Superconducting Devices in Silicon
The project focuses on the study of superconducting devices with silicon as a semiconductor. Those include standard silicon transistors with superconducting source and drain contacts and superconducting resonators. The common properties is the superconducting material which is elaborated with the constrain of being compatible with the silicon CMOS technology.
In the actual situation of the project, devices with CoSi2, PtSi and Si:B superconducting contacts have been fabricated using the 300 mm clean room facility at the LETI and in collaboration with our partners at Uppsala university and C2N Paris Saclay. The main issue is now to characterize the electronic transport properties at very low temperature.
Impact of fission products and microstructure on the oxidation mechanisms of (U,Pu)O2 fuels
The widespread use of MOX fuels (based on (U,Pu)O2 mixed oxides) in nuclear reactors is an option currently being studied in France. Such a strategy could help to stabilise the plutonium inventory while conserving natural uranium resources. Such scenario involves the multi-recycling of plutonium, which requires an upgrade of the existing infrastructures to enable the reprocessing of spent MOX fuel at industrial scale. Consequently, the development of innovative processes and related basic research is then imperative.
The oxidation of MOX spent fuel by ad hoc thermal treatment could overcome a major technological barrier identified, i.e. how to separate the fuel from its cladding prior to the dissolution step. However, there is limited data available on the oxidation of (U,Pu)O2 and even less has investigated the impact of fission products and the fuel microstructure properties. The aim of this PhD thesis is to help fill this gap. The selected student will study (U,Pu)O2 samples with a microstructure identical to that of industrial MOX fuels, as well as (U,Pu)O2 doped with inactive fission products, thus simulating irradiated fuels, as shown in a thesis defended in the laboratory. The experimental work will focus on oxidation experiments coupled with in-situ and multi-scale analyses using laboratory technics and synchrotron radiation-based characterizations. These results will lead to the proposal of a phenomenological description linking the kinetics of (U,Pu)O2 oxidation with the fission products chemistry, the O2 partial pressure and the temperature and duration of the thermal treatment.
By the end of this PhD, the graduate student with a background in physical chemistry of materials will have developed expertise in a broad range of experimental techniques. These skills will open up many career opportunities in academic research or industrial R&D, both within and beyond the nuclear sector.
High-throughput experimentation applied to battery materials
High throughput screening, which has been used for many years in the pharmaceutical field, is emerging as an effective method for accelerating materials discovery and as a new tool for elucidating composition-structure-functional property relationships. It is based on the rapid combinatorial synthesis of a large number of samples of different compositions, combined with rapid and automated physico-chemical characterisation using a variety of techniques. It is usefully complemented by appropriate data processing.
Such a methodology, adapted to lithium battery materials, has recently been developed at CEA Tech. It is based, on the one hand, on the combinatorial synthesis of materials synthesised in the form of thin films by magnetron cathode co-sputtering and, on the other hand, on the mapping of the thickness (profilometry), elemental composition (EDS, LIBS), structure (µ-DRX, Raman) and electr(ochim)ical properties of libraries of materials (~100) deposited on a wafer. In the first phase, the main tools were established through the study of Li(Si,P)ON amorphous solid electrolytes for solid state batteries.
The aim of this thesis is to further develop the method so as to enable the study of new classes of battery materials: crystalline electrolytes or glass-ceramics for Li or Na, oxide, sulphides or metal alloys electrode materials. In particular, this will involve taking advantage of our new equipment for mapping physical-chemical properties (X-ray µ-diffraction, Laser-Induced Breakdown Spectroscopy) and establishing a methodology for manufacturing and characterising libraries of thin-film all-solid-state batteries. This tool will be used to establish correlations between process parameters, composition, structure, and electrochemical properties of systems of interest. Part of this work may also involve data processing and programming the characterisation tools.
This work will be carried out in collaboration with researchers from the ICMCB and the CENBG
The solid-state systems, presently considered for quantum computation, are built from localized two-level systems, prime examples are superconducting qubits or semiconducting
quantum dots. Due to the fact that they are localized, they require a fixed amount of hardware per qubit.
