US20190003048A1 - Method for depositing a coating by dli-mocvd with direct recycling of the precursor compound - Google Patents

Method for depositing a coating by dli-mocvd with direct recycling of the precursor compound Download PDF

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US20190003048A1
US20190003048A1 US16/063,405 US201616063405A US2019003048A1 US 20190003048 A1 US20190003048 A1 US 20190003048A1 US 201616063405 A US201616063405 A US 201616063405A US 2019003048 A1 US2019003048 A1 US 2019003048A1
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precursor
deposition
transition metal
process according
reactor
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Frédéric Schuster
Francis Maury
Alexandre MICHAU
Michel Pons
Raphaël BOICHOT
Fernando LOMELLO
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4486—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D8/00—Cold traps; Cold baffles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD

Definitions

  • the present invention belongs to the field of treatments for the protection of structural parts operating under severe conditions against wear, corrosion and/or oxidation at high temperature. It more particularly relates to a process for chemical vapor deposition of coatings on surfaces to be protected.
  • a subject matter of the invention is a process for the deposition by the dry route of metal or ceramic layers under reduced pressure and at low temperature, by direct injection into a reactor of a solution of molecular precursor of a metal to be deposited, the effluent from the reaction being collected in order to feed said process with a recycled solution of precursor.
  • parts made of ceramics, steels or alloys are coated with a layer with a thickness of a few microns composed of a non-oxide ceramic material of carbide, nitride or carbonitride type or of a metal element, alone or alloyed.
  • This coating improves the mechanical properties of these parts, and also their wear and corrosion resistance. It can be produced in a monolithic form or nanostructured form as multilayers of the same or different nature.
  • the coatings based on chromium or on other transition metals with similar properties are widely used for the protection of parts against wear and corrosion.
  • the coatings deposited are even thinner films which contribute the functional property essential to the system.
  • organometallic molecular precursors have been used (process abbreviated in English as “MOCVD” for “Metal Organic CVD”), which are described in more detail below.
  • MOCVD Metal Organic CVD
  • MOCVD Metal Organic CVD
  • This DLI-MOCVD process exhibits the advantage of operating at low temperature and under reduced pressure (or even at atmospheric pressure) but imposes very specific reaction conditions for the deposition of protective layers based on a metal or on a carbide of this metal, having the required characteristics of homogeneity and of robustness.
  • the first path is an optimization of the yield varying the parameters of the DLI-MOCVD process in order to reduce the deposition times.
  • the quality requirements of the coatings are so great and so sensitive to the deposition conditions that the windows for variation in the production parameters are too narrow to reconcile all the constraints.
  • the second path would be to reduce the consumption of the reactants and of the process gases (gases used in the process but which are not involved as reactants, such as a carrier gas). Attempts to modify the reaction conditions in order to reduce the amount of reactants which is injected into the reactor have not, unfortunately, made it possible to obtain the desired coatings. For the above-mentioned reasons, the possibilities of varying the parameters of the process are here again greatly reduced.
  • CVD processes employing a recycling step have already been provided.
  • CVD processes where a graphene/Cu substrate is recycled, the metal also being the catalyst are known (Wang, Y., et al., ACS Nano, 2011, 5(12), pp 9927-9933).
  • the recovery of the precious metals used in electronics (Pt, Ru, Au, and the like) in the effluents, in the form either of metals or of precursors, recycled for subsequent use, after the appropriate chemical treatments, is also known (International, R. 2010; accessible on the site http://www.recyclinginternational.com/recycling-news/3464/research-and-legislation/japan/Japanese-recycling-process-ruthenium-precursors).
  • These technological solutions, which are targeted at lowering the overall cost are very limited and are not applicable in DLI-MOCVD.
  • VOCs Volatile Organic Compounds
  • PAHs Polycyclic Aromatic Hydrocarbons
  • Recycling systems are also used in the bulk production by CVD of polycrystalline silicon for photovoltaic and microelectronic applications.
  • the beneficial effect of the loop recycling on the uniformity in thickness of the polycrystalline silicon films obtained in a tubular reactor by low-pressure CVD using the reactant mixture SiH 4 /H 2 is known.
  • the thickness of the film is all the more uniform as the gases are continually and perfectly stirred, which the recycling contributes to producing (Collingham, M. E., et al., Journal of the Electrochemical Society, 1989, 136(3), pp 787-794).
