High performance graphene for non-metallic contact in perovskite devices

Despite their many positive impacts, PV panels production face threat of sustainability of growth in terms of raw materials, energy, and environment. The PV industry is very dependent on critical raw materials and this dependence is getting worse as the production and consumption of solar panels are increasing considerably.

The main goal of this project is to develop the next generation of transparent/non-transparent conductive layers based on non- critical raw materials. These layers will be used as contact, interconnections in innovative solar panels. Guiding principle of this project is to construct competitive high quality/low-cost conductive line to replace silver contact. Due to these outstanding properties, Graphene could play an essential role in replacing critical material and enhancing electrical conductivity. This Ph-D project will be devoted to the development of low and high temperature conductive graphene inks. These inks will be designed for serigraphy, inkjet, or any suitable low-cost printing deposition techniques to print contact and interconnection. i) Inks properties in terms of composition, viscosity will be tuned. ii) The behavior of printed conductive ink will be investigated after being exposed to different stress (mechanical, temperature, moisture, electrical, light, oxygen….). iii) Finally the focus will be on conductivity characterization as a function of electrode morphology (thickness, porosity, …) and mechanical resistance. The overall aim is to optimize conductivity, mechanical resistance, and durability and finally incorporate these improvement in perovskite solar cells.

Stable tandem perovskite solar cells based on new cross-linked electron transport layers

Perovskite solar cells (PSCs) have become a trending technology in photovoltaic research due to a rapid increase in efficiency in recent years. In 2020, a record efficiency of 25.5% close from Shockley-Queisser theoretical limit of 30% was reported. Tandem solar cells offer an alternative to go beyond but stability still remains an issue.

In our project, we will bring together our complementary expertise in molecular and macromolecular syntheses, thin film morphology tuning and cell device engineering to improve the stability of highly efficient inverted perovskite cells using new electron transport layers (ETL) with high electron mobility and high stability. We will design and synthesize new n-type fullerene free semiconductors. Introduction of cross-linkable groups will lead to stabilized ETLs by thermally-induced cross-linking after film formation. The efficiency and stability of these ETLs will be finally evaluated through their incorporation in tandem configuration.

Durable radially polatised tubular nanoreactors for catalysis

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. This nanotube belongs to a family sharing the same local structure with different curved morphologies (nanosphere and nanotile). In addition, several modifications of these materials are possible (coupling with metal nanoparticles, functionalization of the internal cavity), enabling their properties to be modulated. These materials are therefore good candidates as nanoreactors for photocatalytic reactions. So far, proof of concept (i.e. nanoreactor for photocatalytic reactions) has only been obtained for the nanotube form. The aim of this thesis is therefore to study the whole family (nanotube, nanosphere and nanotile, with various functionalizations) as nanoreactors for proton and CO2 reduction reactions triggered under illumination.

Compact source of electrons-positrons/muons-antimuons pairs

### Context
The context of this PhD thesis deals with laser plasma electron accelerators (LPA), which can be obtained by focusing a high-power laser into a gas medium. At focus, the laser field is so intense that it quasi-instantly ionizes matter into an undersense plasma, in which it can propagate. During laser propagation, the ponderomotive laser pressure expels plasma electrons from its path, forming a cavity void of electrons in its wake. This cavity, called ‘bubble’, can sustain accelerating fields (100GV/m) that are roughly three orders of magnitude larger than what can be provided by Radiofrequency cavities, which equip the current generation of conventional accelerators. These accelerating structures can trap some plasma electrons and accelerate them at relativistic energies (few GeVs) over distances of a few centimeters. This offers the prospect of producing much more compact and affordable accelerators, with the following goals: (i) democratizing their usage for existing applications currently reserved to only a few installations in the world (ii) enabling new applications in strategic sectors (fundamental research, industry, medicine, defense).

Among the applications for which a strong international competition exist we remark:

> The usage of these accelerators to provide the first high-energy (100 MeV) electron radiotherapy machine for medical treatmes

> The usage of these accelerators as a building block of a future large scale TeV electron/positron collider for high-energy physics

> The usage of these accelerators to develop a compact and mobile relativistic muon source to perform active muon tomography. Such a tool would be a major asset for industrial applications (e.g., safety diagnostic of nuclear reactors), and for defense applications (non-proliferation). It is worth to mention that in these two sectors the american agency DARPA has already funded an ambitious program ( Muons for Science and Security, MuS2) in 2022, with the aim of providing a first conceptual report of a relativistic moun source based on a plasma accelerator (cf. https://www.darpa.mil/news-events/2022-07-22).