Propagating or “flying” qubits have distinct advantages with respect to localised ones: the hardware footprint depends only on the gates and the qubits themselves (photons) can be created on demand making these systems easily scalable. A qubit that would combine the advantages of localised two-level systems and flying qubits would provide a paradigm shift in quantum technology. In the long term, the availability of these objects would unlock the possibility to build a universal quantum computer that combines a small, fixed hardware footprint and an arbitrarily large number of qubits with long-range interactions. A promising approach in this direction is to use electrons rather than
photons to realise such flying qubits. The advantage of electronic excitations is the Coulomb interaction, which allows the implementation of a two-qubit gate.
The aim of the present Phd will be the development of the first quantum-nanoelectronic platform for the creation, manipulation and detection of flying electrons on time scales down to the picosecond and to exploit them for quantum technologies.
Development of high-halogen argyrodites for all-solid all-sulfide battery
All-solid-state batteries have been enjoying renewed interest in recent years, as this technology offers the prospect of higher energy densities due to the use of lithium as a negative electrode, as well as increased battery safety compared with Li-ion technology. The use of sulfides as positive electrode materials coupled with argyrodite as solid electrolyte are interesting systems to develop. The argyrodites achieve ionic conductivities close to those of liquid electrolytes. Moreover, the electrochemical stability window of sulfides is close to that of argyrodite, making all-sulfide technology a promising one for the development of all-solid batteries.
In order to improve the conduction properties of argyrodites, recent studies have shown that ionic conductivity is highly dependent on their local structure. Solid-state NMR thus appears to be a promising technique for probing the local environments of the nuclei mentioned, and in particular for quantifying the variety of different local environments favoring an increase in ionic conductivity. Some compositions enriched in halides appear to promote ionic conduction, and the synthesis of corresponding materials and their structure will be studied.
The thesis will focus on two main areas: the study of all-sulfide batteries and the fine characterization of argyrodite with controlled local structures. Halogen-rich argyrodites will be developed and studied to determine the influence of different local environments on conduction properties.
Novel oxynitride based artificial multiferroic oxynitride thin films
N-doped oxides and/or oxinitrides constitute a booming class of compounds with a broad spectrum of useable properties and in particular for novel technologies of carbon-free energy production, surface coatings for improving the mechanical strength of steels or protection against corrosion and multifunctional sensors. In this research field the search for new materials is particularly desirable because of unsatisfactory properties of current materials. The insertion of nitrogen in the crystal lattice of an oxide semiconductor allows in principle to modulate its electronic structure and transport properties enabling new functionalities. A detailed understanding of these aspects requires materials that are as perfect as possible. The production of corresponding single crystalline thin films is however highly challenging. In this thesis work, single crystalline oxynitride heterostructures will be grown by atomic plasma-assisted molecular beam epitaxy. The heterostructure will combine two N doped layers: a N doped BaTiO3 will provide ferroelectricity and a heavily doped ferrimagnetic ferrite whose magnetic properties can be modulated using N doping to obtain new artificial multiferroic materials better suited to applications. The resulting structures will be investigated with respect to their ferroelectric and magnetic characteristics as well as their magnetoelectric coupling, as a function of the N doping. These observations will be correlated with a detailed understanding of crystalline and electronic structures. The later will be modelled thanks to electronic structure calculation to reach a comprehensive description of this new class of materials.
The student will acquire skills in ultra-high vacuum techniques, molecular beam epitaxy, ferroelectric and magnetic characterizations as well as in state-of-the-art synchrotron radiation techniques. X-ray magnetic dichroism is particularly suited to this study and the project will give rise to close collaboration and/or co-supervision with the DEIMOS beamline of SOLEIL synchrotron.
Synthesis, characterization and modeling of (Mn,Co)3O4 thin films applied to corrosion layers and spintronics
Spinel-type transition metal oxides (AB2O4) appear spontaneously during the generalized corrosion of steels or alloys in aqueous or gaseous environments at high temperatures. This spinel phase forms a continuous corrosion layer and thus regulates corrosion processes by controlling conductivity and material transport between the material and the oxidizing medium. They are also applied voluntarily as protective coatings against degradation phenomena. In particular, the Mn-Co-O spinel system is very promising as protective conductive layers on ferritic stainless steel used to fabricate interconnects in solid oxide fuel cells for green hydrogen production. The composition of the spinel phase determines the protective performance of the coatings. This feature is particularly delicate for materials used in high-temperature electrolyzers, as electronic transport must be optimal (high electrolysis), but must not be accompanied by material transport (low cation diffusion).
