Control of two-dimensional magnetism by structural and chemical engineering of van der Waals interfaces
2D materials exhibit tunable interlayer interactions due to weak van der Waals bonding, which influences magnetic ordering in 2D magnets. The stacking sequence and internal chemistry impact ferromagnetic (FM) or antiferromagnetic (AFM) ordering, as seen in materials like CrBr3, CrI3, and Fe5GeTe2, where doping with Co raises the Curie temperature and alters magnetic phases. Chemical disorder also affects magnetic properties, with Mn/Sb substitution promoting FM ordering in Mn(Bi,Sb)2Te4. However, understanding how the atomic structure affects macroscopic magnetic properties remains limited due to the coexistence of metastable configurations. Precise control over stacking and chemical order is needed to harness 2D materials' magnetic and quantum properties. Transmission electron microscopy (TEM), especially aberration-corrected STEM, is today one of the most powerful techniques, enabling atomic-scale imaging and spectroscopy, for studying structural and chemical properties of 2D materials. This PhD project aims to study the relationship between atomic structure, chemistry, and magnetic properties in epitaxial 2D layers like (Fe,Co)5GeTe2, combining growth via molecular beam epitaxy (MBE) with STEM-based structural and chemical analysis.
Design and implementation of cryogenic electronics for signal acquisition at cryogenic temperatures
The aim of our proposed thesis is to demonstrate that it is possible to integrate at cryogenic temperatures the entire instrumentation chain for reading and controlling quantum components at cryogenic temperatures
qubits. In other words, we are seeking to place in-situ, in the cryostat and as close as possible to the quantum components
(qubits), all the systems that are currently located outside. In addition, to achieve a major breakthrough
we are aiming for a fully programmable microwave chain (> 2 GHz). This is the subject of an ongoing thesis
financed by the Agence Innovation Défense (AID) and the Commissariat à l'Énergie Atomique (CEA) and a RAPID-type project application.
RAPID type project.
As part of this thesis, we will start at a few hundred MHz. Several main problems
are identified and need to be solved, including
- design and integration of chiplets in System-in-Packages (SiPs) compatible with cryogenic temperatures ;
- interfacing and integrating the Analog to Digital Converter (ADC), Digital to Analog
Converter (DAC) and processing components;
- manage high data rates (several tens of Gbit/s per qubit);
- maximum roundtrip latency of 200 ns;
- energy management (a few tens of mW budget per qubit);
- choice of cryogenic stages adapted to the different processing stages;
- choice of independent technologies
Innovative syntheses of perovzalates and rationalization of the formation mechanism by synchrotron methods
“Perovzalates” are a new family of hybrid perovskites based on oxalate, with around ten examples listed since 2019 (AILi3MII(C2O4)3, with A = K+, Rb+, Cs+, NH4+; M = Fe2+, Co2+, Ni2+). Just like conventional perovskites, they are potentially interesting for countless applications (catalysis, optics, solar etc.), presenting additional advantages linked to the oxalate anion, which allows the incorporation of larger cations than in other hybrid pervovskites, while preserving a crystal structure similar to oxide perovskites.
However, this class of new materials is still barely explored, and the syntheses far from being mastered: the few reports to date systematically produce mixtures of phases, and relate to single crystals taken from heterogeneous solutions. In this context, the major problem is to synthesize an extended class of pure perovzalates.
This thesis addresses this challenge by exploiting a property discovered in the laboratory: the crystallization of metal oxalates by co-precipitation in water passes through transient “mineral emulsions”, that is to say nano-droplets rich in reagents which separate from water. The originality of this thesis is to exploit the nanostructuring provided by these mineral emulsions, and to test in particular using nanotomographic techniques accessible in synchrotron if they make it possible to confine the cations until crystallization.
Optimization of the catalytic layer for CO2 electroreduction integrated into a PEM electrolyzer
This thesis focuses on optimizing the catalytic layer for CO2 electroreduction in an acidic medium, integrated into a proton-exchange membrane (PEM) electrolyzer. The aim is to upgrade CO2 by converting it into valuable chemicals, such as carbon monoxide. The acidic environment inherent to PEM electrolyzers helps limit carbonate formation, improving CO2 conversion efficiency. However, CO2 reduction in acidic media competes with the hydrogen evolution reaction, which reduces the selectivity of electroreduction products. This work seeks to develop noble-metal-free catalysts inspired by those used for oxygen reduction in fuel cells, improve the properties of carbon supports, and optimize the design of the catalytic layer, in particular thickness, porosity and hydrophobicity, to maximize CO2 conversion into target molecules. Finally, the active layer will be integrated into a 16 cm² PEM electrolyzer to assess overall performance and gain insights into the mechanisms involved through electrochemical characterization.
Disequilibrium chemistry of exoplanets’ high-metallicity atmospheres in JWST times
In little more than two years of scientific operations, JWST has revolutionized our understanding of exoplanets and their atmospheres. The ARIEL space mission, to be launched in 2029, will soon contribute to this revolution. A main finding that has been enabled by the exquisite quality of the JWST data is that exoplanet atmospheres are in chemical disequilibrium. A full treatment of disequilibrium is complex, especially when the atmospheres are metal-rich, i.e. when they contain in significant abundances elements other than hydrogen and helium. In a first step, our project will numerically investigate the extent of chemical disequilibrium in the atmospheres of JWST targets suspected to have metal-rich atmospheres. We will use towards that end an in-house photochemical model. In a second step, our project will explore the effect of super-thermal chemistry as a driver of chemical disequilibrium. This will offer previously-unexplored insight into the chemistry of metal-rich atmospheres, with the potential to shed new light into the chemical and evolutionary paths of low-mass exoplanets.
