Singlet oxygen, an excited state of molecular oxygen is a highly reactive species, relevant for an array of applications, ranging from sustainable oxidation catalysis to photodynamic therapy (PDT). The development of tailored materials capable of precisely controlling the generation and manipulation of singlet oxygen is paramount for advancing these applications. PDT, in particular, serves as a compelling example highlighting the importance of controlled singlet oxygen management. It relies on the interplay between a photosensitizer (PS), light, and ground state oxygen (3O2), producing highly reactive oxygen species such as the cytotoxic singlet oxygen (1O2) that is used to destroy cancer and microbial pathogens. Currently PDT faces two key limitations: the control of oxygen supply and limited light penetration inside the tissues. MOFSONG project addresses these limitations by proposing innovative materials capable of decoupling the light irradiation and the 1O2 release steps. The proposed approach involves the design and synthesis of porous Metal Organic Frameworks (MOFs) combining two types of organic linkers: arenes and porphyrins in a single porous structure. Porphyrins are excellent PSs capable of generating 1O2, and arenes are aromatic molecules capable of trapping this 1O2 in their structure upon a cycloaddition reaction and endoperoxide (EPO) formation, while porosity favors the concentration and fast diffusion of oxygen species. Thus, MOFs containing EPO can be generated by illumination at the optimum porphyrin excitation wavelength and stored at low temperature until being used to controllably release 1O2 in a desired environment upon heating. The project objectives involve the synthesis of molecular building units, the development of porous materials assisted by the design of experiments and robotic synthesis, comprehensive structural and spectroscopic investigations and the study of 1O2 dynamics. The success of the project is assured through an interdisciplinary consortium of five research partners providing all the necessary expertise and state of the art facilities.

The proposal HETEROBN-C aims at the controlled synthesis of freestanding one dimensional (1D) hexagonal Boron Nitride (hBN)/Carbon nanotube (CNTs) van der Waals (VdW) heterostructures and at the investigation of their structural and optical properties. In line with the spectacular improvement and emergence of new physical properties in 2D VdW heterostructures, the curvature and confinement effects provided by the reduced dimensionality of 1D VdW heterostructures make them highly attractive. These new 1D materials are of particular interest for applications ranging from sensing and quantum optics, to biological labeling. The project will focus on the understanding of the controlled growth of hBN by atomic layer deposition (ALD) onto/into suspended single wall CNTs as well as on the investigation of the relationship between the structure and the optical properties (excitonic luminescence yield, spectral properties,...). Particular attention will be paid at developing highly-controlled method of hBN deposition inside and outside CNTs, studying the growth mechanism and the resulting interaction at the nanoscale. In this regard, single-wall carbon nanotubes (SWCNTs), used as support, will be coated with a thin (from a few nm down to one monolayer) hBN layer using ALD. By means of advanced analytic transmission electron microscopy combined with DFT calculation, the relationship between the deposited hBN and the graphitized carbon support will be deeply investigated as the function of the fabrication parameters. Understanding of the BN growth on the inner and outer part of the SWCNT wall is indeed the key for a fine tuning of VdW heterostructure interfaces. On the optical side, the interface features (inter-tube spacing, orientational correlation…), expected to strongly influence the VdW coupling and thus the electronic and optical properties of this 1D heterostructure, will be studied both (1) in the near-IR spectral domain of the CNT optical response in the prospect of reaching the intrinsic limit (truly one-dimensional radiative-limited excitonic emission) of the CNT properties thanks to the hBN-encapsulation, and (2) in the deep-UV spectral domain of the BN optical response for observing the luminescence of BN layer deposited in the inner CNT wall.

STREAM project deals with a breaking innovation process for assembling and structuring at molecular level 3-D functional metal organic frameworks (MOFs) into thin films. For this purpose, a solvent-free molecular layer deposition (MLD) approach is proposed. MLD is based on self-saturating gas/surface chemical reactions allowing building films with molecular scale precision and is strongly innovative in the field of coordination polymer assembling. Thin film structuration is required to envision industry-compatible technological solutions. The functional MOFs considered in this project are metalloporphyrin-based materials that have been recently proven in our group to be interesting materials for electrocatalytic oxygen reduction reaction. Their nano-scale structuration into thin films will allow an unprecedented study of the influence of the film composition and topology on electrochemical properties. To achieve this ambitious goal, a step by step approach is proposed, based on the optimization of the hetero-interface between the MOF and the substrate through lattice matching compounds selection. Reference MOFs will first be tested on suited oxide substrate surfaces to optimize growth parameters. This will pave the way for film growth of redox active porphyrin based networks. In the last step the composition will be tuned along the films layers by controlling the sequence of deposition.

