Exploration of the energy deposition dynamic on short time scale with laser-driven electron accelerator in the context of the Flash effect in radiotherapy
The objective of the thesis project is to analyze the physicochemical processes resulting from the extreme dose rates that can now be obtained in water with the ultra-short (fs) pulses of relativistic electrons produced by laser-plasma acceleration. Indeed, first measurements show that these processes are probably not equivalent to those obtained with longer pulses (µs) in the FLASH effect used in radiotherapy. To achieve this, we propose to analyze the dynamics of formation/recombination of the hydrated electron, an emblematic species of water radiolysis, to qualify and quantify the dose rate effect over increasingly shorter times. This will be done in three stages in support of the necessary and now accessible technological progress, to have a dose per pulse sufficient to directly detect the hydrated electron. First, with the existing UHI100 facility, using the scavenging of the hydrated electron by producing a stable species; then producing a less stable but detectable species in real time and increasing the repetition rate of the electron source. Finally, by using an innovative concept named a “hybrid target”, based on a plasma mirror as an electron injector coupled to a laser-plasma accelerator, delivering larger doses with a narrower energy spectrum, we will be able to develop pump-probe detection allowing access to the shortest times, and to the formation in clusters of ionization, of the hydrated electron and measuring its initial yield.
All solid-state lithium batteries based on Pyrochlore solid electrolyte
Due to the increasing energy demand, developing efficient storage systems, both stationary and portable, is crucial. Among these, lithium-ion batteries stand out as the most advanced, capable of being manufactured using liquid or solid electrolytes. All-solid-state batteries have a bright future thanks to their non-flammable electrolytes and their ability to use metallic lithium to increase energy density. Although research on these batteries is dynamic, their commercialization is not yet a reality. Indeed, two significant obstacles to their development remain: the low intrinsic ionic conductivity of solids and the difficulty of obtaining good solid/solid interfaces within the composite electrodes and the complete system.
This thesis explores the potential of pyrochlore oxyfluoride as a new class of superionic material for all-solid-state batteries, which are more stable in air and have higher ionic conductivity than current solid oxide electrolytes. The electrochemical properties of all-solid-state batteries will be carefully examined using a combination of in situ and operando techniques, such as XRD, Raman, ion beam/synchrotron analysis, solid-state NMR, X-ray tomography, etc.
Keywords :
Solid electrolyte, All-solid battery, Nuclear magnetic resonance, Electrochemistry, Pyrochlore Oxyfluoride, in situ/operando, Spectroscopy, Synchrotron
From angstroms to microns: a nuclear fuel microstructure evolution model whose parameters are calculated at the atomic scale
Controlling the behavior of fission gases in nuclear fuel (uranium oxide) is an important industrial issue, as fission gas release or precipitation limit the use of fuels at extended burn-ups. The gas behavior is strongly influenced by the material’s microstructure evolution due to the aggregation of irradiation-induced defects (gas bubbles, dislocation loops and lines). Cluster dynamics (CD) (a kind of rate theory model) is relevant for modelling the nucleation/growth of the defect clusters, there gas content and the gas release. The current model has been parameterized following a multiscale approach, based on atomistic calculations (ab initio or empirical potentials). This model has been successfully applied to annealing experiments of UO2 samples implanted with rare gas atoms and has emphasized the impact of the irradiation damage on gas release. The aim of this PhD thesis is now to improve the model, particularly the damage parameterization, and to extend its validation domain through in depth comparison of simulation with a large set of recently obtained experimental results, such as gas release measurement by annealing of sample implanted in ion beam accelerator, bubble and loop observation by transmission electrons microscopy, and positron annihilation spectroscopy. This global analysis will finally yield an improved parameterization of the CD model.
The research subject combines a “theoretical” dimension (improving the model) with an “experimental” one (interpreting existing experiments or designing some new ones). The variety of techniques will introduce the candidate into the experimental world and thus broaden his scientific skills. The candidate will also have to manage collaborations for the experiments analysis, for the model development and for the specification of additional atomistic calculations. He will be at the interface of atomistic techniques, large-scale simulation and various experimental techniques. Therefore, he will develop a broad view of irradiation effects in materials and of multi-scale modelling in solids in general.
This project is an opportunity to contribute to the overall development of numerical physics applied to multi-scale modeling of materials, occupying a pivotal position and adopting a global viewpoint. This will allow experiencing oneself the way computed fundamental microscopic data finally helps solving complex practical issues.
Further readings:
Skorek et al. (2012). Modelling Fission Gas Bubble Distribution in UO2. Defect and Diffusion Forum, 323–325, 209.
Bertolus et al. (2015). Linking atomic and mesoscopic scales for the modelling of the transport properties of uranium dioxide under irradiation. Journal of Nuclear Materials, 462, 475–495.
Synthesis and optical properties of quantum dots
Graphene as a constituent of graphite was close to us for almost 500 years. However, it is only in 2005 that A. Geim and K. Novoselov (Nobel Prize in 2010) reported for the first time the obtaining of a nanostructure composed by a single layer of carbon atom. The exceptional electronic properties of graphene make it a very promising material for applications in electronic and renewable energies.
For many applications, one should be able to modify and control precisely the electronic properties of graphene. In this context, we propose to synthesize chemically graphene nanoparticles and study their absorption and photoluminescence properties. We will focus on families of elongated nanoparticles, with the aim of studying how size can enable us to observe and control multiexcitonic processes in these materials. This project will be developed in collaboration with Physicists so the candidate will work in a multidisciplinary environment.