In contrast, electronic transport properties of spinel-type transition metal oxides are generally not well understood. Measurements are made on complex corrosion layers (or coatings) of variable composition, low crystallinity, complex microstructure and low thickness. Furthermore, spinel oxides exhibit magnetic properties and composition-dependent cationic disorder that are usually ignored, even though they have a strong impact on electronic transport. The properties highlighted here are the ones that also hold significant importance within the field of spintronics. Thus, tuning the chemical composition of these spinel-structured oxides (normal, inverse or mixed) offers a wide range of magnetic (ferrimagnetic, antiferromagnetic) and electronic (semimetallic, semiconductor, insulator) properties. In particular, CoMn2O4 is expected to exhibit a complex magnetic configuration [1], mainly related to the arrangement of Co2+ and Mn3+ cations in interstitial sites, which needs to be analyzed in detail. Unlike corrosion layers, these physical studies require the synthesis of thin films of well-controlled composition and high crystallinity.
The aim of the thesis is to build up knowledge of physicochemical and structural properties of (Mn,Co)3O4 in order to contribute to the elaboration of Mn-Co-O phase diagrams and electronic transport models based on the relationship between order/disorder, magnetic properties and resistivity of (Mn,Co)3O4. Eventually, the whole (Fe,Cr,Mn,Co)3O4 system will be also considered. The study will be carried out on thin films of perfectly controlled composition and high crystallinity, and will be enhanced by numerical simulations. The experimental and theoretical work will be based on the results of previous studies on (Ni,Fe,Cr)3O4 epitaxial thin films [2,3].
The thesis will be divided as follows:
- Growth of thin films and multilayers by MBE (Molecular Beam Epitaxy) (J.-B. Moussy)
- Spectroscopic characterization using XPS (X-ray photoemission spectroscopy) (F. Miserque)
- Fine structure characterization by DRX and X-ray absorption (XMCD) (P. Vasconcelos)
- Modeling of core-level spectra (XPS, XAS and XMCD) and atomistic modeling (A. Chartier)
- Magnetic characterization by SQUID/VSM magnetometry and electric transport characterization (J.-B. Moussy)
[1] Systematic analysis of structural and magnetic properties of spinel CoB2O4 (B= Cr, Mn and Fe) compounds from their electronic structures, Debashish Das, Rajkumar Biswas and Subhradip Ghosh, Journal of Physics: Condensed Matter 28 (2016) 446001.
[2] Stoichiometry driven tuning of physical properties in epitaxial Fe3-xCrxO4 thin films, Pâmella Vasconcelos Borges Pinho, Alain Chartier, Denis Menut, Antoine Barbier, Myrtille O.J.Y. Hunault, Philippe Ohresser, Cécile Marcelot, Bénédicte Warot-Fonrose, Frédéric Miserque, Jean-Baptiste Moussy, Applied Surface Science 615 (2023) 156354.
[3] Elaboration, caractérisation et modélisation de films minces et multicouches à base d’oxydes (Ni,Fe,Cr)3O4 appliquées à la corrosion et à la spintronique, A. Simonnot, thèse en cours.
Investigation and use of uranium glasses for optical neutron detection
The Dosimetry, Sensors and Instrumentation Laboratory of the CEA/IRESNE Cadarache develops, manufactures and operates neutron flux detectors used in the vicinity of and inside nuclear reactor cores. In addition to conventional detectors (fission chambers, collectrons, etc.), the laboratory is working on innovative measurement methods such as optical detectors, semiconductors, fiber scintillators, etc. As part of this PhD thesis, the laboratory wants to explore the potential of Uranium-doped glasses. These glasses are known to show bright fluorescence under various types of radiations. The main idea of this thesis is to try to exploit this fluorescence to detect the fission reactions induced when the glass is exposed to a neutron flux. This could enable the development of a new generation of optical neutron detectors halfway between a fission chamber and a scintillator.
The thesis will focus on two main topics:
- firstly, a detailed understanding of fluorescence mechanisms, and the synthesis of uranium glass with properties optimized for our needs (sensitivity, emission spectrum, isotopic vector, etc.). Synthesis will be carried out in partner laboratories;
- secondly, the development of a dedicated instrumentation, probably in the form of optical fibers, to test these prototypes in a reactor.
HPC Parallel Integrodifferential Solver for Dislocation Dynamics
Context : Understanding the behavior of metals at high deformation rate [4] (between 104 and 108 s-1) is a huge scientific and technologic challenge. This irreversible (plastic) deformation is caused by linear defects in the crystal lattice : these are called dislocations, which interact via a long-range elastic field and contacts.