  • the CVD process uses SiCl 4 and H 2 in large excess, a converter transforming SiCl 4 into HSiCl 3 for more rapid growth of Si. Only 20% of HSiCl 3 is consumed and byproducts are formed (chlorosilanes, HCl, H 2 ). The effluents are collected, separated and stored for another use, while unconsumed HSiCl 3 is recycled in the process (Project, P. P. 2010; Vent Gas Recovery and Recycle Process Technology Package, accessible on the site: www.polyplantproject.com/offgasrecoveryrecycling.html).
  • reaction byproducts are small in number. They are hydrides derived from SiH 4 , halides derived from SiCl 4 or hydrocarbons resulting from CH 4 in the case of the deposition of carbon which are all gaseous at the operating temperature and have the same thermal behavior as the initial precursor. They constitute reactive sources for the deposition which have virtually no effect on the mechanism of growth or on the reaction kinetics.
  • the document WO 2007106462 provides for recycling at least one portion of the effluents produced by an MOCVD deposition process while recommending a step of purification of these effluents which is targeted in particular at separating the unreacted organometallic precursors from the byproducts of the reaction.
  • One of the aims of the invention is thus to avoid or to alleviate one or more of the disadvantages described above, and in particular to reduce, indeed even eliminate, the use, the generation and the discharge of substances harmful to the environment, during the preparation of protective coatings on mechanical parts or other parts.
  • one objective of the invention is to provide an environmentally friendly chemical deposition process, by avoiding as much as possible the production of waste resulting from the chemical deposition reactions rather than investing in their removal.
  • Another objective of the invention is to offer a deposition process which minimizes the industrial constraints and the energy needs, so as to limit the economic and environmental impact of the process.
  • Another objective of the invention is to reuse the compounds formed and/or unconsumed.
  • a subject matter of the invention is a process for the deposition of a protective coating on a substrate according to the DLI-MOCVD technique, in which process some effluents present at the reactor outlet are collected and then recycled in the deposition process without damaging its performance levels or the quality of the deposits.
  • the present invention thus relates to a process for the deposition on a substrate of a protective coating composed of one or more layers, at least one being a protective layer comprising a transition metal M in the form of at least one protective material chosen from a carbide, an alloy or a metal, the deposition process being a process for the chemical vapor deposition of an organometallic compound by direct liquid injection (DLI-MOCVD) which comprises the following steps:
  • said organometallic compound composed of a precursor of bis(arene) type having a decomposition temperature of between 300° C. and 600° C. and comprising the transition metal M, and
  • step a) pouring the daughter solution thus obtained into the feed tank in order to obtain a new mother solution capable of being used in step a).
  • a verb such as “to comprise”, “to incorporate”, “to include”, “to contain”, “composed of”, and its conjugated forms are open terms and thus do not exclude the presence of one or more supplementary elements or steps additional to the initial elements or steps set out after these terms.
  • These open terms are targeted further at a specific embodiment in which only the initial element(s) and/or step(s), with the exclusion of any other, are targeted; in which case, the open term is further targeted at the closed term “to consist of”, “to be constituted of” and its conjugated forms.
  • any alloy is generally a base alloy.
  • “Base alloy” of the metal participating among others in the composition of the protective layer or of the substrate to be covered denotes any alloy based on the metal in which the content of the metal is at least 50% by weight of the metal of the alloy, more particularly more than 90%, indeed even more than 95%.
  • the base metal is more particularly a transition metal M preferably chosen from Cr, Nb, V, W, Mo, Mn or Hf, which forms the corresponding base alloy of the transition metal M.
  • An alloy can also contain other chemical elements (for example at a content of greater than 0.5 atomic %), in particular a second metal element (such as, for example, a second transition metal M), in order to constitute a mixed alloy.
  • a second metal element such as, for example, a second transition metal M
  • the element carbon inserted into an alloy forms a carbide of the alloy which can also be mixed in the presence of a second metal element (for example, a second transition metal M).
  • a second metal element for example, a second transition metal M
  • the deposition process according to the invention essentially comprises deposition steps a) and b) and recycling steps c) and d).
  • the deposition steps are carried out according to the DLI-MOCVD technique.
  • This method is described, for example, in the following documents: “F. Maury, A. Douard, S. Delclos, D. Samelor and C. Tendero; Multilayer chromium based coatings grown by atmospheric pressure direct liquid injection CVD; Surface and Coatings Technology, 204 (2009), 983-987”, “A. Douard and F. Maury; Nanocrystalline chromium-based coatings deposited by DLI-MOCVD under atmospheric pressure from Cr(CO) 6 ; Surface and Coatings Technology, 200 (2006), 6267-6271”, WO 2008009714 and WO 2008009715.