Functionalized aluminosilicate nanotubes for photocatalysis
Rising energy demand and the need to reduce the use of fossil fuels to limit global warming have created an urgent need for clean energy collection technologies. One interesting solution is to use solar energy to produce fuels. Low-cost materials such as semiconductors have been the focus of numerous studies for photocatalytic reactions. Among them, 1D nanostructures are promising because of their interesting properties (high and accessible specific surface areas, confined environments, long-distance electron transport and facilitated charge separation). Imogolite, a natural hollow nanotubes clay, belongs to this category. Its particularity does not lies in its chemical composition (Al, O and Si) but in its intrinsic curvature, which induces a permanent polarization of the wall, effectively separating photo-induced charges. Several modifications of these materials are possible (coupling with metal nanoparticles, functionalization of the internal cavity), enabling their properties to be modulated.We have demonstrated that this clay is a nanoreactor for photocatalytic reactions (H2 production and CO2 reduction) under UV illumination. In order to obtain a useful photocatalyst, it is necessary to extend photon collection into the visible range. One strategy considered is to encapsulate and covalently graft dyes acting as antennae in the cavity. The aim of this thesis is to synthesize imogolites with different internal functionalizations, to study the encapsulation and grafting of dyes into the cavity of these functionalized imogolites, and finally to study the photocatalytic properties.
Nuclear reactions induced by light anti-ions - contribution of the INCL model
The interaction of an antiparticle with an atomic nucleus is a type of reaction that needs to be simulated in order to answer fundamental questions. Examples include the PANDA (FAIR) collaboration with antiproton beams of the order of GeV, which plans to study nucleon-hyperon interactions, as well as the neutron skin by producing hyperons and antihyperons. This same neutron skin is also studied with antiprotons at rest in the PUMA experiment (AD - Cern). At the same site, we are collaborating with the ASACUSA experiment to study the production of charged particles. To respond to those studies, our INCL nuclear reaction code has been extended to antiprotons (thesis by D. Zharenov, defended at the end of 2023). Beyond the antiproton there are antideuterons and antiHe-3. These antiparticles are of more recent interest, notably with the GAPS (General AntiParticle Spectrometer) experiment, which aims to measure the fluxes of these particles in cosmic rays. The idea is to highlight dark matter, of which these particles are thought to be decay products, and whose measured quantity should emerge more easily from the astrophysical background noise than in the case of antiprotons. The proposed subject is therefore the implementation of light anti-nuclei in INCL with comparisons to experimental data.
Investigating the nature of Gamma-Ray Bursts with SVOM
Gamma-Ray Bursts are short lived (0.1-100 s) gamma-ray transient sources that appear randomly on the entire sky. Even if they have been discovered at the end of the 1960s, their nature remained mysterious until the end of the 1990s. It is only thanks to the observations of the BeppoSAX satellite at the end of the last century and especially thanks to the observations of the Swift satellite starting from 2004, that the mysterious nature of GRBs started to be elucidated.
These emissions are related to the final stages of very massive stars (30-50 times the mass of the Sun) for the long GRBs (<2 s) or to the merger of two compact objects (typically two neutron stars) for the short GRBs (< 2s). In either case there is the creation of a powerful relativistic jet, which is at the origin of the electromagnetic emission that is measure in gamma-rays and in other energy bands. If this jet points towards the Earth, GRBs can be detected up to very long distances (z~9.1) corresponding to a young age of the Universe (~500 Myr).
Svom is a sino-french space mission dedicated to GRBs, which has been successfully launched on June 22nd 2024, and in which CEA/Irfu/DAp is deeply involved. The PHD subject is aimed at exploiting the multi-wavelength data of SVOM and its partner telescopes in order to investigate the nature of GRBs, and in particular to make use of X-ray data from the MXT telescope in order to try to constrain the nature of the compact object which is at the origin of the relativistic jets.
Quantum computing with nuclear spins
Nuclear spins in solids are amongst the quantum systems with the longest coherence times, up to minutes or even hours, and as such are attractive qubit candidates; however, controlling and reading out individual nuclear spins is highly challenging. In our laboratory, we have developed a new way to do so. The nuclear spin qubits are interfaced by an electron spin ancilla to which they are coupled by the hyperfine interaction. The electron spin is then measured by microwave photon counting at millikelvin temperatures [1,2]. Nuclear-spin single-shot readout is performed via the electron spin [3], and coherent control is achieved through the use of microwave Raman transitions [4]. The electron spins are Er3+ ions in a CaWO4 crystal, and the nuclear spins are 183W atoms in the matrix, which have a spin 1/2.
[1] E. Albertinale et al., Nature 600, 434 (2021)
[2] Z. Wang et al., Nature 619, 276 (2023)
[3] J. Travesedo et al., arxiv (2024)
[4] J. O'Sullivan et al., arxiv (2024)
Unraveling the mechanism of enzymatic carbon fixation
The Synchrotron Group at the Institut de Biologie Structurale in Grenoble is currently developing an innovative method called TR-FOX (Time-Resolved Functional Oscillation Crystallography). This technique aims to elucidate, firstly, the global dynamics of biological macromolecules in action and, secondly, their fine catalytic mechanism. It relies on the use of an injector capable of depositing onto the crystal, during the course of the X-ray diffraction data collection, a nanoliter droplet containing the substrate and cofactor of the studied reaction. This triggers the enzymatic reaction within the crystal. The approach can be combined with UV-Visible absorption spectroscopy to characterize the reaction kinetics more precisely. The goal is to obtain a series of structures during the catalytic cycle in order to make a molecular movie depicting the functioning of the enzyme. This thesis has two objectives: (i) improve and validate the TR-FOX method and, (ii) study the catalytic mechanism of two enzymes involved in carbon fixation either by capture or conversion of CO2.