Alexa Courty

In situ liquid-cell electron microscopy of silver–palladium galvanic replacement reactions on silver nanoparticles

Galvanic replacement reactions provide an elegant way of transforming solid nanoparticles into complex hollow morphologies. Conventionally, galvanic replacement is studied by stopping the reaction at different stages and characterizing the products ex situ. In situ observations by liquid-cell electron microscopy can provide insight into mechanisms, rates and possible modifications of galvanic replacement reactions in the native solution environment. Here we use liquid-cell electron microscopy to investigate galvanic replacement reactions between silver nanoparticle templates and aqueous palladium salt solutions. Our in situ observations follow the transformation of the silver nanoparticles into hollow silver-palladium nanostructures. While the silver-palladium nanocages have morphologies similar to those obtained in ex situ control experiments the reaction rates are much higher, indicating that the electron beam strongly affects the galvanic-type process in the liquid-cell. By using scavengers added to the aqueous solution we identify the role of radicals generated via radiolysis by high-energy electrons in modifying galvanic reactions.

Stability of self-ordered thiol-coated silver nanoparticles: oxidative environment effects.

Here, we study the stability of the 2D organization of thiol-coated silver nanoparticles (NPs) by transmission electron microscopy. Whatever the alkyl chain length and the nature of the silver precursor, we show the rapid corrosion (over a few days) of the NPs by O2 from laboratory air whereas they remain stable for several weeks under a nitrogen atmosphere. We show that this phenomenon is amplified by the humidity in the air and by thiols trapped in the NP monolayers. We obtain evidence of these thiols in excess by infrared and energy-dispersive spectroscopies. This study of stability has been extended to gold nanoparticles (AuNPs) coated with dodecanethiols. The AuNPs remain stable under laboratory air because of the higher redox potential of Au compared to that of Ag and O2.

Optical response and SERS properties of individual large scale supracrystals made of small silver nanocrystals

AbstractThere is a considerable interest in producing and understanding the optical and spectroscopic properties of ordered nanoparticle assemblies. Herein, we describe and interpret the optical absorbance and Raman properties of 5.9 nm ± 0.3 nm diameter silver nanocrystals coated with dodecanethiol and organized in highly ordered 3D superlattices of different heights. Each superlattice was studied individually, which allowed to elaborate a model based on Maxwell-Garnett theory to reproduce qualitatively the height and wavelength dependence of the absorbance. Importantly, because of their small size compared to that of traditional nanoparticles used in Surface Enhanced Raman Spectroscopy (SERS), the large 3D distribution of hot spots generated by the silver superlattices allowed to easily obtain SERS spectra of the surrounding ligands despite their intrinsic low Raman cross section. Accordingly, traces of thiophenol could be detected very easily.

Light Driven Design of Dynamical Thermosensitive Plasmonic Superstructures: A Bottom-Up Approach Using Silver Supercrystals

When narrowly distributed silver nanoparticles (NPs) are functionalized by dodecanethiol, they acquire the ability to self-organize in organic solvents into 3D supercrystals (SCs). The NP surface chemistry is shown to introduce a light-driven thermomigration effect, thermophoresis. Using a laser beam to heat the NPs and generate steep thermal gradients, the migration effect is triggered dynamically, leading to tailored structures with high density of plasmonic hot spots. This work describes how to manipulate the hot spots and monitor the effect by holography, thus providing a complete characterization of the migration process on a single object basis. Extensive single object tracking strategies are employed to measure the SCs trajectories, evaluate their size, drift velocity magnitude and direction, allowing the identification of the physical chemical origins of the migration. The phenomenon is shown to happen as a result of the combination of thermophoresis (at short length scales) and convection (long-range), and does not require a metallic substrate. This constitutes a fully optical method to dynamically generate plasmonic platforms in situ and on demand, without requiring substrate nanostructuration and with minimal interference on the chemistry of the system. The importance of the proof-of-concept herein described stems from the numerous potential applications, spanning over a variety of fields such as microfluidics and biosensing.