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- Cold plasma processes for thin-film deposition and plasma etching
- Processes coupling plasma and chemistry in solution during and after plasma treatment
- Multi-scale modelling of plasma processes
- Cold plasma diagnostics (OES, Mass Spectrometry, probes)
- Characterisation of thin films and in particular X-ray Photo Electron Spectroscopy (XPS), electronic microscopies (TEM) and X-ray diffraction (XRD)
Bi-Based nanOmaterials for Photocatalysis
From October 2024 to September 2028
Coordinator Laboratory of the project : Institut de Chimie de Clermont-Ferrand, ICCF
Coordinator : Angélique BOUSQUET
IMN coordinator of the project: Mireille RICHARD-PLOUET, DR (équipe PCM)
Partners :
Institut Pascal-Clermont-Ferrand, ICCF
Institut Français du Pétrole Energie Nouvelle, IFPEN
Persons of IMN involved :
Maryline LE GRANVALET (MC UNIV), Nicolas GAUTIER (IE CNRS), Christophe CARDINAUD (DR CNRS), Aurélie GIRARD (MC UNIV), Etienne JANOD (DR CNRS), Bernard HUMBERT (PR UNIV), Jean-Yves MEVELLEC (IR CNRS), Franck PETITGAS (AI UNIV)
Total financing : 511 151,80 € with 171 601,79 € for IMN
Discovering new materials is still the most pivotal topics in production of solar fuels or chemical products from CO2 photoconversion. Bismuth oxyfluorides seem attractive photocatalysts since we can adapt their composition for band engineering. At ICCF, it was demonstrated, that this control is achieved by sputtering a Bismuth target in various Ar/O2/CF4 atmospheres. Moreover, by tuning the reactive gas flow rates, we are able to form in one-pot Bi/ BiOxFy heterojunctions, where the controlled content of Bi leads to enhanced photocatalytic activity. First tests at IFPEN showed that they present a promising photoconversion efficiency and a good selectivity for CO, a solar fuel. To improve these performances, the BiBOP project proposes to use Oblique Angle Deposition (OAD) and “sputtering onto ionic liquid” techniques, compatible with PVD one, to control the nano-hierarchization of these photocatalytic heterojunctions and to investigate its influence on CO2 photo-conversion.
ICCF, which possesses an expertise in reactive sputtering, will be in charge of the Bi-based material nano-structuration by these innovative techniques. The project will also benefit from expertise in materials characterization of IMN, which will perform its advanced local techniques, such as their S/TEM “Nant’Themis”, and will develop in situ analyses, under stimuli. This experimental data will be confronted to simulation of electromagnetic properties, thanks to the IP’s skills. The BiBOP project will also gather a major French actor in catalysis, IFPEN, which will evaluate the CO2 photo-conversion performance of Bi-based nanostructures and bring its knowledge on photo-catalytic phenomena.
Finally, the BiBOP project will use innovative synthesis processes but is mainly focused on the development of new Bi-based functional materials in a characterization / simulation approach and aims to address societal issue about the production of safe and clean energy.
The Plasmas and Thin Films team conducts research on the development of cold plasma processes. The research strategy uses other physico-chemical processes than plasmas alone: sol-gel, chemical desalloying. The activities are structured according to three research themes: etching, the deposition of thin layers and the deposition of nano-objects and nano-materials which are complemented by a transversal modelling theme. The research projects concern a wide range of sectors:
-microelectronics,
-micro- and nano-technology,
-opto-electronics,
-sensors,
-energy,
-coatings and surface treatments.
The detailed study of plasma/surface interaction mechanisms, the development of new plasma processes, the implementation of modelling in support of experimental activity and the optimisation of the synthesis of a material with a given property are at the heart of the team's activities.
The team collaborates with external partners who have the technological means of microfabrication for the integration of materials in a device.
Etching and deposition low pressure plasma reactors used by the team
Cathodic reactive sputtering (PVD)
- 4 reactors (PEPVD) magnetron either DC, RF, IPVD, HiPIMS
- 1 cluster with sas and 2 chambers : 1 PECVD/PVD (ICP + 3 cathodes) + 1 chamber PVD 4 cathodes (3’’) + polarisable and heatable substrate RF (max 800°C)
- 1 reactor with sas and 3 cathodes magnetron 4’’ (site La Chantrerie, Polytech)
- 2 IMN mutualized cathodic sputtering
PECVD
-1 ICP reactor for Plasma enhanced chemical vapour deposition(PECVD), with 3 organo-metallic injection lines and 1 injection system for liquid solution (DLI)
Etching
- 2 ICP reactors chlore, fluor, hydrocarbon, organic precursors
- Plateform Optimist, holder -180°/+1100°C
Advanced Dielectric Nanocomposite thin films processed by hybrid aerosol /Pressure plasma for microelectronic capacitor applications
March 2025 – Sept 2029
Coordinator Laboratory of the project : LAPLACE, Toulouse
IMN Coordinator of the Project: Antoine GOULLET PR UNIV (PCM team)
Persons of IMN involved :
Marie-Paule BESLAND (DR CNRS), Mireille RICHARD (DR CNRS), Nicolas GAUTIER (IE CNRS), Nicolas STEFFANT (IE UNIV), Franck PETITGAS (AI UNIV)
Total Financing: 389,15 k€ with 156,5k€ for IMN
According to the state of the art, the improvement of the dielectric materials performances for microelectronics applications and more particularly for Metal‐Insulator‐Metal (MIM) capacitor requires the development of nanostructured
materials. The main issue is related to the increase of the dielectric permitivity and the breakdown electric field, as well as maintaining a low leakage current. In this
context, the objective of the ADN project is to design and optimize a nanostructured material (nanocomposites and / or multilayers), based on TiO2 and SiO2, to increase the dielectric permitivity while keeping leakage currents low.
