Contribution of metal-semiconductor interfaces to the operation of the latest generation of infrared photodiodes

This thesis concerns the field of cooled infrared detectors used for astrophysical applications. In this field, the DPFT/SMTP (Infrared Laboratory) of CEA-LETI-MINATEC works closely with Lynred, a world leader in the production of high-performance infrared focal planes. In this context, the infrared laboratory is developing new generations of infrared detectors to meet the needs of future products.
One of the current development axes concerns the quality of the p-type semiconductor metal interface. These developments are driven by the increase in the operating temperature of the detectors, as well as by the very strong performance requirements for space applications.
The challenge of this thesis is to contribute to a better understanding of the chemical species present at the interface of interest as a function of different surface treatment types and to link them to the electrical properties of the contact made.
The candidate will join the infrared laboratory, which includes the entire detector production process. He/she will produce these samples using the technological means available in the LETI clean room, in collaboration with experts in the field. He/she will also have access to the necessary characterization tools (SIMS, XPS, AFM…) available on the nano-characterization platform (PFNC) or in the CEA clean room. Finally, he/she will be involved in the electro-optical characterization of the material, in collaboration with the Cooled Infrared Imaging Laboratory (LIR), which specializes in fine material characterization.

Stabilisation of Perovskite photovoltaic devices by passivation with Metal-Organic Frameworks type materials

MOFs are a type of porous organic-inorganic hybrid material with interesting properties in terms of the passivation of defects in the perovskite and its stability, particularly versus light. For example:
- Direct effect of MOF components as passivation agents: Metal ions and organic ligands can passivate defects at the MOF/PK interface.
- Downconversion of incident radiation: Certain metals (such as europium) or ligands (with aromatic groups) can absorb high-energy radiation (typically violet/near-UV), then re-emit this energy in the form of lower-energy radiation or transmit it directly in a non-radiative manner to the perovskite by Förster resonance (or FRET). This protects the perovskite from high-energy photons, and therefore a priori improves light stability, with little energy loss.
The thesis work will focus on
- integrating MOFs into the perovskite layer, either as a surface treatment or as a mixture of suspensions
- Materials studies (in particular advanced studies using XPS and UPS)
- Favrication of single-junction devices and then tandem devices with silicon sub-cells
- Study of lifetime under illumination (continuous, cycling) with associated characterisations (electrical measurements, photoluminescence, etc.).

Combination study of high throughput screening techniques and artificial intelligence (AI) to identify innovative materials for next generation of battery

In recent years, the CEA has set up an experimental high-throughput screening (HTS) activity for lithium battery materials, based on combinatorial synthesis by sputtering and various high-throughput characterisation techniques on large substrates (typically 4 inches). Optimisation of material compositions is traditionally carried out by analysing experimental designs. In the framework of this thesis, we propose to compare the results of this conventional method with the Artificial Intelligence tools developed at CEA-LIST (symbolic AI) and CEA-CTREG (connectionist AI). The objetive is to demonstrate that AI can advantageously replace standard experimental design in order to offer an innovative, high-performance high-throughput screening tool.

Epitaxial layer on GaAs or Ge transfer to sapphire or silicate for gravitational waves mirror realization

Gravitational waves were predicted by the theory of general relativity, they are created in the universe by extreme cosmic events. Their measurement on earth in large instruments such as VIRGO in Italy is a challenge in terms of measurement sensitivity. These instruments are large interferometers (several kilometers), and the entire optical chain must minimize noise to be sensitive to very small modifications in space-time. Mirrors are one of the key elements of the optical chain.
In this thesis, we propose to create a new type of mirror making it possible to significantly improve the sensitivity of an interferometer. This mirror is based on a sequence of thin epitaxial layers with variations in optical index between each of them. These thin layers must be on a silica or sapphire base. Such a structure is not achievable by additive manufacturing (ie by depositing the layers on the sapphire or silica substrate), because the thin layers are monocrystalline, and the silica is amorphous when the sapphire has an unsuitable lattice parameter. Only thin layer transfer techniques allow the creation of such a stack.
This thesis will study thin layer transfer technologies to study one or more options permitting the transfer of monocrystalline layers from the donor substrate to the receiver substrate. Each of the necessary steps will be studied, and mechanisms will be proposed to explain the experimental observations. Demonstrators will be produced and their optical performances evaluated to determine if they are in line with the required sensitivity.

