Functional Thin Films for Energy Applications group

Thermochromism for thermal regulation and stealth

This topic concerns thermochromism. The thermochromic effect is a phenomenon that occurs when a material is subjected to temperature variations. It results in a change in colour of the material at a temperature called the transition temperature. Several types of thermochromic coatings exist and the team is particularly interested in vanadium dioxide (VO2), as well as some perovskites of the REMO3 type (with RE: rare earth and M: transition metal). This axis has been extended to integrate the new applications on IR stealth initiated. A calculation component using optical indices, thicknesses and simulation of stacks has been initiated to predict the optical properties of layers dedicated to thermal regulation or IR stealth.

Project:

• LabCom SOLARIS

Theses:

• LUE/Viessmann Zil Fernandez (2019-2022)
• LUE Alexis Garcia-Wong (2017-2020)

Articles:

• Thermochromic SmNiO3- thin films deposited by magnetron sputtering and crystallized by a soft-annealing in air, Scripta Materiala 218 (2022) 114795. Z. Fernandez-Gutiérrez et al.
   
• Thermochromic properties of LaCoO3 selective layers for thermal solar collectors, Solar Energy Materials and Solar Cells 240 (2022) 111690. D. Kharkhan et al.
   
• Surface morphology-optical properties relationship in thermochromic VO2 thin films obtained by air oxidation of vanadium nitride, Journal of Materiomics, 7 (2021) 657. A. Garcia-Wong et al.
   
• Oxidation of sputter-deposited vanadium nitride as a new precursor to achieve thermochromic VO2 thin films, Solar Energy Materials and Solar Cells, 201  (2020) 110474. A. Garcia-Wong et al.

Thin films and nanostructures for optoelectronics and adaptive optical properties

Metal nano-objects placed in a dielectric environment can be associated of a significant interaction between the free electrons of the metal and electromagnetic radiation. Indeed, when the electromagnetic radiation is of the same frequency as the natural vibration frequency of the free electrons (plasmon frequency), a resonant coupling is established between the dipole created by the oscillation of the electrons within the nano-object and the dipole of the electromagnetic field. This phenomenon, known as localized surface plasmon resonance, gives rise to novel properties that stimulate numerous studies. The team is working on the nanostructuring of materials for plasmonics or the interfacing of metallic nano-objects with semiconductors and on the study of the optical and electrical properties of such couples. Thus, photodetectors operating by injecting "hot" carriers from metallic nano-objects into semiconductors, films and devices with novel optical emission properties have been produced.

Thanks to the use of dual processes, combining magnetron sputtering and non-equilibrium techniques for nanoparticle synthesis (laser ablation, liquid discharges), the team can synthesise microstructurally complex or even metastable particles, which is very complicated or even impossible by conventional synthesis methods. This approach allows the study of a new field of nano-optics: the effect of microstructure on linear (plasmonics) and non-linear (second harmonic generation) optical responses.

This topic is also extended to adaptive optical properties, allowing the integration of work on the photoemission of nanoparticles (plasmonic effect), reflectivity (nanometric topography), and the non-linear optical properties of high-entropy alloy coatings. High entropy coatings exhibit chemical disorder associated with crystalline order, allowing for non-linear optical properties that we wish to characterize. We are also studying the hybrid coupling of dielectric and plasmonic materials in order to obtain synergetic effects giving rise to particularly interesting optical responses such as IR-white light conversion. Similarly, the study of metastable alloys, obtained by dual processes (sputtering + laser ablation) developed in collaboration with the IJL's 201 team, represents a strong potential for the development of new materials with novel properties such as their dynamic optical response when returning to the equilibrium state.

Theses:

• Cotutelle avec l’Université de la Havane 2019-2023, Yerila Rodriguez
• Ambassade d’Arabie Saoudite 2021-2024, Yahya Ghazwany
• Thèse ministérielle 2020-2023, Adrian Benedit-Cardenas

Articles:

• Tunable Localized Surface Plasmon Resonance and Broadband Visible Photoresponse of Cu Nanoparticles/ZnO Surfaces, ACS Applied Materials and Interfaces, 10 (2018) 40958. C. De Melo et al.
   
• Synergistic Effect of Plasma and Laser Processes in Liquid for Alloyed-Nanoparticle Synthesis, Physical Review Applied 13 (2020) 014021. N. Tarasenka et al.
   
