy as a complementary tool to surface-enhanced Raman spectroscopy in order to probe the surface chemistry of metallic nanoparticles is illustrated by taking advantage of the optical amplification induced by the coupling to the localized surface plasmon resonance. A short review of the first developments of SFG applications in nanomaterials is presented to span the previous emergent literature on the subject. Afterwards, the emphasis is put on the recent developments and applications of the technique over the five last years in order to illustrate that SFG spectroscopy coupled to plasmonic nanomaterials is now mature enough to be considered a promising research field of non-linear plasmonics.

Within semiconductor quantum dots (QDs), exciton recombination processes are noteworthy for depending on the nature of surface coordination and nanocrystal/ligand bonding. The influence of the molecular surroundings on QDs optoelectronic properties is therefore intensively studied. Here, from the converse point of view, we analyse and model the influence of QDs optoelectronic properties on their ligands. As revealed by sum-frequency generation spectroscopy, the vibrational structure of ligands is critically correlated to QDs electronic structure when these are pumped into their excitonic states. Given the different hypotheses commonly put forward, such a correlation is expected to derive from either a direct overlap between the electronic wavefunctions, a charge transfer, or an energy transfer. Assuming that the polarizability of ligands is subordinate to the local electric field induced by excitons through dipolar interaction, our classical model based on nonlinear optics unambiguously supports the latter hypothesis.

Demonstration of a high performance PIERS signal based on a highly crystalline ZnO film with Au nanoparticles irradiated by UV.

We unveil the competitive mechanisms driving the FRET between quantum dots, leading to unexpectedly high enhancements of acceptors’ fluorescence, especially when their local environment is initially unfavourable for their radiative relaxation.

Modeling of the fluorescence spectra of quantum dots altered by inner filter effects is applicable to any type of fluorophore.