Pascal Berto

Electrochemistry of Single Nanodomains Revealed by Three-Dimensional Holographic Microscopy

Interest in nanoparticles has vigorously increased over the last 20 years as more and more studies show how their use can potentially revolutionize science and technology. Their applications span many different academically and industrially relevant fields such as catalysis, materials science, health, etc. Until the past decade, however, nanoparticle studies mostly relied on ensemble studies, thus leaving aside their chemical heterogeneity at the single particle level. Over the past few years, powerful new tools appeared to probe nanoparticles individually and in situ. This Account describes how we drew inspiration from the emerging fields of nanoelectrochemistry and plasmonics-based high resolution holographic microscopy to develop a coupled approach capable of analyzing in operando (electro)chemical reaction over one single nanoparticle. A brief overview of selected optical strategies to image NPs in situ with emphasis on scattering based methods is presented. In an electrochemical context, it is necessary to track particle behavior both in solution and near a polarized electrode, which is why 3D optical observation is particularly appealing. These approaches are discussed together with strategies to track NPs beyond the diffraction limit, allowing a much finer description of their trajectories. Then, the holographic setup is used to study electrochemically triggered Ag NP oxidation reaction in the presence of different electrolytes. Holography is shown to be a powerful technique to track and analyze the trajectory of individual NPs in situ, which further sheds light on in operando behaviors such as electrogenerated NP transport, aggregation, or adsorption. We then show that spectroscopy and scattering-based optical methods are reliable and sensitive to the point of being used to investigate and quantify NP (electro)chemical reactions in model cases. However, since real chemical reactions usually take place in an inherently complex environment, approaches based exclusively on optical imaging only reach their limitations. The strategy is then taken one step further by merging together electrochemical nanoimpact experiments with 3D optical monitoring. Previous strategies are validated by showing that in simple cases, these two independent ways of probing NP size and reactivity yield the same results. For more complicated reactions (e.g., multistep reactions), one must go beyond either technique by showing that the two approaches are perfectly complementary and that the two signals contain information of different natures, thus providing a much better characterization of the reaction. This point is illustrated by studying Ag NP oxidation (single or agglomerates) in the presence of a precipitating agent, where the actual oxidation is uncoupled from the dissolution of the particle, thus proving the point of our symbiotic approach.

Electrochemical transformation of individual nanoparticles revealed by coupling microscopy and spectroscopy

Although extremely sensitive, electrical measurements are essentially unable to discriminate complex chemical events involving individual nanoparticles. The coupling of electrochemistry to dark field imaging and spectroscopy allows the triggering of the electrodissolution of an ensemble of Ag nanoparticles (by electrochemistry) and the inference of both oxidation and dissolution processes (by spectroscopy) at the level of a single nanoparticle. Besides the inspection of the dissolution process from optical scattering intensity, adding optical spectroscopy reveals chemical changes through drastic spectral changes. The behaviours of single NPs and NP agglomerates are differentiated: in the presence of thiocyanate ions, the transformation of Ag single nanoparticles to AgSCN is investigated in the context of plasmonic coupling with the electrode; tentative interpretations for optically unresolved groups of nanoparticles are proposed.

Opto-electrochemical in situ monitoring of cathodic single-cobalt nanoparticle formation

Single-particle electrochemistry at a nanoelectrode is explored by dark-field optical microscopy. The analysis of the scattered light allows in situ dynamic monitoring of the electrodeposition of single cobalt nanoparticles down to a radius of 65u2005nm. Larger sub-micrometer particles are directly sized optically by super-localization of the edges and the scattered light contains complementary information concerning the particle redox chemistry. This opto-electrochemical approach is used to derive mechanistic insights about electrocatalysis that are not accessible from single-particle electrochemistry.

Programmable single-pixel-based broadband stimulated Raman scattering

We report a simple add-on for broadband stimulated Raman scattering (SRS) microscopes to enable fast and programmable spectroscopy acquisition. It comprises a conventional dispersive spectrometer layout incorporating a fast digital micromirror device (DMD). The approach is validated by acquiring SRS spectra of standard chemicals. We demonstrate a DMDs advantage in broadband SRS by showing higher signal-to-noise ratio using a multiplexed Hadamard spectral basis and compressive sensing detection. Our results apply to a variety of frequency-domain pump-probe spectroscopy.

