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.

Use of Spray flash evaporation to Improve high explosives with crystal structuration

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.

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.

Thermally conductive yet electrically insulating polymer nanocomposite based on core-shell (nano)fillers oriented by magnetic field

Advances in power electronics, electric motors and batteries, for example, are leading to a significant increase in heat production during operation. This increase in power density combined with reduced heat exchange surfaces amplifies the challenges associated with heat dissipation. The absence of adequate dissipation leads to overheating of electronic components, impacting on their performance, durability and reliability. It is therefore essential to develop a new generation of heat dissipating materials incorporating a structure dedicated to this structure.

The objective and innovation of the PhD student's work will lie in the use of highly thermally conductive (nano)fillers that can be oriented in an epoxy resin in a magnetic field. The first area of work will therefore be to electrically isolate the thermally conductive (nano)charges with a high form factor (1D and 2D). The electrical insulation of these charges of interest will be achieved by a sol-gel process. The synthesis will be controlled and optimised with a view to correlating the homogeneity and thickness of the coating with the dielectric and thermal performance of the (nano)composite. The second part will focus on the grafting of magnetic nanoparticles (NPM) onto thermally conductive (nano)fillers. Commercial NPMs will be evaluated as well as grades synthesised in the laboratory. The (nano)composites must have a rheology compatible with the resin infusion process.

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)

Modeling and experimental validation of a catalytic reactor and optimization of the process for the production of e-Biofuels

During the past 20 years, « Biomass-to-liquid » processes have considerably grown. They aim at producing a large range of fuels (gasoline, kerozene, diesel, marine diesel oil) by coupling a biomass gazéification into syngaz unit (CO+CO2+H2 mixture) and a Fischer-Tropsch (FT) synthesis unit. Many demonstration pilots have been operated within Europe. Nevertheless, the low H/C ratio of bio-based syngaz from gasification requires the recycling of a huge quantity of CO2 at the inlet of gaseification process, which implies complex separation and has a negative impact on the overall valorization of biobased carbon. Moreover, the possibility to realize, in the same reactor, the Reverse Water Gas Shift (RWGS) and Fischer-Tropsch (FT) reaction in the same reactor with promoted iron supported catalysts has been proved (Riedel et al. 1999) and validated in the frame of a CEA project (Panzone, 2019).
Therefore, this concept coupled with the production of hydrogen from renewable electricity opens new opportunities to better valorize the carbon content of biomass.
The PhD is based on the coupled RWGS+FT synthesis in the same catalytic reactor. On the one hand a kinetic model will be developed and implemented in a multi-scale reactor model together with hydrodynamic and thermal phenomena. The model will be validated against experimental data and innovative design will be proposed and simulated. On the other hand, the overall PBtL process will be optimized in order to assess the potential of such a process.

Magnetic DIsks as Transducer of Angular Momentum

The proposed topic is a collaborative project to exploit suspended magnetic disks as novel microwave transducers of orbital angular momentum. Our goal is to develop ultra-high fidelity opto-mechanical modulators operating at GHz frequencies by integrating magnetic materials into optical components. This innovative concept arises from recent progress in the study of angular momentum conservation laws by magnon modes in axi-symmetric cavities, leading to new opportunities to develop a more frugal, agile, and sustainable communications technology. Our proposed design has the potential to achieve coherent interconversion between the microwave frequency range in which wireless networks or quantum computers operate and optical network frequencies, which is the optimal frequency range for long-distance communications. In this regard, our proposal not only proposes new applications of magnonics to the field of optics not previously envisioned, but also builds a bridge between the spintronics and the electronic and quantum communities.
In this proposal, the elastic deformations are generated by the magnetization dynamics through the magneto-elastic tensor and its contactless coupling to a microwave circuit. We have shown that coherent coupling between magnons and phonons can be achieved by precisely tuning the magnetic resonance degenerate with a selected elastic mode via the application of an external magnetic field. We expect to achieve ultra-high fidelity conversion by focusing our study on micron-sized single crystal magnetic garnet structures integrated with GaAs photonic waveguides or cavities. In addition, we propose the fabrication of suspended cavities as a means to minimize further energy leakage (elastic or optical) through the substrate.
The first challenge is to produce hybrid materials that integrate high quality garnet films with semiconductors. We propose a radically new approach based on micron-thick magnetic garnet films grown by liquid phase epitaxy (LPE) on a gadolinium-gallium-garnet (GGG) substrate. The originality is to bond the flipped film to a semiconductor wafer and then remove most of the the GGG substrate by mechanical polishing. The resulting multi-layer is then processed using standard lithography techniques, taking advantage of the relative robustness of garnet materials to chemical, thermal or milling processes.
The second challenge is to go beyond the excitation of uniform modes and target modes with orbital angular momentum as encoders of arbitrarily large quanta of nJ? for mode multiplexed communication channels or multi-level quantum state registers. The project will take advantage of recent advances in spin-orbit coupling between azimuthal spin waves as well as elastic scattering of magnons on anisotropic magneto-crystalline tensors. In this project, we also want to go beyond uniformly magnetized state and exploit the ability to continuously morph the equilibrium magnetic texture in the azimuthal direction as a means of engineering the selection rules and thus coherently access otherwise hidden mode symmetries.

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