### Challenges:

In order to enable the aforementioned applications, strong limitations of current laser-plasma accelerators need to be addressed. An important limitation is the low amount of charge at high-energies (100 MeV – few GeV) provided by these accelerators. The main reason behind the low accelerated charge is the fact that present-day injection techniques are based on the injection of electrons from the gas, whose density is very low. In order to address this limitation, we have recently proposed a new injection concept based on a remarkable physical system called “plasma-mirror”. This concept relies on the use of a hybrid solid-gas target. When impinging on such a target, the high-power laser fully ionizes the solid and the gas. The solid part is so dense that it can reflect the incident laser, forming a so-called ‘plasma mirror’. In the gas part, the laser propagates and drives a LPA. Upon reflection on the plasma mirror, ultra-dense electron bunches can be highly-precisely injected into the bubble of the LPA formed by the reflected laser field. As the solid offers orders of magnitude more charge than the gas medium and as charge is injected from a highly-localized region from the plasma (plane), it has the potential to level up the injected charge in LPAs while keeping a high electron beam quality.

The PHI group is an international leader in the study and control of these systems. In collaboration with LOA, by using a 100TW-class laser, we have demonstrated that this new concept allows for a significant increase of the accelerated charge while preserving the quality of the beam.

### Goals

The first objective of this PhD thesis will be to develop a multi-GeV laser-plasma accelerator based on a plasma-mirror injection on Petawatt-class laser installations like the APOLLON laser facility. With a Petawatt-class laser this accelerator should produce electrons beams at 4 GeV with a total charge of hundreds of pC and a few % energy spread. Such a beam quality would represent a substantial progress in the domain.

The second objective will be to send this electron beam into a high-Z converter in order to generate muons/anti-muons pairs. Our estimations show that we could obtain roughly 10^4 relativistic muons per shot, which would allow for the radiography of a high-Z material in a few minutes.

This PhD subject foresees:
> Theoretical/numerical modeling activities based on our exascale code WarpX (to model the laser-plasma accelerator) and on the Geant4 code (for the modeling of the high-Z converter).

> Experimental activities (high-intensity laser-plasma interaction, detection of relativistic muons)

The project involves several partner laboratories:

> The Laboratoire d’Optique Appliquée for the laser-plasma acceleration activities (A. Leblanc)

> The Lawrence Berkeley National Lab for code development activities (WarpX, J.L Vay)

> The CEA-IRFU for the detection part (micromegas technology, O. Limousin)

For the experimental part, we will use several laser facilities:

> The UHI100 laser installation for the setup and testing of the laser-plasma accelerator at reduced power

> The APOLLON installation for the setup and testing of the plasma accelerator with a PW-class laser. A first experience implementing the concept of a plasma-mirror injector at the PW-level is scheduled for May 2024 in the framework of a collaboration between CEA and LOA. Following this experiment, we will perform a second experiment (2025-2026) to generate muons on APOLLON or other laser facilities in Europe (e.g., the ELI installations).

Electrical polarisation mapping in ferroelectric devices at the nanoscale

Ferroelectric materials, with their high dielectric constant and spontaneous polarisation, are the subject of intense research in microelectronics. Polarisation is an essential parameter for these materials while its characterization remains mainly limited to the macroscopic scale by conventional electrical methods. To deepen the understanding of these materials, particularly in thin layers, and built new devices, local measurements are essential. This thesis project aims to develop a new methodology to directly map polarisation in devices at nanoscale. By combining the expertise of SPEC in thin film growth and of C2N in nanostructuration and electric measurements, we will elaborate and design a particular geometry of nanostructures allowing the use of operando electronic holography (collaboration with CEMES-CNRS, ANR POLARYS) to quantitatively map the local electrical potential in nanodevices upon application of a voltage.

Virtual neutron scattering experiments from the moderation to the neutron detection.

The French neutron scattering community is proposing to build a new High-Current Accelerator-driven Neutron Source (HiCANS). Such a source would use a low-energy proton accelerator, a few tens of MeV, to produce thermal and cold neutrons and power an instrumental suite of around ten spectrometers. The aim of the thesis project is to build a multi-scale description of the operation of a neutron scattering spectrometer, ranging from the description of microscopic neutron moderation processes and neutron interactions with atomic structure and sample dynamics, to the propagation of neutrons through advanced optical elements and the production of background by secondary particles. The ultimate aim is to be able to carry out virtual neutron scattering experiments and accurately predict instruments performances on the future ICONE source.

Hyperpolarised, continuous-mode NMR based on parahydrogen and grafted catalysts

Nuclear Nuclear magnetic resonance (NMR) is a robust, non-invasive technique of analysis. It provides valuable information about chemical reactions, which can then be better characterised and optimised. However, NMR is poorly sensitive, and low-concentrated solutes, such as intermediates of reaction, may be unobservable by conventional NMR. One method known to drastically but temporarily increase the sensitivity of NMR is to create a hyperpolarised state in the system of nuclear spins, i.e. a polarisation much greater than that accessible with available magnetic fields. One hyperpolarisation method uses the specific properties of parahydrogen. A catalyst is required to add parahydrogen to a multiple bond or a metal.