In such a way, we will develop and optimize an innovative elaboration process based on a low pressure hydrid plasma method with injection of colloidal solutions
containing TiO2 nanoparticles. This process optimization needs a fine understanding of the plasma/aerosol interactions, leading to the modification of nanoparticle/matrix interface and consequently to the formation of the nanocomposite thin inorganic layer. Following this, we will investigate how the nanostructuration (nanoparticle concentration and dispersion state, interfaces...) influence on dielectric properties.
To reach this goal, multilayers and nanocomposites thin film will be modelled and characterized at macro and nanoscale using techniques derived from atomic force microscopy (AFM). The most efficient nanocomposite films, in term of high dielectric permitivity and low leakage current will be identified. Finally, leveraging the insights gleaned from nanocomposites and multilayer stacks characterization, along with the results from electrical modeling, we will proceed to design and evaluate advanced multilayer structures comprising alternating SiO2 and nanocomposite layers.
Advanced Dielectric Nanocomposite thin films processed by hybrid aerosol /Pressure plasma for microelectronic capacitor applications
Mars 2025 – Sept 2029
Laboratoire coordinateur du projet : LAPLACE, Toulouse
Coordinateur IMN du projet : Antoine GOULLET PR UNIV (équipe PCM)
Personnels IMN impliqués :
Marie_Paule BESLAND (DR CNRS), Mireille RICHARD (DR CNRS), Nicolas GAUTIER (IE CNRS), Nicolas STEFFANT (IE UNIV), Franck PETITGAS (AI UNIV)
Financement total: 389,15 k€ dont 156,5k€ pour l’ IMN
Les capacités Métal‐Isolant‐Métal (MIM) passe par le développement de nouveaux matériaux nanostructurés 2D ou 3D. Le principal verrou réside en l’augmentation de la permitivité diélectrique et du champ de claquage, tout en maintenant un courant de fuite faible.
Dans ce contexte, le projet ADN vise à concevoir et élaborer des couches minces nanostructurées (nanocomposites et multicouches), à base de TiO2 et SiO2. Elles permettront d’augmenter la permitivité diélectrique tout en conservant des courants de fuite faibles. Pour ce faire, nous utiliserons un procédé de fabrication innovant basé sur un procédé plasma hydride à basse pression couplant l’injection de solutions colloïdales de nanoparticules de TiO2 et le dépôt de la couche de SiO2 par dépôt chimique en phase vapeur assisté par plasma (PECVD pour Plasma Enhanced Chemical Vapor Deposition).
L’optimisation de ce procédé passe par la compréhension de l’interaction plasma/aérosol conduisant à la formation de la couche nanocomposite. En parallèle, nous étudierons les propriétés électriques de ces couches et plus particulièrement l’influence de la nanostructuration du matériau nanocomposite (concentration et dispersion des nanoparticules, interfaces, …) sur les propriétés diélectriques. Pour cela, les structures nanocomposites et/ou multicouches seront modélisées et caractérisées à l’échelle macroscopique et nanométrique par des techniques dérivées de la microscopie à force atomique (AFM).
Les couches minces nanocomposites les plus performantes, en termes de permitivité diélectrique élevée et de faible courant de fuite seront identifiées. Enfin, grâce aux informations extraites de la caractérisation électrique des empilements et matériaux nanocomposites, ainsi que des résultats de la modélisation, nous proposerons une architecture innovante multicouches constituée d’une alternance de couches de SiO2 et de nanocomposites. Ce nouveau dispositif sera élaboré et évalué.