  • the CVD reactor used in the DLI-MOCVD technique is generally a hot-wall reactor conventionally used in this field and operating under reduced pressure.
  • the reactor in its entirety is heated to the temperature required for the deposition, so that the walls, the reactive gas phase circulating in the reactor and thus the atmosphere of the reactor, and the substrate to be covered are at the same temperature.
  • This type of reactor is also known as “isothermal” (or “quasi-isothermal” when several temperature gradients exist).
  • a cold-wall reactor can also be used.
  • the cold-wall reactor only the substrate is heated, with the result that the reaction is carried out only at the heated substrate.
  • the yield of the reactor, determined from the consumption of precursor, is then low, which increases the advantage of a recycling of the reactants.
  • the evaporator is heated to a temperature such that the precursor and its solvent are vaporized, without, however, bringing about decomposition at this stage.
  • the vaporization temperature is generally between the boiling point of the solvent and the decomposition temperature of the precursor (and incidentally of the solvent), typically between 100° C. and 250° C., for example in the vicinity of 150° C., indeed even 200° C.
  • the parameters for injection of the precursor solution are preferably fixed using a computer program. They are adjusted so as to obtain a mist of very fine and numerous droplets, in order to obtain a satisfactory flash evaporation under reduced pressure.
  • the liquid injection thus constitutes a well-controlled source of organometallic precursor, which does not limit the possibilities of optimization of the parameters of the process for deposition of the coating.
  • the vaporized precursor and the vaporized solvent are entrained by a stream of neutral gas (or generally a gas which is chemically inert with regard to the chemical entities present in the CVD reactor) from the evaporator toward the deposition zone of the reactor.
  • the substrate to be covered does or does not rest on a sample holder placed in the reactor.
  • the carrier gas used is preferably preheated at the most to the temperature of the evaporator, in order to obtain effective vaporization.
  • Nitrogen is generally chosen for its low cost but helium, which benefits from a better thermal conductivity, or argon, the protective capacity of which is greater, can also be employed.
  • the transition metal M to be deposited is typically chromium, or any other metal, the chemistry and the metallurgy of which are similar to those of chromium.
  • the transition metal M is furthermore capable of forming a bis(arene) compound.
  • the transition metal M to be deposited can be chosen from Cr, Nb, V, W, Mo, Mn or Hf. More particularly, the transition metal is chosen from Cr, Nb, V or Mo as their carbides are very stable.
  • the deposits produced are generally ceramic coatings (for example of carbide type) or metal coatings (metal or alloy).
  • the transition metal M generally retains its degree of oxidation in the protective coating deposited, as the precursor decomposes thermally without complex reaction, such as, for example, an oxidation/reduction reaction, which generates numerous byproducts.
  • the transition metal M (more particularly chromium) is at the zero oxidation state in the precursor of bis(arene) type and also in the protective material deposited by the process of the invention. This is because, in the specific case of carbides, for example, the latter being insertion carbides, the transition metal M generally retains the zero oxidation state.
  • the mother solution employed in the deposition process of the invention contains a precursor of bis(arene) type containing the transition metal M, a hydrocarbon solvent devoid of oxygen atom and, if appropriate, a carbon-incorporation inhibitor.
  • the precursor organometallic compound is a molecular compound in which a transition metal M, intended to react in order to form a protective coating on the substrate, is complexed with organic ligands which are two arene groups, in order to form a precursor of bis(arene) type. These ligands confer, on the precursor, the desired thermal stability in the chosen temperature range.
  • the protective layer comprises several transition metals M (for example in the case of a mixed carbide or of an alloy)
  • the mother solution comprises a mixture of the precursors of bis(arene) type, each comprising its own transition metal M.
  • the precursor is preferably a sandwich compound of bis(arene) type devoid of oxygen atom, of general formula (Ar)(Ar′)M, where M is the transition metal M at the zero oxidation state (M 0 ) and Ar and Ar′, which are identical or different, each represent an aromatic group of the type of benzene or benzene substituted by at least one alkyl group.
  • the stability of the metal-ligand bond substantially increases with the number of substituents of the benzene ring.
  • a precursor in which Ar and Ar′ represent two low substituted aromatic ligands can be chosen.
