Phase Change Random Access Memories (PCRAM), which are based on the reversible amorphous-crystalline transition in phase change materials (PCMs), constitute a very promising alternative to Flash technology, which is reaching fundamental limits. One of their key advantages is their scalability but, for ultimate miniaturization, energy consumption is critical and a promising solution is the geometrical confinement of the memory points. Mastering this with PCMs at ultimate dimensions (typically 5 nm) is, however, a real challenge, which calls for a fundamental understanding of the interplay between strain (the amorphous-to-crystal transition is accompanied by density increase of several %) and interface energies at the nanoscale. The objective of the SESAME project is to study the influence of strain and size on the PCM phase transition at ultimate dimensions. To address these issues we will use advanced in situ characterization techniques applied to ultra-thin layers, confined nanostructures and nanoclusters in order to investigate the early stages of phase transition and also to measure local strains and microstructure changes at crystallization. Five partners with complementary know-how will participate in the project: IM2NP-Marseille, CEA-LETI-Grenoble, CEA-INAC-Grenoble, synchrotron SOLEIL – St Aubin, CINaM-Marseille. The SESAME project will be organized along 5 tasks: 1. Coordination, 2. Sample preparation and characterization, 3. High resolution synchrotron X-ray scattering, 4. Transmission Electron Microscopy (TEM), 5. Simulation. Thin/ultra-thin GeTe and Ge2Sb2Te5 (GST) PCM films and PCM materials in confined structures will be prepared at CEA-LETI. Various thickness (100 to 5 nm), size (down to 10 nm width) and capping materials (Ta, TaN, Ta2O5, SiN, SiO2, Ti, TiN …) will be studied. CEA-INAC has the unique capability of preparing sub-10 nm GeTe and GST clusters by gas phase condensation. This will allow us to address the ultimate sizes, far beyond existing capabilities of lithography. Clusters with different composition or doping will be embedded in matrices with various thermo mechanical properties in order to evaluate the impact of mechanical stress on PCM clusters properties. Preliminary in situ sample characterizations will be performed at CEA: in situ ellipsometry, reflectivity, Raman spectroscopy or four-point-probe resistivity measurements. On these well-characterized samples unique in situ High-resolution synchrotron x-ray scattering and state-of-the-art transmission Electron microscopy (TEM) investigations will be performed. An original combination of resistance, X-ray diffraction and X-ray reflectivity that allows correlating structural and electrical PCM properties upon crystallization has been developed jointly by IM2NP and ESRF and will be used at synchrotron SOLEIL to characterize in situ the phase transition of ultrathin PCMs. Also the in situ combination of X-ray diffraction and optical curvature measurements developed jointly by IM2NP and DiffAbs beamline at SOLEIL will allow for an in-depth understanding of the mechanics involved in the amorphous-to-crystal transition. State-of-the-art TEM performed at CEA-INAC and CEA-LETI will bring valuable knowledge on local distribution of elements, defects and strains. In situ TEM observations during crystallization will offer invaluable information on the nucleation sites for crystallization. It is worth noting that these highly original in situ techniques (based either on TEM or Synchrotron radiation) will be used also to investigate structural changes in the amorphous phase. The issue of resistance drift in the amorphous phase is a key point for the stability of stored information in the memory cell. Atomistic simulations (Density Functional Theory, Molecular Dynamics) will be performed at CINaM in order to simulate the atomistic structure and the properties (structural, electronic, spectroscopic) of phase change materials in amorphous and crystalline form.

Water is a fundamental resource for human and economical welfare and modern society depends on complex, interconnected infrastructures to provide safe water to consumers. Water Distribution Systems (WDSs) are constantly exposed to deliberate or accidental contaminations or may undergo a partially or full system collapse. This could be caused by terrorist attacks, cascade effects, major technical accidents or natural disasters. The project ResiWater aims to develop tools to prepare water utilities for crisis management and enhance their resilience with regards to three specific case studies: collapse of WDS, water quality deterioration and cascade effects between water, energy and IT infrastructures. For the realization five main steps were defined: specification of critical case studies, design of integrated and secure sensor networks, development of a self-learning module for abnormal event detection, development of robust hydraulic and water quality simulation tools for modelling of extreme events, and decision support tools for improving resilience of WDSs. The French-German cooperative research project consists of end users (BWB in Germany, CUS and VEDIF in France), technical and socio-economic research institutions (Fraunhofer IOSB, Fraunhofer IGB, TZW, CEA, Irstea, ENGEES) and industrial partners on French and German sides (VEDIF, 3S Consult and Pretherm). It ideally combines top-level research with the practical needs of water supply utilities. Among the main expected results, two simulation software tools are planned to be extended for crisis management and preparedness: those of partners Irstea and 3S Consult. The three water utilities will benefit from the outputs, training and decision support tools.