The present thesis will investigate the combined contribution of (i) parahydrogen-based hyperpolarisation [1], (ii) the grafting of the appropriate catalyst onto nanoparticles [2], and (iii) a continuous analysis method [3] to detect and identify chemical intermediates, areas in which the laboratory has acquired experience. This subject involves a major investment in instrumentation, as well as skills in synthetic chemistry and NMR.

The thesis will be carried out at NIMBE, a joint CEA/CNRS unit at CEA Saclay. The hyperpolarised NMR and the synthesis will take place under the respective responsibility of Gaspard HUBER, from LSDRM, and Stéphane CAMPIDELLI, from LICSEN. These two NIMBE laboratories are located in nearby buildings.

[1] Barskiy et al, Prog. Nucl. Magn. Reson. Spectrosc. 2019, 33, 114-115,.
[2] Hijazi et al., Org. Biomol. Chem., 2018, 16, 6767-6772.
[3] Carret et al., Anal. Chem. 2018, 90, 11169-11173.

4D printing of thermo-magnetic composite materials using light-driven additive manufacturing techniques

This PhD research project explores the cutting-edge field of 4D printing, a field that integrates smart materials into additivemanufacturing processes. The aim is to create nanocomposite objects with multifunctional capabilities, enabling them to change shapeand properties in response to external stimuli.

In this PhD project, we will primarily focus on liquid crystal elastomers (LCEs) as the active matrix. LCEs are a versatile class ofprogrammable polymer materials that can undergo reversible deformation under various stimuli, such as light, heat, electric fields, andmagnetic fields, transitioning from disordered to oriented phases. Because of their actuation properties, LCEs are promising candidatesin applications like artificial muscles in medicine and soft robotics.

Consequently, the project's first objective is to devise a method for 3D printing LCE resins using light-driven printing processes, includingdigital light processing (DLP), direct ink writing (DIW), and two-photon polymerization. The project also explores the possibility of co-printing using two laser sources with different wavelengths. This will result in designed objects capable of programmed deformationsand reversibility. To further enhance the actuation capabilities of the LCE matrices, magnetic particles will be incorporated into thethermoresponsive LCE resin. Thus, the second objective of the project is to develop a strategy for self-assembling and spatiallyorienting embedded magnetic nanoparticles in LCE resins during light-driven printing processes (DLP, DIW, 2PP). Ultimately, the thirdobjective of this project is to combine these two strategies to create sophisticated multifunctional soft machines and devices suitable forcomplex environments. Experiments will follow an incremental trial-and-error research approach, with the aim of improving machinelearning models by designing purpose-built objects.

The envisioned research work can be summarized into the following macro-steps:
- Specification of target shape-changes depending on the multiple stimulation scenarios
- Selection of active particles, formulation of the LCE, and synthesis of the particles
- Development of hybrid additive manufacturing strategies with possible instrumentation
- Printing proofs-of concept and conducting mechanical and actuation tests
- Characterization of composite structures
- Development of simulation models
- Realization of a demonstrator (e.g., crawling robot, actuators for the automotive sector…)

Multi-level functionality in ferroelectric, hafnia-based thin films for edge logic and memory

The numerical transition to a more attractive, agile and sustainable economy relies on research on future digital technologies.

Thanks to its non-volatility, CMOS compatibility, scaling and 3D integration potential, emerging memory and logic technology based on ferroelectric hafnia represents a revolution in terms of possible applications. For example, with respect to Flash, resistive or phase change memories, ferroelectric memories are intrinsically low power by several orders of magnitude.

The device at the heart of the project is the FeFET-2. It consists of a ferroelectric capacitor (FeCAP) wired to the gate of a standard CMOS transistor. These devices have excellent endurance, retention and power rating together with the plasticity required for neuromorphic applications in artificial intelligence.

The thesis will use advanced characterization techniques, in particular photoemission spectroscopy and microscopy to establish the links between material properties and the electrical performance of the FeCAPs.

Operando experiments as a function of number of cycles, pulse amplitude and duration will allow exploring correlations between the kinetics of the material properties and the electrical response of the devices.

The thesis work will be carried out in close collaboration with NaMLab (Dresden) and the CEA LETI (Grenoble).

Innovative concepts for particles plasma acceleration and radiation emission in laser – overdense plasma interaction at ultra-high intensity

The present PHD work aims at exploring theoretically and numerically the generation of fast particle beams in ultra-relativistic (above 10^21 W/cm2) laser-overdense solid interaction by using properly-structured or shaped targets. Surface characteristics inducing local electromagnetic modes more intense than the laser field and where nonlinear and relativistic effects play a major role will be investigated.

On the basis of the work already carried out, the new scheme for particle acceleration will be extended in the ultra-relativistic regime of laser plasma interaction. It may lead to groundbreaking ultra-short synchronized light and electron sources with applications in probing ultrafast electronic processes. In this context, this theoretical and numerical study will allow to suggest new experimental schemes feasible on the Apollon facility and multi-PW lasers.