Plasma Mirrors: towards extreme intensity light sources and high-quality compact electron
Research objectives:
expand the capabilities of the WarpX Partice-In-Cell code for lower cost-to-convergence using mesh refinement.
Devise a high-charge high quality injector for laser-plasma accelerators.
Determine feasibility of the proposed scheme on a 100-TW-class laser system.
The researcher will benefit from a large variety of training available at CEA on HPC and computer programming as well as training at our industrial partners (ARM, Eviden) and Université Paris Saclay. The activities will be carried out in the framework of the Marie Sklodowska Curie Action Doctoral Network EPACE (European compact accelerators, their applications, and entrepreneurship)
TeraHertz Landau emission in HgTe/CdTe topological quantum wells
Quantum well heterostructures of HgTe/CdTe are known as topological insulators. They inherit very peculiar electronic properties. One of them is the ability of producing TeraHertz emission from inter-Landau energy level optical transitions. These transitions can be envisioned to lead to coherent optical sources in spectral range where they are basically absent. The PhD Thesis consists in elaborating and characterizing HgTe/CdTe multiple quantum well structures by epitaxy, process them in order to add functionality through optical cavities metallic report or deposition and electrical gating, and finally carry out full range optical spectroscopy of Landau emission in magnetic fields. The PhD will be carried out in a collaborative environment between CEA-Leti and Institut Néel (CNRS) in Grenoble, France, two leading laboratories in the expertise in material growth and Physics of HgTe/CdTe topological insulator systems. The results will help to understand the potential of application of this peculiar material system in TeraHertz laser sources and hopefully lead to the first demonstration of spontaneous emission in the TeraHerz range.
Electrocatalyzed Reductive Couplings of Olefins and Carbonyls for the synthesis of sustainable molecules.
The LCMCE aims to develop a sustainable method for the reductive functionalization of carbonyl derivatives with olefins via electrochemistry. Traditional redox processes in organic synthesis often rely on thermochemical methods using stoichiometric oxidants or reductants and produce waste products. The electrification of these processes will improve their atom- and energy economy. The novelty of this project lies in the generation of "metal-hydride" catalytic species by cathodic reduction of organometallic complexes in the presence of protons rather than by adding chemical reductants, as described in the literature. Inserting an alkene function into the metal-hydride bond will lead to the formation of reactive intermediates for coupling with electrophilic carbonyls. The substrates for this project have been selected to provide rapid proof of concept and allow the study of more ambitious reactivities, including carboxylation reactions in which CO2 is the electrophile. Particular attention will be paid to the design of homogeneous catalysts and their synergy with electrochemical conditions to lead to active and selective species. The project will also focus on deciphering the mechanisms involved in these reactions.
Theoretical design of quasi-atomic systems in the band gap of semiconductors/insulators for quantum application
The rise of room-temperature applications like single photon emission of the negatively charged nitrogen-vacancy NV center in diamond has renewed the interest in the search for materials having a quasi-atomic system QAS analogous to that of NV, mainly characterized by the presence of well localized in-gap defect levels generate occupied by electrons and leading to high spin states. In this Ph.D. work, theoretical methods will be used to design new QASs analogous to the NV center as well as, in selected QAS, to predict charge states and explore the effect of the proximity of the surface on the thermodynamic stability and on the spin state structure. The objectives are to design new QASs; To predict charge states of selected QASs in the bulk of the host material; To study changes in the charge state brought by the proximity of the surface; To extend the Hubbard model used to compute the excited states and to account for the electron-lattice interaction in the calculation of the excited states; To study the effect of the presence of deep level states in the band gap on the transport of electrons and phonons. The methodology developed at LSI to design new QASs with high spin states will be exploited and new systems analogous to the NV center will be looked for. Density functional theory (DFT) and a Hubbard model developed at LSI will be the main tools of this PhD.
Porphyrin-based nanostructures
The aim of this project is the synthesis of new molecular structures based on porphyrins for the formation of 0D, 1D and 2D nanostructures. Porphyrins are an important class of molecules that are essential to life through oxygen transport or photosynthesis. Beyond, their importance in Nature, porphyrin derivatives exhibit outstanding optical, electronic, chemical and electrochemical properties that make them promising candidates for applications in catalysis, electrocatalysis, optoelectronics and medicine.
In this project, the porphyrins will be studied in collaboration with several groups of Physicists in order to fabricate 1D or 2D covalent networks on surface via the "bottom-up" approach and to study their electronic and optical properties.
Interfaces in super-concentrated aqueous electrolytes: machine learned simulations at the exascale era
Improving the performance of liquid electrolytes is one of today's major challenges in the field of batteries, with the aim of improving efficiency, safety and economy. Recent advances include superconcentrated media such as WIS (“Water-In-Salts”) solutions. Their properties depend crucially on the chemistry and physics of the interfaces between water and ions (Li+ for lithium-ion batteries, but also Na+, K+, Zn2+), both at a distance and close to the electrodes.
Atomic-scale modeling of these superconcentrated liquid electrolytes requires the study of nanoscopic structures and phenomena taking place over long timescales. One relevant solution is to build potentials by machine learning, based on ab initio molecular dynamics (AIMD) trajectories. This method combines an accurate description of the interactions between ions and water molecules, including the breaking and forming of chemical bonds, with fast calculation speed. In particular, the DeePMD kit has recently been successfully ported to GPU architectures, paving the way for calculations on exascale supercomputers (whose power exceeds 10^18 floating-point operations per second).
This theoretical study will be supported by an experimental counterpart, thanks to direct collaboration with a team in the unit specializing in electrochemistry.