DUVNANO is a multidisciplinary project that intends to respond to the demand of new simple processes toward functional thin film by proposing a novel approach that combines colloidal nanocrystals solution and Deep-UV (DUV: 266 & 193 nm) photolithography processes. DUVNANO is a PRC project gathering 2 partners highly specialized on colloidal chemistry and DUV photolithography processes respectively: Laboratory for Innovative Key Materials and Structure-LINK (CNRS UMI 3629) and Institut de Science des Matériaux de Mulhouse-IS2M (CNRS UMR7361). In agreement with Axis 2 of Challenge 3, DUVNANO will focus on a wide range of materials in order to develop a new process rather than aiming for a particular application. The control of this new process will be validated through the realization of simple components such as field effect transistors (FET) or optical networks that can find applications in domain such as “smart windows” for instance. The originality of DUVNANO lies in the use of colloidal nanocrystals solutions as negative tone photoresists for direct writing of functional microstructures by DUV photolithography, without any further process step. DUV irradiation has indeed the unique property to allow the crosslinking of nanocrystals (NCs) or nanoparticles (NPs) without any additional thermal treatment. With this process, inorganic micro-nanostructured thin films will be obtained in a single step, at room temperature, by a simple process compatible with flexible substrates. The research in coating material and process suitable for solution route is of great interest for industrial point of view. Indeed, thin films are playing a very important and indispensable role in daily life with a material market value estimated to be around $10 billion by 2018. The project is organized in 4 main tasks: Task 0 will address the project management and will be led by LINK who will cover all administrative and technical management. Task 1 (led by LINK) will be focused on the synthesis and characterization of colloidal solution and thin films based on monodispersed and size-controlled NCs of typical oxides (ZnO, Fe2O3, HfO2…) or metals clusters ( Mo, Ta, Nb, Cu). The synthesis of colloidal solution could be done in aqueous or organic (ethanol, propanol, cyclohexane…). Chemical solution processes (dip and spin-coating, electrophoretic deposition) will be used to address the formation of thin films with good optical quality. Task 2 (led by IS2M) will deal with the DUV photopatterning. Patterning will be achieved by mask lithography, laser direct writing and interference lithography to cover a wide variety of structures and resolutions. The photopatterning will be adapted to the different categories of materials (semi-conductive oxides, dielectric oxides or metal clusters). Basic devices will be produced as described above. Task 3 (co-led by LINK & IS2M) will deal with the physical characterizations (optical, electrical or magneto-optical and magnetic properties). In comparison to previous works (Wang et al, Science 2017), DUVNANO propose to develop a simpler and quicker process for preparing thin films without photoresists. Very recently, IS2M demonstrated the possibility of crosslinking NP synthetized by LINK. This gives the proof of concept of our goal in this project that is to obtain, directly after DUV irradiation, patterned fully inorganic and nanocrystalized materials. The methodology has been thought in order to minimize the risks using the complementary skills and know-how of each partner.

NanoLEtsGOs is a multidisciplinary project aiming at designing original inorganic photoelectrodes built from abundant metal and low-toxic metal cluster (MC)-based nanobuilding blocks. MCs will be used as new light-harvesters to propose innovative, clean and efficient devices for sunlight conversion applications. NanoLEtsGOs will develop all inorganic solar cells reaching photoconversion efficiency above 10% by optimizing the optoelectronic properties of photoactive layers, based on the controlled assembling of MC building blocks, in terms of light absorption and transport properties. NanoLEtsGOs will implement 3 strategies to improve light absorption and transport properties within the photoactive layers: i) the progressive substitution of halogen ligands by sulfur ligands in order to form bridges between MCs, ii) the integration of the MCs into a (semi)conductive polymeric matrix and/or iii) the structuration of the light-harvester layer.

CLIMATE aims at preparing new composite coating materials for glass solar control as well as straightforward processes for their surface coating. The originality of CLIMATE lies in the use of functional cluster-based composite materials as glass coater. The M6@silice-PDMS composite (PDMS = polydimethylsiloxane) will be made by embedding inorganic octahedral clusters (M6 = Nb6, Ta6 for mononuclear clusters, heteronuclear clusters M6 = Nb or Ta associated with 3d or 4d metal atoms) into hybrid silica-PDMS matrix using a sol gel process. The metal atom clusters will be associated with halogen or with both halogen and oxygen. They will combine UV absorption, NIR blocking properties as well as inorganic dye with color ranging from green, green blue to brown-grey colors. The new composites will answer the criteria of Saint Gobain (SG) with dual benefits of (i) optimization of daylighting & energy savings and (ii) aesthetics. Indeed, energy efficient smart glass or plastic transparent materials aims at reducing the energy consumption for houses, cars and greenhouses, leading to a better thermal insulation by controlling near-infrared (NIR) and UV solar radiation without reducing the standard of living. Thus, NIR/UV reflective or absorptive coating materials should be ideally transparent in the visible and only block transmission of NIR/UV light from solar radiation or heat transfer for evident great interest in worldwide challenge of reducing energy consumption. Currently, commercially-available active layers are mainly deposited by vacuum processes, which are expensive. The research in active layered materials suitable for solution route is of great interest for SG. These layers consist in a matrix (organic, inorganic or hybrid) in which are introduced several actives species with NIR and/or UV absorption properties. However, in order to reach good solar control capabilities, large amounts of active particles within the matrix are introduced up to now. Such large amounts induce alterations of mandatory properties for industrial applications. Moreover, the chemistry of each nanoparticle can be very different making trickier the embedding processing. The originality in the use of M6 cluster lies in the flexibility of compositions (metals and ligands) and metal oxidation states that enable to tailor-made functional building blocks with optimized color, UV absorption and NIR blocking properties. Moreover, the nanosized metal clusters reduce drastically the scattering of visible light and increase the transparency that are faced using larger nanoparticles. To reach optimum optical properties, it could be necessary to embed several kind of M6 clusters within the same matrix possessing different optical properties. Note that their chemical behavior will be very similar. Consequently, it will favor straightforward one pot embedding processes. CLIMATE is a PRCE project gathering 3 partners: Institut des Sciences Chimiques de Rennes-UMR 6226 (P1), the Laboratory for Innovative Key Materials and Structure LINK-UMI 3629-SG-CNRS-NIMS (P2) and SG Research Center – Aubervilliers (P3) which is an industrial research and development center working for the subsidiaries of the SG Group. The methodology of this project has been thought in order to minimize the risks thanks to complementarities of partners. As PRCE proposal, SG will beneficiate from the expertise of P1 in chemistry and theoretical rationalizations of clusters and that of P2, specialized in integration and characterization of cluster based thin film nanocomposites. P1 and P2 will beneficiate from the expertise of industrials partner P3 in the optimization of large coating of glass surfaces as well as in technology transfer to industrial scale. CLIMATE is at the frontier between materials development and the underlying material science. It will produce both new fundamental knowledge on composite materials and their processing as well as potential patentable results.