Wavefront sensing with a thin diffuser

We propose and implement a broadband, compact, and low-cost wavefront sensing scheme by simply placing a thin diffuser in the close vicinity of a camera. The local wavefront gradient is determined from the local translation of the speckle pattern. The translation vector map is computed thanks to a fast diffeomorphic image registration algorithm and integrated to reconstruct the wavefront profile. The simple translation of speckle grains under local wavefront tip/tilt is ensured by the so-called memory effect of the diffuser. Quantitative wavefront measurements are experimentally demonstrated, both for the few first Zernike polynomials and for phase-imaging applications requiring high resolution. We finally provided a theoretical description of the resolution limit that is supported experimentally.

Temperature Rise under Two-Photon Optogenetic Brain Stimulation

In recent decades, optogenetics has been transforming neuroscience research, enabling neuroscientists to drive and read neural circuits. The recent development in illumination approaches combined with two-photon (2P) excitation, either sequential or parallel, has opened the route for brain circuit manipulation with single-cell resolution and millisecond temporal precision. Yet, the high excitation power required for multi-target photostimulation, especially under 2P illumination, raises questions about the induced local heating inside samples. Here, we present and experimentally validate a theoretical model that makes it possible to simulate 3D light propagation and heat diffusion in optically scattering samples atxa0high spatial and temporal resolution under the illumination configurations most commonly used to perform 2P optogenetics: single- and multi-spot holographic illumination and spiral laser scanning. By investigating the effects of photostimulation repetition rate, spot spacing, and illumination dependence of heat diffusion, we found conditions that make it possible to design a multi-target 2P optogenetics experiment with minimal sample heating.

Tutorial: Coherent Raman light matter interaction processes

Coherent Raman scattering processes such as coherent anti-Stokes Raman scattering and stimulated Raman scattering are described in a tutorial way keeping simple physical pictures and simple derivations. The simplicity of the presentation keeps however most of the key features of these coherent and resonant processes and their intimate relation with spontaneous Raman scattering. This tutorial provides a digest of introduction to the fundamental physics at work, and it does not focus on the numerous technological implementations; rather, it provides the concepts and the physical tools to understand the extensive literature in this field. The presentation is made simple enough for under-graduate students, graduate students, and newcomers with various scientific backgrounds.Coherent Raman scattering processes such as coherent anti-Stokes Raman scattering and stimulated Raman scattering are described in a tutorial way keeping simple physical pictures and simple derivations. The simplicity of the presentation keeps however most of the key features of these coherent and resonant processes and their intimate relation with spontaneous Raman scattering. This tutorial provides a digest of introduction to the fundamental physics at work, and it does not focus on the numerous technological implementations; rather, it provides the concepts and the physical tools to understand the extensive literature in this field. The presentation is made simple enough for under-graduate students, graduate students, and newcomers with various scientific backgrounds.

Monitoring Cobalt-Oxide Single Particle Electrochemistry with Subdiffraction Accuracy

By partially overcoming the diffraction limit, superlocalization techniques have extended the applicability of optical techniques down to the nanometer size-range. Herein, cobalt oxide-based nanoparticles are electrochemically grown onto carbon nanoelectrodes and their individual catalytic properties are evaluated through a combined electrochemical-optical approach. Using dark-field white light illumination, edges superlocalization techniques are applied to quantify changes in particle size during electrochemical activation with down to 20 nm precision. It allows the monitoring of (i) the anodic electrodeposition of cobalt hydroxide material and (ii) the large and reversible volume expansion experienced by the cobalt hydroxide particle during its oxidation. Meanwhile, the particle light scattering provides chemical information such as the Co redox state transformation, which complements both the particle size and the recorded electrochemical current and provides in operando mechanistic information on particle electrocatalytic properties.

Electrically Driven Varifocal Silicon Metalens

Optical metasurfaces have shown to be a powerful approach to planar optical elements, enabling an unprecedented control over light phase and amplitude. At that stage, where a wide variety of static functionalities have been accomplished, most efforts are being directed toward achieving reconfigurable optical elements. Here, we present our approach to an electrically controlled varifocal metalens operating in the visible frequency range. It relies on dynamically controlling the refractive index environment of a silicon metalens by means of an electric resistor embedded into a thermo-optical polymer. We demonstrate precise and continuous tuneability of the focal length and achieve focal length variation larger than the Rayleigh length for voltage as small as 12 V. The system time-response is of the order of 100xa0ms, with the potential to be reduced with further integration. Finally, the imaging capability of our varifocal metalens is successfully validated in an optical microscopy setting. Compared to conven...

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.