In situ study of the impact of the electric field on the properties of chalcogenide materials

Chalcogenide materials (PCM, OTS, NL, TE, FESO, etc.) are the basis of the most innovative concepts in microelectronics, from PCM memories to the new neuromorphic and spinorbitronic devices (FESO, SOT-RAM, etc.). Part of their operation relies on out-of-equilibrium physics induced by the electronic excitation resulting from the application of an intense electric field. The aim of this thesis is to measure experimentally on chalcogenide thin films the effects induced by the intense electric field on the atomic structure and electronic properties of the material with femtosecond (fs) time resolution. The 'in-operando' conditions of the devices will be reproduced using a THz fs pulse to generate electric fields of the order of a few MV/cm. The induced changes will then be probed using various in situ diagnostic methods (optical spectroscopy or x-ray diffraction and/or ARPES). The results will be compared with ab initio simulations using a state-of-the-art method developed with the University of Liège. Ultimately, the ability to predict the response of different chalcogenide alloys on time scales fs under extreme field conditions will make it possible to optimise the composition and performance of the materials (e- switch effect, electromigration of species under field conditions, etc.), while providing an understanding of the underlying fundamental mechanisms linking electronic excitation, evolution and the properties of the chalcogenide alloys.

On the role of the elastic deformation field on the formation of irradiation defects in pure metals

In the context of extending the operational lifetime of nuclear power plants (NPPs), currently operating in France, a materials ageing surveillance strategy is in place. It is essential for ensuring their mechanical properties. During the operation of the plant, materials are subjected to irradiation. Under this exposure, the internal structure of materials evolves, leading to the creation of numerous defects that degrade macroscopic properties and may result in a limitation of the long-time operation (LTO) of components. The proposed work is a fundamental study conducted on model materials, aiming to better understanding the behavior under irradiation of metallic alloys. It will contribute to the predictive modelling of materials, covering defects created at the nanoscale up to the level of nuclear components.

The irradiation of materials with high-energy particles such as neutrons, ions, or electrons generates a large number of defects called point defects (PD). These mobile PDs can migrate and aggregate to form 2D or 3D-objects like prismatic loops or cavities respectively. They can also be eliminated at PD sinks. The system is then submitted to PDs flows directed towards these sinks. These flows are then responsible for phenomena such as radiation-induced segregation (RIS) or precipitation (RIP) of solute atoms [1] [2]. The presence of clusters of PDs and of PD flows alters the microstructure and can deteriorate the physical response of the irradiated materials. In particular, the formation of prismatic loops degrades the mechanical properties of materials as they can impede dislocations and induce embrittlement [3]. In a previous study, we focused on vacancy defects in the form of cavities and investigated the facetting of defects formed in a weakly anisotropic metal, aluminum, using in-situ irradiations in a high-resolution transmission electron microscope (HRTEM).
The work aims to go further in the role of the elastic deformation field on the morphology of irradiation defects. More precisely, it aims to carry out a systematic study on different metals with different anisotropy coefficients. We have chosen reference metals with body-centered cubic (BCC) and face-centered cubic (FCC) structures with low or high anisotropy coefficients. The study will concern Cr and Fe with a BCC structure, and Al and Cu with a FCC structure and may be extrapolated to alloys of higher complexity such as high entropy alloys (HEA). The work will be mainly experimental but will also include a theoretical part. The effects of the crystal anisotropy on the morphology of prismatic loops will be carried out by phase field modelling [4]. The spatial arrangement of the loops will be studied by Object Kinetic Monte-Carlo (OKMC) simulations [5], as recently done in aluminium.
The work will be mainly experimental. We will studied [100]-oriented single crystals to avoid any surface effect on the shape of the objects formed. They will be irradiated with heavy ions at temperatures normalized with respect to their melting temperature either in-situ within the Jannus Orsay platform, or ex-situ within the Jannus Saclay platform [6]. Loops will be imaged by conventional TEM or STEM with a FEI Tecnai and Jeol NeoARM type microscopes. The latter is equipped with a double spherical aberration corrector. The work will be carried out within the framework of the joint research laboratory (LRC) MAXIT.
The work will also include a modelling part. The effects of crystallographic anisotropy on the morphology of prismatic loops will be investigated using a phase-field code [4]. The spatial arrangement of the loops will be studied using Object Kinetic Monte Carlo (OKMC) [5], as recently done in aluminum.
This work follows a 2-year postdoctoral fellowship scheduled to conclude in December 2023, during which deep learning (DL) approaches were developed to accelerate the automatic detection of defects created under irradiation [7]. The utilization of these approaches will significantly enhance the statistical robustness and precision of the results.

Advantage for the student: The PhD is situated in a laboratory composed by 25 researchers and approximately 25 students (PhD, postdoctoral fellows), creating a simulating scientific environment. The activities involve both experimental and simulation sides, offering the opportunity to interact with experts from both sides.