MONICA is a multidisciplinary project focusing on the innovative, environmental and scalable synthesis of doped molybdenum (oxy)nitrides or carbides nanomaterials prepared by the Laser pyrolysis process. Achieving this new approach relies on the complementary expertise of the 3 academic partners (NIMBE, LINK and ISCR) and 1 industrial partner (Nanomakers). The final objective of this study is to evaluate the potential of a one-step reaction by Laser pyrolysis for the large production of doped molybdenum carbides or (oxy)nitrides, noted M:MoyXz/GC (M : Ni, Co, Cu, Fe; X = C, N). For environmental and industrial targets, two different Laser pyrolysis strategies will be used: (i) one using water solvent and commercial soluble molybdenum sources and (ii) another one based on an all solid process. Both strategies will use low-cost environmentally friendly precursors for Laser pyrolysis. In addition, the nanomaterials will be characterized finely and their electrocatalytic performances for water splitting reactions (hydrogen evolution reaction and oxygen evolution reaction) will be carefully studied as proof of concept, with the aim of applying the most promising materials as anode and cathode in an electrolyzer. In comparison to other works, we believe that our method is simpler, more efficient and quicker for preparing nanocomposite electrocatalysts. This project is based on preliminary results of the consortium on molybdenum carbide nanocomposites synthesized by Laser pyrolysis.

This project is focused on thermoelectric materials with potential industrial applications at very high temperature, from 600°C to 1000°C and possibly higher, to harvest waste heat and convert it into usable energy. This particular temperature range targets the steel, non-ferrous, ceramics and glass industries that use a lot of energy, 50% of which being lost during the production process. this project will target the research and development of high temperature stable thermoelectric materials based on the cubic structure Th3P4. In this family of intermetallics, n-type La3Te4-x are already known as good thermoelectric materials with ZT above the unity above 1000°C. This project therefore proposes to develop a p-type counterpart of the same structure type, e.g rare-earth antimonides crystallizing in the anti-Th3P4 structure, making it easier to fabricate p-n thermoelectric couples. However, there is only scarce information about the p-type counterparts, even if a few reports have shown very promising thermoelectric properties and stability at high temperature, for instance a ZT of 0.75 was reported in La0.5Yb3.5Sb3 at 1000°C. These materials, their optimization (using modeling tools) and their implementation within a thermoelectric uni-couple and the subsequent demonstrator tests and qualifications are the focus of this proposal. The materials will be made via mechanical alloying followed by annealing and spark plasma sintering. These particular techniques have already proven that they allow the control of whole process, thus assuring the reproducibility of the obtained thermoelectric properties. With the development of powerful methods to compute the electronic band structure of solids and the increasing complexity of the formulations of advanced thermoelectric materials such as those targeted in this project, quantum chemical calculations based on density functional theory (DFT) will be used for the optimization of thermoelectric material properties. DFT programs embedding the most advanced approximation of the exchange-correlation functionals and taking into account relativistic effects will be employed to calculate the electronic structures required to use band engineering approach for the optimization of the thermoelectric properties of the studied materials. The third step of the project will focus on the making of the TE legs, namely, the active materials contacted on both side by metallic electrodes. This will be achieved using the LINK facilities and equipment and will be fed by the data available on the n type material (La4Te3-x) developed by NASA-JPL. CRISMAT will participate in the making of the metallized legs, metallographic studies will be performed on the different bondings and transport properties will be monitored upon ageing of the assemblies. Finally, the last challenge will be to actually build a thermoelectric converter. In essence, it consists of several unicouples connected electrically in series to form a module. The power delivered by such device obviously depends on the number of unicouples. In order to keep the project realistic and in order to be able to respond quickly to necessary design modification, small demonstrators will be privileged over large units. Besides characterization of the TE modules, these tests would serve to anticipate the applicability of the modules in industrial conditions, and anticipate potential modifications to the original design. The efficiency and durability of the module, will be used to estimate how much energy can be recovered and the economic advantage for an industrial application. Data will serve to identify other potential application domains for the modules, according to industrial process characteristics. The consortium ideally combines the expertise of well know research center, CRISMAT laboratory, IRSN Rennes, NIMS Tsukuba via the UMI LINK, and an end user: St Gobain via the CREE research center and also via its belonging to the LINK UMI