• Plasmonic nanosponges filled with silicon for enhanced white light emission, Nanoscale 12(2) (2020) 1013, E. Larin et al.
   
• Optical and electrical properties of hard (Hf,Nb,Ti,V,Zr)Nx thin films, Vacuum, 193 (2021) 110517. K. von Fieandt et al.
   
• Rapid ellipsometric determination and mapping of alloy stoichiometry with a neural network, Optics Letters 47 (2022) 2117. A.Y. Battie et al.

Nanostructured materials for energy conversion or transfer

Traditional photovoltaic cells are based on silicon or CIGS absorbers, which have to be used with high thicknesses and have high toxicity and low raw material availability. The manufacture of traditional transparent electrodes from tin-doped indium oxide also poses problems of toxicity and raw material supply.

The studies are oriented towards the optimization and synthesis of materials for photovoltaic devices and the realization of innovative devices. The materials synthesized are based on elements that are abundant in the earth's crust: zinc oxide, ZnO, as an n-type semiconductor, or copper oxide, Cu2O, as an absorber and p-type semiconductor, coupled to transparent electrodes made of abundant materials such as aluminium-doped ZnO, AZO, or copper iodide, CuI.

Original architectures allowing the realization of photovoltaic devices or transparent or semi-transparent photodetectors are proposed by coupling PVD methods to atomic layer deposition (ALD). In addition, near-ambient synthesis temperatures are sought in order to achieve devices on organic substrates.

The team is also studying the potential applications of new solar absorbers such as family II-VI nitrides like ZnSnN2, ZnGeN2 or MgSnN2. The current work is a continuation of the ANR-funded OPERA project (partners: IEMN, GEEPS and CEA) which ended in 2021.

Within the framework of a project of the Institut Carnot Energie Environnement Lorraine, the team is collaborating with a group from LMOPS (University de Lorraine, Metz) on the synthesis of all-oxide solar cells using a spray pyrolysis process.

Our activities also relate to the development and preparation of heat transfer fluids which can play a major interest in solar thermal. Nanoparticles such as carbon nanotubes or graphene, possessing a remarkable intrinsic thermal conductivity, are here chemically modified to induce their stable dispersion in solvents such as water or glycol water to develop new nanofluids.

Thesis:

• Co-tutelle avec l’Université de la Havane 2019-2023, Yerila Rodriguez

Post-doctorate:

• Agathe VIRFEU

Projects:

• LUE 2020-2023

Articles:

• Semi-Transparent p‑Cu2O/n-ZnO Nanoscale-Film Heterojunctions for Photodetection and Photovoltaic Applications, ACS Applied Nano Materials, 2 (2019) 4358. C. de Melo et al.
   
• Local structure and point defects-dependent Area-Selective Atomic Layer Deposition Approach for Facile Synthesis of p-Cu₂O/n-ZnO Segmented Nano-junctions, ACS Applied Materials and Interfaces 10 (2018) 3761. C. de Melo et al.
   
• Approaching theoretical band gap of ZnSnN2 films via bias magnetron co-sputtering at room temperature, ACS Applied Electronic Materials, 3 (2021) 3855, A. Virfeu et al.
   
• Binary copper oxides: recent progress in materials and applications as photovoltaic absorbers, Journal of Physics D: Applied Physics, 54 (2021) 263002. Y. Wang, J.F. Pierson – Review paper
   
• A critical review on thermal conductivity enhancement of graphene-based nanofluids, Advances in Colloid and Interface Science, 294 (2021) 102452. M. Pavía et al. – review paper
   
• Theoretical and experimental approaches for the determination of functional properties of MgSnN₂ thin films, Solar Energy Materials and Solar Cells, 244 (2022) 111797, F. Alnjiman et al. https://doi.org/10.1016/j.solmat.2022.111797

Functionalized surfaces and interfaces for living and environment applications

This more recent activity conducted in the FTFEA group embraces the studies on both the matter of antibacterial coatings already started several years ago and on hybrid carbon-inorganic nanomaterials. Chemical modifications of carbon nanomaterials (carbon nanotubes, graphene, nanodiamonds) are one of the pillars for the development of these new materials since they are expected to strongly impact the interface and adhesion between the two types of materials (carbon and inorganic). The developed materials we are interesting in are in particular dedicated to sustainable technologies such as nanoadsorbents and electrocatalysts but also neutron reflectors. We aim at maximizing the interactions at the interface between the functional carbonaceous surface and its environment or at controlling the adhesion forces with a nanostructured inorganic deposit (under the form of thin films or nanoparticles). The resulting synergistic effects induced between the two types of nanomaterials are expected to enhance or create novel properties. These activities perfectly match with the current challenges of research dedicated to the development of new complex nanomaterials with high potential for application in the field of energy and the environment: CO2 capture, water electrolysis and green chemistry etc.