2D materials exhibit promising properties for key European industrial areas including high-speed computing and communication technologies. However, mainly focused on crystalline materials, these applications are currently limited by the lack of direct and reproducible low cost-synthesis methods, due to high temperature growth. Recently, structurally disordered 2D materials, produced at much lower temperatures, have been shown to manifest a large degree of uniformity over large areas, and performant properties for device applications. Amorphous boron nitride (aBN) is found to exhibit ultra-low dielectric-constant, and excellent field emission performance, being suitable for interconnects technologies and high performance electronics, such as flexible dielectric devices or conductive bridging RAM. MINERVA aims to grow aBN thin films over large area on various substrates, and evaluate their properties as coatings for thermal, electronic and spintronic applications. Particular attention will be paid to achieve nanoscale control of the amorphicity, thickness of the films as well as doping rate and substrate interaction. The relationship between processing and atomic structure will be studied by an appropriate combination of analytical techniques. Modelling to understand the structures and properties of the materials will support and validate the experiments at every stage. The expected physical properties of such deposited layers, coupled with the versatility and adaptability in materials processing, as well as the large-area and uniform coverage at low temperature, should allow their integration as electronic components in ultimate nanoelectronic systems. More concretely, the added value of large scale aBN will be studied for resistive switching devices, magnetic tunnel junctions and spin injection tunnel barriers. The possible dependence of aBN electronic properties in contact to ferromagnetic electrodes will be explored in detail, predicting the possible fruitful potential of spin manipulation by proximity effect at the hybridized aBN/ferromagnet interface. This is expected to generate new scientific knowledge of charge and spin transport across novel 2D hybrid junctions. In addition, these newly tuned aBN materials, on which no studies have yet been conducted within the Graphene Flagship, will be added to the Samples and Materials Database as standard references. MINERVA brings together complementary expertises and is characterized by a high level of interaction between partners. UCBL will coordinate MINERVA and synthesize controlled aBN samples. ICN2 and UU will respectively perform measurements of thermal conductivity and charge and spin transport. UCLouvain and ICN2 will simulate spin-dependent transport throughout aBN films and investigate the coupling between aBN electronic properties and ferromagnetic materials. MINERVA will bring new materials and technological devices to the Flagship consortium, thereby supporting its industrial objectives.

WEPRINT aims to develop new biodegradable scaffolds designed at the nanoscale for future medical applications, in particular in dental application regarding this project. The fabrication technology of the present project relies on a combination of a three-dimensional (3D) printer and wet spinning under electric field. Compared to the existing biomaterials and processes, WEPRINT project would lead to the fabrication of new scaffolds presenting more suitable mechanical properties and functionalization for future needs as medical devices. This new generation of biodegradable architectures will be nanostructured and contain a large and adjustable porosity at the microscale in order to facilitate the cell invasion and proliferation. It is thus possible to combine a high surface to volume ratio, a high cell proliferation rate and adequate mechanical properties, with a fast production of 3D biodegradable structures. One of the major interests of this work relies on the insertion of bioactive fillers inside the polymer filaments forming the walls of the scaffold. Three polymers with different resorption times will be used to facilitate and guide the cell invasion and proliferation from the bottom to the upper part of scaffold. At the end of the project, a multiscale hybrid resorbable scaffold will be composed of three types of polymers, each one containing at least one bioactive filler of the following ones: a cell recruiting agent (for cell proliferation) and a growth factor or inorganic nanoparticles (for cell differentiation). The project is divided in four tasks, from setup optimization to biological tests, for duration of 42 months. The stability of the raw solutions as well as the printing conditions will be investigated step by step, as described in the tasks of the project. The final task of the work is dedicated to investigate the scaffold bioactivity, including degradation time, cell cytotoxicity, antibacterial properties and cell differentiation.