This project focuses on three iron-base alloys that have growing potential for high-temperature, high-strength and strong- magnet applications: Fe-Cr, Fe-Mn and Fe-Co. Because of the key role of magnetism, an innovative materials design based on advanced modeling approaches is necessary to control key properties of these materials. Such a design strategy requires the combination of (i) highly accurate methods to determine atomic features with (ii) efficient coarse-graining techniques to access target physical properties and to perform the screening of materials compositions. For the former, density functional theory (DFT) has for many materials classes already proven to be a highly successful tool. For Fe-based alloys, however, a critical bottleneck is the role that magnetic ordering, excitations and transitions have on thermodynamic, defect and kinetic properties. Therefore, a complete and accurate modeling of magnetism is urgently needed to address the materials-design challenges: the resistance to radiation damage related to the chemical decomposition in Fe-Cr, the grain-boundary embrittlement in ferritic Fe-Mn and the high-strength of austenitic Fe-Mn, and the phase ordering and the relative stability of a and ? phases in Fe-Co cannot be fully understood without properly accounting for the magnetic effects. The novelty of the current approach is twofold: First, on the DFT-side, we will make use of the recent important progress in treating magnetism in pure idealized Fe lattices, in order to go towards an accurate modeling of magnetic multi-component systems with point/extended defects, and beyond the standard collinear approximation. Second, we will develop new methods that allow us to bridge the gap between (i) highly accurate electronic calculations and (ii) large-scale atomistic thermodynamic and kinetic simulations for iron based alloys by – and this is decisive – fully taking into account the impact of magnetism on defect properties, diffusion and microstructural evolution. For the latter, lattice-based effective interaction models (EIMs) and tight-binding (TB) models will be developed based on data from DFT, including magnetic configurations, excitations and transitions. This will allow us to provide a coherent description of the role of magnetism on various properties of Fe-based alloys at different length scales and at finite temperature. It will further give us the ability to perform the optimization of key parameters controlling the relevant properties like phase decomposition in Fe-Cr, phase ordering in Fe-Co or decohesion of grain boundaries in Fe-Mn. Dedicated experiments in bulk alloys and along intergranular / interphase boundaries grown on demand will be performed in the project, which are essential for verifying the robustness of the theoretical predictions. The three chosen alloys exhibit a large variety of magnetic behavior. The methods developed and applied in this proposal are therefore expected to be transferrable to the modeling of other magnetic materials. The results of our simulations will lead to the improvement of thermo¬dynamic and diffusion databases and tools (such as DICTRA) that are nowadays routinely used in industrial R&D but that at present have difficulties in accounting for magnetism. In this way a better and more systematic understanding of the role of magnetism in Fe-based alloys will help to improve significantly the predictive power of the simulations and thus contribute to a more efficient and accurate development of new steel grades. Once fully implemented, the availability of such computational tools is expected to boost the efficiency, change the strategy in designing new steel grades and to form an important contribution for the future competitiveness of steelmakers.