  • the aromatic groups Ar and Ar′ each preferably represent a benzene radical or a benzene radical substituted by from 1 to 3 identical or different groups chosen from a methyl, ethyl or isopropyl group.
  • the mother solution could provide the reaction with different precursors without negatively influencing the process.
  • the exact nature of the aromatic ligands of the transition metal M is not critical, provided that these ligands belong to the same chemical family of low substituted monocyclic aromatic compounds.
  • the reintroduction into the reactor of byproducts of the CVD reaction derived from the initial reactants is then possible, this being the case even if the products collected at the reactor outlet have different chemical structures.
  • the purity of the initial mother solution is not a critical point either, which makes it possible to use commercial solutions which can contain up to 10% of derived compounds.
  • the recycled mother solutions which will be used for a subsequent deposition will contain different bis(arene)s as precursors.
  • said mother solution can contain a mixture of several precursors of bis(arene) type comprising the metal M, of different general formulae (Ar)(Ar′)M, in particular of different general formulae (Ar)(Ar′)M 0 .
  • the precursor when the metal is chromium, in particular in the zero oxidation state, can be a sandwich chromium compound, such as bis(benzene)chromium (known as BBC, of formula Cr(C 6 H 6 ) 2 ), bis(ethylbenzene)chromium (known as BEBC, of formula Cr (C 6 H 5 Et) 2 ), bis(methylbenzene)chromium (of formula Cr(C 6 H 5 Me) 2 ) and bis(cumene)chromium (of formula Cr(C 6 H 5 iPr) 2 ), or their mixture.
  • a sandwich chromium compound such as bis(benzene)chromium (known as BBC, of formula Cr(C 6 H 6 ) 2 ), bis(ethylbenzene)chromium (known as BEBC, of formula Cr (C 6 H 5 Et) 2 ), bis(methylbenzene)chromium (of formula Cr(C 6 H 5 Me) 2 ) and bis(cumene)chromium (
  • It can also be an asymmetric derivative of formula (Ar)(Ar′)Cr, where Ar and Ar′ are different; or a mixture of these bis(arene)chromium compounds which can be rich in one of these compounds.
  • These precursors all decompose starting from approximately 300° C.
  • the precursors exhibiting a decomposition temperature of greater than 600° C. are excluded, in order to prevent the decomposition of the solvent, for the reasons explained later.
  • the chemical formulae of the chromium precursors which precede can be transposed to the precursors comprising the transition metal M by replacing the chromium therein with one of the other transition metals M, in particular in the zero oxidation state.
  • the precursor of bis(arene) type comprising the element M 0 can thus be chosen from at least one compound of formula M 0 (C 6 H 6 ) 2 , M 0 (C 6 H 5 Et) 2 , M 0 (C 6 H 5 Me) 2 or M 0 (C 6 H 5 iPr) 2 .
  • the other precursors mentioned by way of example are liquid and can be directly injected without solvent, but it is then more difficult to control the microstructure of the deposits. Their use in solution is thus preferred as this makes possible a wide variation in the concentration of said mother solution, better adjustment of the injection conditions and consequently of the physical properties.
  • the concentration in the mother solution of the precursor of bis(arene) type comprising the transition metal M can be between 0.1 mol.1 ⁇ 1 and 4.4 mol.1 ⁇ 1 (concentration of the pure precursor), generally between 0.1 mol.1 ⁇ 1 and 1 mol.1 ⁇ 1 , typically 0.35 mol.1 ⁇ 1 .
  • the solvent of the precursor compound plays an important role in the satisfactory implementation of the deposition process according to the invention. It preferably meets all of the following chemical and physical criteria:
  • its boiling point is less than the temperature of the evaporator in order to make possible flash evaporation in the evaporator.
  • the standard conditions are atmospheric pressure and a temperature of 25° C.
  • the solvent is preferably a monocyclic aromatic hydrocarbon of general formula C x H y which is liquid under the standard conditions and which has a boiling point of less than 150° C. and a decomposition temperature of greater than 600° C.
  • the solvent advantageously belongs to a chemical family close to that of the ligands of the precursor compound, namely the family of the aromatic hydrocarbons, also known as “arenes”. This is because, during the passage through the reactor, the precursor decomposes thermally, releasing its ligands one after the other. The byproducts of the reaction are thus essentially free arenes which mix all the better with the solvent as they are chemically close to it, indeed even identical to it. For this reason, the compounds collected in the effluent at the reactor outlet (precursor, byproducts of the CVD reaction and solvent) are generally all aromatic hydrocarbons.