[1] M. Nastar, L. T. Belkacemi, E. Meslin, et M. Loyer-Prost, « Thermodynamic model for lattice point defect-mediated semi-coherent precipitation in alloys », Communications Materials, vol. 2, no 1, p. 1-11, mars 2021, doi: 10.1038/s43246-021-00136-z.
[2] L. T. Belkacemi, E. Meslin, B. Décamps, B. Radiguet, et J. Henry, « Radiation-induced bcc-fcc phase transformation in a Fe3%Ni alloy », Acta Materialia, vol. 161, p. 61-72, 2018, doi: https://doi.org/10.1016/j.actamat.2018.08.031.
[3] M. Lambrecht et al., « On the correlation between irradiation-induced microstructural features and the hardening of reactor pressure vessel steels », Journal of Nuclear Materials, vol. 406, no 1, p. 84-89, 2010, doi: http://dx.doi.org/10.1016/j.jnucmat.2010.05.020.
[4] A. Ruffini, Y. Le Bouar, et A. Finel, « Three-dimensional phase-field model of dislocations for a heterogeneous face-centered cubic crystal », Journal of the Mechanics and Physics of Solids, vol. 105, p. 95-115, août 2017, doi: 10.1016/j.jmps.2017.04.008.
[5] D. Carpentier, T. Jourdan, Y. Le Bouar, et M.-C. Marinica, « Effect of saddle point anisotropy of point defects on their absorption by dislocations and cavities », Acta Materialia, vol. 136, p. 323-334, sept. 2017, doi: 10.1016/j.actamat.2017.07.013.
[6] A. Gentils et C. Cabet, « Investigating radiation damage in nuclear energy materials using JANNuS multiple ion beams », Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, vol. 447, p. 107-112, mai 2019, doi: 10.1016/j.nimb.2019.03.039.
[7] T. Bilyk, A. M. Goryaeva, E. Meslin, M.-C. Marinica, Quantification of radiation damage in high entropy alloys by deep learning approach, 2-7/10/2022, MMM2022, Baltimore, USA

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.

Impact of microstructure in uranium dioxide (UO2) on ballistic and electronic damage

During reactor irradiation, fuel pellets undergo a partial evolution of their microstructure. At high levels of burnup, a subdivision of grains into smaller grains in the peripheral areas of the fuel pellets - called high burn-up structure (HBS) - is observed. Similar changes also occur in the central regions of the pellets at elevated temperatures. These evolutions result from the combination of several factors, including the loss of energy from fission products. The effect of this damage could vary depending on the crystal orientation and grain size.
The main objective is therefore to understand how crystal orientation and grain size influence the damage caused by irradiation. Ion irradiation experiments will be conducted on single- and poly-crystalline UO2 samples at the JANNUS Saclay facility. In situ and ex situ characterizations using Raman and Rutherford backscattering (RBS-C) spectroscopy, transmission and scanning electron microscopy with Electron backscatter diffraction (EBSD) will be carried out.

Electronic stopping power simulations for heavy ion irradiations

The interaction between charged particles and matter has been the focus of physicists' attention for over a hundred years. Niels Bohr, Enrico Fermi and many others have contributed to this field fundamental for physics, but also for industrial fields such as nuclear, space photovoltaics, or electronics. Today, the time for models is gone and realistic calculations are now carried out using supercomputers.

We propose to use our time-dependent quantum-mechanical computer code to simulate precisely and without experimental input, the energy loss of fast ions in condensed matter. This quantity is called the stopping power.

In particular, our attention will be focused on the materials and ions for which we know that empirical models fail. Our contribution with numerical simulations will be crucial for our experimental collaborators.

Atomistic modelling of magnetic metal alloys : finite-temperature effects

An accurate modelling of magnetic alloys requires a correct description of thermal effects, such as lattice vibration, thermal expansion together with magnetic excitations and transitions. All these effects are correlated to each other and they strongly impact on the stability of chemical phases and numerous kinetic processes. A proper treatment of the various involved degrees of freedom and their coupling is higly challenging for atomistic modelling and simulations, particularly due to the dependency on temperature and alloy composition.

In this thesis, we aim at developing and applying a multiscale modelling approach to predict thermodynamic and kinetic properties of magnetic metal alloys as a function of temperature.
We will focus on Fe alloys as a representative case. The target properties include the chemical and magnetic phase boundaries, point-defects concentrations, atomic diffusion coefficients and kinetics of precipitation. In order to investigate these properties, we will employ ab-initio density functional theory (DFT), coarse-grained tight-binding (TB) and effective-interaction models (EIM) and Monte Carlo simulations. Besides the methodological advance, the outcome of the thesis will be also very promising from the materials science point of view, due to the multiple technological applications of these alloys, for example, as the basis of steels.

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