In the context of green chemistry, cascade catalytic reactions appear as ideal solutions for industry. Combining strategies from biocatalysis to chemocatalysis, the Ni(k)AGARA project aims at experimentally demonstrating the concept of cascade catalysis in cristallo on oxidative transformations of alkenes, performed in multi active sites cross-linked artificial enzyme crystals (CLEC). It will consist of an evolution of our mastered CLEC application that will require innovative chemical modifications in NikA protein crystals for the insertion of a second inorganic catalytic site. Our knowledge in high performance of alkenes’ degradation using dioxygen as oxidant will drive us to add downstream transformations in an original cascade of catalytic oxidation reactions, implying carbonation, aldehyde oxidation, or degradation of polyunsaturated biomolecules. Never performed on hybrid solid catalysts, such a catalytic process could eventually reach the requirements for an industrial use. he project is divided into two main objectives: first, the construction of two catalytic sites within a protein, distinguished by their mode of insertion. The first will be based on supramolecular interactions as mastered by the consortium today, while the latter will be covalently linked to the solvent channels of the protein crystal. the method of attachment will be obtained by the mutation of an amino acid of the N-terminal chain with a cysteine; this one will then react with related functions on the ligand of the metal complex to integrate. An alternative will be to perform click chemistry on an unnatural azido amino acid. Catalysis of transformation will be the second objective, a choice resulting from the recent discoveries of the consortium. Oxidative cleavage of alkene has been shown to be catalytic with artificial protein crystals, based on the insertion of iron complexes within the NikA protein. On this basis, the activation of CO2 will be undertaken in the second stage of the cascade reaction: a transformation of epoxides into carbonates or the subsequent oxidation of polyenes are an illustration of this. The interdisciplinary project Ni(k)AGARA deals with the conception of innovative solutions for a sustainable chemistry. It will cover research at the interface of biotechnology and chemistry. Accordingly, the project concerns basic science to develop new catalytic solutions for green chemistry, involving a bio-inspired design of heterogeneous biocatalysts. The outstanding quality of the present project relies into the right combination between sustainability and catalysis, creating new innovative solutions for catalysis while targeting pollutants, or bio-based molecules building blocks. The scientific benefits will be numerous at various levels. Firstly, the consortium will develop new tools to transform chemically crystalline proteins and understand the catalytic mechanisms at molecular level. Secondly, the application for polymer transformation should open new greener routes. Accordingly, it fulfills the requirements of “stimuler le renouveau industriel” and should be evaluated by the CES “chimie moléculaire, chimie durable et procédés associés” since catalysis is associated to eco-efficiency and to the development of new molecules. A second reading level of the project deals with the search of new reactions processes for high value products combining the valorization of CO2 with polymer functionalization, a very active field for polymers with low environmental impacts. Partner 1 and 2 have been involved in collaborative projects since 2008 and their common publications in journals of high impact attest of their efficacy. Partner 3 will afford its knowledge in CO2 activation and polymer science, making the targeted reactions eventually appreciable by the industry world and open a new field of possibilities for this original catalytic approach.

TRAMP addresses the scientific and technical details of the origin and potential use of the giant piezoresponse observed in silicon nano-objects. After a 10 year debate about the veracity of the giant piezoresistance (PZR) in silicon nanowires, the TRAMP partners (all of whom have been visible participants in this debate) have preliminary evidence for a giant piezocapacitive (PZC) effect. Experiments suggest a central role for stress-induced changes to the charge state of intrinsic defects at the silicon/oxide interface (specifically the Pb0 defect). The capacitive (rather than resistive) nature of the phenomenon is a surprise and the TRAMP partners have the opportunity to be ‘first-in-field’, both in terms of the fundamental science, but also for device applications of this novel phenomenon that occurs in scalable, top-down fabricated silicon nano-objects. In the initial phase of the project, the TRAMP partners will fabricate ohmically contacted, top-down silicon nanomembranes to be tested in a taylor-made apparatus that allows for the frequency and voltage dependence of the piezoresponse to be measured under uniaxial tensile and compressive stresses up to ˜150 MPa. The dependence of the piezoresponse on doping, temperature and nano-object geometry will be explored and then used to improve the design of a second process batch. This method of rapid prototyping has been used previously by the TRAMP partners, and will yield a map of the relative importance of the PZR and PZC responses as a function of these parameters. This is not only essential from the point of view of developing a microscopic understanding of the phenomenon, but also in terms of optimizing conditions for its use as a stress or motion transduction mechanism. Proper characterization of the piezoresponse will employ two techniques specifically adapted to nano-objects: micro-Raman spectroscopy for the measurement of the local stress in nano-objects, with the option to use TERS for the smallest objects, and Laplace current transient spectroscopy for the identification of the electromechanically active defects thought to be responsible for the giant, anomalous piezoresponse. This latter method is not yet widely used but is adapted to defect spectroscopy on any electrically connected nano-objects whose capacitance is too small to permit the use of more traditional capacitive spectroscopies. Once the optimal conditions (i.e. for maximum, stable PZC) have been determined, the TRAMP partners will undertake a technical study of two potential applications: the electrical detection of process induced microstrains in the active layer of ultra-thin commercial silicon-on-insulator wafers for quality control purposes; and as a means to detect motion in a nano-mechanical resonator where standard optical or capacitive methods lose sensitivity. The second application requires the fabrication of in-plane nanoresonators in which the TRAMP partners are expert. In the final task of the project the results of these two technical studies will be used as the basis for discussions with potential industrial partners. Impacts of a successful TRAMP project will therefore include high visible scientific and technical results, the first steps in the characterization of devices exploiting the PZC that are based on a scalable, top-down silicon technology, the patenting of intellectual property, and exploratory talks with partners from the semiconductor manufacturing industry aimed at licensing or collaborative opportunities.