  • the solvent is preferably chosen from benzene or benzene substituted by one or more identical or different groups chosen from a methyl, ethyl or isopropyl group.
  • the solvent is benzene, toluene, ethylbenzene, mesitylene (1,3,5-trimethylbenzene) or their mixtures.
  • benzene is excluded due to its high toxicity, among others as known carcinogen.
  • a carbon-incorporation inhibitor is preferably added to the mother solution, for example at a concentration equal to 1% to 10% of the molar concentration in the mother solution of the precursor of bis(arene) type, for example 2%.
  • This additive preferably a chlorine-comprising or sulfur-comprising additive, has the role of preventing or limiting the heterogeneous decomposition of the aromatic ligands of the precursor. This is because, during the dissociation of the metal-ligand bonds, a portion of the hydrocarbon ligands decompose under the catalytic effect of the surface of the substrate and contribute their carbons, which bond with the transition metal to form ceramics of carbide or mixed carbide type. A small amount of carbon can also be deposited with the transition metal M during step b), without, however, forming a carbide, even in the presence of the inhibitor.
  • said mother solution further contains a chlorine-comprising or sulfur-comprising additive, devoid of oxygen atom and with a decomposition temperature of greater than 600° C., in order to obtain the protective material composed of the transition metal M or of the alloy of the transition metal M.
  • this additive is furthermore miscible in the mother solution.
  • the additive is thus preferably a monocyclic aromatic hydrocarbon substituted by a thiol group or at least one chlorine. More preferably, the additive is thiophenol (C 6 H 5 SH) or hexachlorobenzene (C 6 Cl 6 ).
  • the chamber of the reactor is heated to a deposition temperature of between 300° C. and 600° C., in order to decompose the precursor of bis(arene)metal type, without, however, degrading the solvent: this prevents or at the very least limits the production and the deposition of undesirable byproducts in the reactor and on its walls, indeed even on the substrate.
  • the deposition temperature generally does not exceed the temperature beyond which the mechanical strength of the metal substrate declines (for example, a withstand temperature of 550° C.). This precaution prevents possible deformations or phase transformations of the metal substrate.
  • the reactor is placed under reduced pressure in order to carry out the main steps of the deposition, from the vaporizing of the mother solution containing the precursor as far as the extraction of the effluent in step c) of collecting the fraction of the gaseous effluent.
  • the reduced pressure is generally from a few Torr to a few tens of Torr. These are thus moderately reduced pressures from the viewpoint of the pressures of approximately 10 ⁇ 3 Torr to 10 ⁇ 4 Torr of industrial PVD processes which require items of high vacuum equipment.
  • step b) of vaporizing and deposition and step c) of collecting said fraction of the effluent are carried out so that the atmosphere of the chamber of the reactor is at a reduced deposition pressure of between 1 Torr and 50 Torr (i.e., in SI units, between 133 Pa and 6666 Pa) and alternatively between 13 Pa and 7000 Pa.
  • a protective coating composed of the protective material covers the substrate.
  • This protective material can contain one or more transition metals M in the form of a carbide, of an alloy or of a metal.
  • the carbide of the transition metal M composing the protective material is obtained in the absence of carbon-incorporation inhibitor in the mother solution. It can be a carbide of CrC, WC, NbC, MoC, VC or HfC type, or of stoichiometric formula Cr 7 C 3 , Cr 3 C 2 , Mo 2 C, Mn 3 C, V 2 C or V 4 C 3 .
  • CrC denotes generally a chromium carbide, which can also be denoted “CrC x ”: the coefficient x indicates that the carbide does not have exactly the stoichiometry of one of the three stable chromium carbide compounds (Cr 23 C 6 ; Cr 7 C 3 ; Cr 3 C 2 ). Its composition may be close to Cr 7 C 3 but intermediate with that of Cr 3 C 2 .
  • the carbide comprising the transition metal M can also be a carbide of an alloy of the transition metal M, optionally a mixed carbide, as mentioned in the present description.
  • the alloy of the transition metal M composing the protective material is preferably a base alloy of the transition metal M.
  • the alloy of the transition metal M or its base alloy can be any alloy known to a person skilled in the art comprising the transition metal M chosen from Cr, Nb, V, W, Mo, Mn, Hf or their mixtures.
