Metal-Organic Frameworks (MOFs) form a family of porous inorganic-organic ordered hybrid materials which have generated huge interest in the scientific community. Whilst sorption, magnetic, catalytic and drug delivery properties have been largely documented, the basic mechanical properties of these materials have not received as much interest. However, the fact that several structures are highly flexible may be of interest to exploit as dampers or springs as an alternative to previous work carried out on hydrophobic silica based materials. The advantage of MOFs being that the almost infinite possibility to modulate the structure and chemical/physical properties of these materials means that the mechanical properties can equally be tuned. The aim therefore of this fundamental project is twofold : 1) To study the thermodynamic and mechanical properties of selected flexible MOFs in view of (i) establishing pore volume phase diagrams as a function of pressure and temperature, (ii) determining the transition energies between the various phases and (iii) characterizing the structural behaviour under operating conditions up to high temperature and moderate pressure, to compare with theoretical calculations; 2) To evaluate the possibility of using these materials for mechanical storage of energy as dampers or springs. This challenging interdisciplinary project that involves the synthesis of materials, the characterization of the properties of interest and modelling, will be conducted by a subtle combination of innovative experimental tools and advanced molecular simulation approaches, which is expected to yield breakthrough in this domain. It will also bring microscopic insight into the mechanism in play during the phase transition under thermal and mechanical stimuli.

In the D-FACTO project, we propose to design and fabricate active optical windows based on nanostructured diamond, combining anti-reflective, superhydrophobic, anti-icing and anti-fouling properties. This research project is motivated by the very promising results obtained within the framework of the ANR ASTRID F-MARS project (2019-2022), coordinated by Thales Research & Technology (TRT). In this project, TRT has already shown its capability to simulate and manufacture “multifunctional” windows with broadband anti-reflective and large incidence, superhydrophobic and anti-rain properties in the range of Visible, Midwave InfraRed. and Longwave InfraRed, by developing nanostructuration processes of glass, silicon and germanium respectively. These optical windows aim to meet the needs of many optical and optronics systems used in civil and military fields: land and sea surveillance systems, airborne sensors for threat detection, autonomous train cameras, etc. However, the superhydrophobic nature of these windows, which is fundamental for some of these applications, does not protect these systems, for example, from the formation of various biofilms (marine, hydrocarbons, etc.), nor from the formation of frost. The aim of the D-FACTO project is to extend the multifunctionality of these optical surfaces, by developing robust “active” diamond windows allowing them to be get anti-fouling and anti-ince properties, by using a low current. electrical, coupled (or not) with adequate surface functionalization. Indeed, diamond has intrinsic qualities of interest: in addition to having very good mechanical properties, it is transparent in the ranges from visible to LWIR and it is an excellent thermal conductor. Once doped, it has remarkable electrochemical properties, among which the capacity for electrochemical self-cleaning of its surface and therefore anti-fouling properties. The work of the consortium, composed of two academic partners, CEA-LIST and ILV, and an industrialist (TRT), will first focus on the development of pre-industrial processes for producing optical windows based on synthetic diamond which will benefit from its optical, mechanical and physicochemical "flexibility" advantages for anti-fouling, anti-ince and anti-reflective applications. They will also focus on the understanding and optimizationof the phenomena involved in the self-cleaning and anti-icing mechanisms of these so-called "active" windows. The manipulation of surfaces by electrochemistry of diamond, or else by more conventional surface treatments, should make it possible to modulate its omniphobic capacities. The consortium will thus have various very original functionalization possibilities for optimal physicochemical adaptation. Considering the state of the art, the challenges of the D-FACTO project are the following: • to develop a large area (2-3 inches) process of diamond nanostructuring for anti-reflective applications in Vis, MWIR and LWIR. • to characterize and optimize the growth of doped diamond by taking into account the application constraints (compliance with optical specifications, nature of the substrates in the case of diamond / silicon, diamond / germanium “hydride” windows, etc.). • to optimize the physicochemical properties of the post-nanostructuring process diamond surface and to develop specific chemical engineering based on various surface treatments: “electroless” chemistry, electrochemical assistance, plasma process, etc. • Set up a robust characterization methodology, able of combining fine wettability analysis and chemical analysis by photoemission or Auger emission of diamond, in order to guide the consortium in optimizing the functionalization of nanostructures.

The progresses in photonic technologies require the independent control of the phase propagation and the energy of light. This is possible using hyperbolic metamaterials, an ultimate case of birefringence with ordinary and extraordinary dielectric constants of opposite sign. Self-organized molecular and/or macromolecular systems offer a route to the realization of such media since they can embed various pi-conjugated mesogens amenable to form a large variety of structures with record-breaking optical anisotropy. Our objective is to develop an innovative self-organized (macro)molecular system incorporating fluorescent moieties in order to combine hyperbolic dispersion with light emission or optical gain. Beyond the compensation of the intrinsic losses of metamaterials, we target the realization of innovative light-emiting devices by embedding the source in the bulk of the metamaterial, whereas most current realizations involve complex nanoscale combinations of different emissive and birefringent media.

Cancer and bacterial infections are two of the main healthcare challenges humanity has to face nowadays. The side effects and limited efficiency of traditional cancer treatments as well as the development of multi resistant bacteria make it urgent to develop new strategies. Beyond the fact that both are two of the main public health concerns, they are intertwined. The DANthe project objective is to elaborate polyoxometalate (POM) decorated gold nanostars (AuNSs) that combine chemotherapy using a new active agent (POM), photothermal (PTT) and photodynamic therapies (PDT) in the NIR window to obtain unprecedented active tri-therapy drugs acting against both cancer and bacterial infections. We propose herein for the first time to prepare AuNSs using hybrid organic-inorganic POM which will combine the POM specific biological properties, the PTT and the generation of ROS of the AuNSs and singlet oxygen storage/release unit on the organic part of the POM. Preliminary test in cellular environnent under irradiation will be performed to evaluate the nano-object efficiency for the targeted applications.

Halide perovskite based solar cells (PSCs) mark a critical turning point for emerging photovoltaic technologies. The French-German project ALSATIAN aims at enhancing the reliability of PSCs by developing new functional thin-film coatings that will improve stability of high efficiency cells. Rapid efficiency-focused progress in PSCs risks pursuing only a particular device heterostructure which may in fact be nonideal in terms of reliability. ALSATIAN will look beyond standard interlayer materials to focus on novel thin-film materials and deposition procedures to process interlayers by atomic layer deposition (ALD) and molecular layer deposition (MLD) adjacent to the perovskite absorber in the cell to serve as transport, recombination, or passivation layer. Using in situ and operando techniques, we plan to assess the impact of the interface between functional interlayer and perovskite on the device performance and stability. A major objective is to evaluate the compatibility of the interlayer deposition process and the interlayer itself with the perovskite film, since chemical reactions can initiate rapid degradation or create defect sites that impede device functionality. However, for a stabilized interface system the functional layer can provide protection of the perovskite film and improve optoelectronic properties. Hence, we will employ advanced spectroscopic tools paired with DFT calculations to investigate chemical reaction pathways that occur during layer growth at the interfaces. In addition, we will study (photo-)electrochemical reactions between the layers that could be induced under operating conditions in various chemical environments. To this end, we will assess buried interfaces by hard X-ray photoemission and determine key electronic properties, which we will correlate to data from spatially resolved optical spectroscopy. In combination, we will investigate the impact of the interface between the functional thin-film coating and perovskite layer on the device performance and stability in-situ, i.e., in between growth steps, or operando, i.e., for operating solar cells in adapted device architectures.