Nowadays, the behavior of metals at high deformation rate can only be studied experimentally by laser shocks. Thus, simulation is of paramount importance. Two approaches can be used : molecular dynamics and elastodynamics simulations. This thesis follows the second approache, based on our recent works [1, 2], thanks to which the first complete numerical simulations of the Peierls-Nabarro Equation (PND) [5] was performed. The latter equation describes phenomena at the scale of the dislocation.
PND is a nonlinear integrodifferential equation, with two main difficulties : the non-locality in time and space of the involved operators. We simulated it thanks to an efficient numerical strategy [1] based on [6]. Nevertheless, the current implementation is limited to one CPU –thus forbidding thorough investigations on large-scale systems and on long-term behaviors.
Thesis subject : There are two main objectives :
- Numerics. Based on the algorithmic method of [1], implement a HPC solver (High Performance Computing) for the PND equation, parallel in time and space, with distributed memory.
- Physics. Using the solver developped, investigate crucial points regarding the phenomenology of dislocations in dynamic regime. For exploiting the numerical results, advanced data-processing techniques will be employed, potentially enhanced by resorting to AI techniques.
Depending on the time remaining, the solver might be employed for investigating dynamic fractures [3].
Candidate profile : The proposed subject is multidisciplinary, between scientific computing, mechanics, and data-processing. The candidate shall have a solid background in scientific computing applied to Partial Differential Equations. Mastering C++ with OpenMP and MPI is recommended. Moreover, interest and knowledge in physics –especially continuum mechanics- will be a plus.
The PhD will take place at the CEA/DES/IRESNE/DEC in Cadarache (France), with regular journeys to Paris, for collaboration with CEA/DAM and CEA/DRF.
[1] Pellegrini, Josien, Shock-driven motion and self-organization of dislocations in the dynamical Peierls model, submitted.
[2] Josien, Etude mathématique et numérique de quelques modèles multi-échelles issus de la mécanique des matériaux. Thèse. (2018).
[3] Geubelle, Rice. J. of the Mech. and Phys. of Sol., 43(11), 1791-1824. (1995).
[4] Remington et coll., Metall. Mat. Trans. A 35, 2587 (2004).
[5] Pellegrini, Phys. Rev. B, 81, 2, 024101, (2010).
[6] Lubich & Schädle. SIAM J. on Sci. Comp. 24(1), 161-182. (2002).
Thermoelectric energy conversion control via coordination chemistry of transition metal redox ions in ionic liquids
Thermoelectricity, a materials’ capability to convert heat in to electric energy has been known to exist in liquids for many decades. Unlike in solids, this conversion process liquids take several forms including the thermogalvanic reactions between the redox ions and the electrodes, the thermodiffusion of charged species and the temperature dependent formation of electrical double layer at the electrodes. The observed values of Seebeck coefficient (Se = - DV/DT, the ratio between the induced voltage (DV) and the applied temperature difference (DT)) are generally above 1 mV/K, an order of magnitude higher than those found in the solid (semiconductor) counterpart. The first working example of a liquid-based thermoelectric (TE) generator was reported in 1986 using Ferro/ferricyanide redox salts in water.
However, due to the low electrical conductivity of liquids, its conversion efficiency was very low, preventing their use in low-temperature waste-heat recovery applications. The outlook of liquid TE generators brightened in the last decade with the development of ionic liquids (ILs). ILs are molten salts that are liquid below 100 °C. Compared to classical liquids, they exhibit many favorable features such as high boiling points, low vapour pressure, high ionic conductivity and low thermal conductivity accompanied by higher Se values. More recently, an experimental study by IJCLab and SPEC revealed that the complexation of transition metal redox couples in ionic liquids can lead to enhancing their Se coefficient by more than a three-fold from -1.6 to -5.7 mV/K, one of the highest values reported in IL-based thermoelectric cells. A clear understanding and the precise control of the speciation of metal ions therefore is a gateway to the rational design of future thermoelectrochemical technology.
Based on these recent findings, we proposes to further study the coordination chemistry of transition metal redox ions in ILs and mixtures. A long-term goal associated to the present project is to demonstrate the application potential of liquid thermoelectrochemical cells based on affordable, abundant and environmentally safe materials for thermal energy harvesting as an energy efficiency tool.