Ahmed Rhallabi, Christophe Cardinaud, Aurélie Girard
Guillaume Le Dain [2018-2020]
The ANR SPOT project aims to develop a reactive plasma etching process to pattern the surface of austenitic and martensitic type steel parts down to the submicron scale. The etchings give the structured metal parts reinforced and durable tribological properties, which can be used in severe environments. Candidates for the replacement of parts usually made of more noble non-recyclable material or covered with a hard thin layer (DLC, TiN), they will then ensure economic and ecological gain. In this context, we have developed an etching simulator of steel under ICP Cl2/Ar plasma. The multi-scale approach has the advantage of predicting the spatio-temporal evolution of structures etched through masks as a function of machine parameters. The chemical composition of different types of steel is taken into account in the cellular approach based on the Monte-Carlo method, which studies the etching kinetics under the fluxes of reactive neutral species and energetic ions. The effects of certain parameters, such as the chemical composition of steels and the probability of Cl adsorption, on certain etching properties such as roughness, lateral over-etching, etch rate were highlighted. Analyzes of etched steel surfaces by XPS will allow a better understanding of the interaction mechanisms between the active species from the plasma and the steel surface. This will help to develop a surface model based on the Monte-Carlo probabilistic technique consistent with experimental observations.
Keywords Plasma, Etching, Modelling, Steel, Chlore
Collaborations IGL, C2N, SILSEF
The field of non-volatile memories is currently dominated by Flash memories, the technological limitations of integration will quickly slow down there expansion. Resistive Random Access Memories (ReRAMs) are one of the most promising candidates for the replacement of Flash technology. Since one decade, research on ReRAMs is an emerging field particularly active at international level. In ReRAMs, non volatile data storage is enabled by a reversible electric-pulse-induced resistive switching (RS) between two different resistance states. This phenomenon, observed in several classes of materials, was mostly so far explained by thermal and/or electrochemical effects.
Recently, IMN researchers discovered the existence of a volatile and a non-volatile resistive transition in single crystals of narrow gap Mott insulators AM4Q8 (A = Ga, Ge; M = V, Nb, Ta; Q = S, Se). The results indicate that the mechanism behind the resistive transition is quite original and based on an electronic avalanche, allowing to consider a new class of RRAM memories from AM4Q8 compounds (Patent CNRS- Nantes Univ. 2007). The application interest was investigated through thin film deposition by magnetron sputtering of GaV4S8 compound. The phenomenon of non-volatile resistive and reversible transition induced by electric pulses was validated on GaV4S8 thin layers which exhibit already memory performances superior to those of single crystals. These materials are now considered in the international roadmap for semiconductors (ITRS 2011 AND 2013) as promising candidates to replace flash memory.
Recent significant progresses on understanding the mechanism behind the resistive transition allowed extending this functionality to a whole class of materials: the narrow gap Mott insulators, and in particular the timed honored Mott insulator (V1-xCrx)2O3 (Patent CNRS- Nantes Univ. 2012). The use of thin layers of such materials paves the way to a new class of ReRAMs, the Mott memories.
In the framework of Madec Querré PhD (2012-2016), the deposition of (V1-xCrx)2O3 Mott insulator in thin film has been investigated in close collaboration with ISCR (Institute Of Chemical Sciences of Rennes).
Thin layers of crystalline V2O3 and (V1-xCrx)2O3 are obtained by two methods: pulsed laser ablation of a composite target composite V2O3/Cr2O3 (ISCR) and DC cathodic magnetron co-sputtering in reactive mode (Ar / O2) of vanadium and chromium targets (IMN). Well controlled thin layers are obtained in terms of purity, crystal quality, chromium content and oxygen stoichiometry, which is highly challenging considering the numerous oxidation states of vanadium and the complexity vanadium oxides phase diagram.
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Thin films of V2O3: Cr deposited by laser ablation (ISCR left, 90 nm) and co-sputtering (IMN right, 800 nm).
Contact: This email address is being protected from spambots. You need JavaScript enabled to view it., ';document.getElementById('cloak5dbb69f250a2225d2042610a44c229e3').innerHTML += ''+addy_text5dbb69f250a2225d2042610a44c229e3+'<\/a>'; This email address is being protected from spambots. You need JavaScript enabled to view it., This email address is being protected from spambots. You need JavaScript enabled to view it.
People involved: Marie-Paule Besland, Madec Querré (2012-2016), PMN team: Laurent Cario, Benoit Corraze, Etienne Janod, SATT Ouest Valorisation: Julien Tranchant
Collaboration: Institute of Chemical Sciences of Rennes (ISCR), Rennes.
1 L. Cario et al., Adv. Mater. 22, 5193 (2010); Corraze B. et al., Eur. Phys. J. Special Topics, 222, 1047 (2013); Guiot V., et al. Nat Commun 2013, 4, 1722; Janod E. et al. Adv. Funct. Mater. (2015).
2 L. Cario et al. Patents PCT / EP2008 / 052968, PCT / EP2013 / 057500
3 M.-P. Besland et al. Patent PCT / EP2010 / 053442; Physica Status Solidi. - Rapid Research Letters 5, 53 (2011)
4 International Technological Roadmap for Semiconductors (ITRS). Emerging Research Devices (2011) - http://www.itrs.net/
5 Link to page PMN team http://www.cnrs-imn.fr/index.php/fr/themes-de-recherche-pmn/materiaux -complexes-a-properties-electronic-unconventional / 32-advanced-materials-for-novel-electric-pulse-induced-electronic-properties