The work on the competitive growth between an amorphous phase and a crystalized phase within films synthesized by sputtering constitutes an original axis of the team. It allows us to envisage a control of the properties linked to the surface topography (optical, antibacterial, tribological, etc.). They will be continued and developed by exploring new chemical systems. The targeted applications are the development of antibacterial surfaces and/or surfaces with controlled optical properties.

Preliminary work undertaken in partnership with team 401 (Nano-bio-materials for life) has made it possible to verify that the growth of thin films on biological or bio-inspired nano-structured surfaces leads to the generation of novel microstructures with high application potential. This approach will be pursued with a particular focus on applications in the photonic/photovoltaic and antibacterial fields.

Similarly, the optical and electrical properties will be studied in the case of carbonaceous films functionalized by nanoparticles (or inorganic thin films).

Theses:

• Ambassade de France (Malaisie), cotutelle Rabita Firdaus 2019-2022
• Bourse ministérielle internationale, cotutelle avec l’Allemagne Quentin Liebgott  2020-2023

Projects:

• PHC Hibiscus 2018-2022
• ANR NERF 2021-2024
• LUE 2020-2023

Articles:

• NiCo2O4 nanostructures loaded onto pencil graphite rod: An advanced composite material for oxygen evolution reaction, International Journal of Hydrogen Energy, 47 (2022) 6650. Z.H. Ibupoto et al.
   
• Progress in adsorption capacity of nanomaterials for carbon dioxide capture: A comparative study. Journal of Cleaner Production, 328 (2021) 129553. R.M. Firdaus et al. – Review paper
   
• Tailor the antibacterial efficiency of copper alloys by oxidation: when to and when not to, Journal of Materials Science, 57 (2022) 3807. J. Luo, A. Ahmed, J.F. Pierson, F. Mücklich.
   
• ZrCuAg thin film metallic glasses: toward biostatic durable advanced surfaces, ACS Applied Materials and Interfaces, 13 (2021) 17062. S. Comby-Dassonneville et al.
   
• Composition-driven transition from amorphous to crystalline films enables bottom-up design of functional surfaces, Applied Surface Science, 538 (2021) 148133. A. Borroto et al.
   
• Growth kinetics and origin of residual stress of two-phase crystalline-amorphous nanostructured films, Journal of Applied Physics, 129 (2021) 145301. A. Borroto et al.

Elaboration

• Preparation of thin and nanostructured films by magnetron sputtering

Characterization

• Structure determination by X-ray diffraction (XRD)
• Analysis of surface morphology by scanning electron microscopy and elemental composition by EDS
• Transmission electron microscopy (TEM) studies of morphology, crystallographic structure (SAED / microdiffraction) and elemental (EDS) and chemical (EELS) compositions at the atomic scale.
• Measurement of optical properties by IR/Visible spectrometry
• Determination of electrical properties at room temperature and at variable temperatures
• Raman spectrometry

Technology transfer

• Market launch with Viessmann Faulquemont SAS of the ThermProtect technology used for the thermal control of Vitosol flat plate solar collectors.

CNRS researchers

• Brigitte VIGOLO

Professors, assistant professors

• Silvère BARRAT
• Stéphanie BRUYERE
• Fabien CAPON
• Alexandre DESFORGES
• Nicolas FRESSENGEAS
• David HORWAT
• Alexandre NOMINE
• Jean-François PIERSON

Tenure tracks

• Valentin MILICHKO

Technical and support staff

• David PILLOUD

PhD students

• Monica AOUN
• Hassan BENAIT
• Salah-Eddine BENRAZZOUQ
• Carlos Ernesto CALVO MOLA
• Killian HENRY
• Miguel PINEIRO SALES
• Pierre-Antoine TOSTIVINT

Post-doctoral researchers

• Zil FERNANDEZ GUTIERREZ

Emeritus

• Elisabeth BAUER-GROSSE