  • it is a chromium-based alloy chosen more particularly from a chromium/vanadium alloy, a chromium/niobium alloy, a chromium/vanadium/niobium alloy or chromium/molybdenum alloy.
  • An alloy of the transition metal M can be obtained by mixing different organometallic precursors in the mother solution: for example, in order to obtain a chromium/vanadium alloy, the mother solution comprises a mixture of a precursor of bis(arene) type comprising chromium and of a precursor of bis(arene) type comprising vanadium, each precursor being, for example, present in the mother solution according to a molar ratio between these two precursors which corresponds to the stoichiometric chromium/vanadium ratio in the corresponding chromium/vanadium alloy.
  • the metal composing the protective material is generally the transition metal M in native form (or virtually pure form) which can preferably be chromium, vanadium, niobium or molybdenum.
  • the protective material comprising the transition metal M can contain manufacturing impurities.
  • the natures and the contents of these impurities are generally the natures and contents typical of the impurities of industrial metal or ceramic materials.
  • the contents of the unavoidable impurities are less than 200 ppm, preferably less than 100 ppm, more preferably still less than 50 ppm.
  • the gases which pass through the reactor are those which were introduced upstream.
  • the gaseous effluent comprises precursor molecules, the solvent (and the chlorine-comprising or sulfur-comprising additive, if appropriate), which have not been consumed or pyrolyzed.
  • the effluent also comprises aromatic byproducts of the precursor, in particular dissociated free ligands originating from the precursor, which are of the same aromatic family as the solvent. They are incorporated in the base solvent, with which they are fully miscible, and then themselves act as solvent.
  • the majority of the compounds at the outlet of the reactor at low temperature are monocyclic aromatic molecules, with a chemical structure similar or identical to that of the initial compounds, which are the precursor or the solvent. It is thus advantageous to save them, namely to collect them during step c). They are gaseous at the reactor outlet as a result of the temperature and pressure conditions, but liquid under the standard conditions. The mixture thus collected forms a solution, known as daughter solution, which can be introduced into the feed tank of the reactor as new mother solution capable of being used in step a) of the coating process.
  • the effluent also comprises compounds derived from the aromatic molecules by thermal fragmentation, and also byproducts of the reaction of the precursor with the substrate.
  • These fragments resulting from the decomposition of C 6 aromatic compounds are essentially light aliphatic hydrocarbons of C 2 to C 4 alkane, alkene or alkyne type.
  • the advantageous entities can be distinguished by their melting point: they can thus be collected in step c) by virtue of a device capable of bringing about their condensation within a predefined temperature interval.
  • the light hydrocarbons although in subsidiary amount, can then be removed.
  • the collecting of said fraction at the outlet of the reactor comprises an operation of selective condensation of the entities present in the effluent at the outlet of the reactor.
  • a suitable device for capturing, by selective condensation, the unconsumed precursor and the unconsumed solvent, and also the aromatic byproducts of the CVD reaction is, for example, a cryogenic trap.
  • This type of trap which can fall as far as the boiling point of liquid nitrogen, consists of a part which forces the gas phase to pass through a pipe which is sufficiently cooled to cause these entities to condense. It can be adjusted within a range of temperatures which is appropriate for condensing and solidifying the gaseous entities to be recycled, preferably between ⁇ 200° C. and ⁇ 50° C. The temperature depends on the cryogenic bath chosen ( ⁇ 100° C. with a supercooled ethanol trap and ⁇ 200° C. approximately with a liquid nitrogen trap), and is adjustable (reference may be made, for example, to the tables of data published in the work “Handbook of Chemistry and Physics, CRC Press”).
  • the selective condensation of the entities present in the effluent is carried out by cryogenic trapping at a temperature of between ⁇ 200° C. and ⁇ 50° C.
  • said condensed fraction is brought back to the standard temperature and pressure conditions, and the entities remaining in the liquid phase, which form a daughter solution, are retained.
  • the gaseous entities are, for their part, removed: this is because, as light and very volatile aliphatic hydrocarbons, they are much less efficiently trapped than the other entities with a cryogenic trap. They are partially removed during the selective condensation. Then, being in the gas state under the standard conditions, they are easily entrained by the vacuum pump equipping the cryogenic trap.
  • the small-sized entities formed during the reaction are not very numerous in amount and in nature. It has been confirmed experimentally that the trapped effluents at the reactor outlet are a mixture a) of unconsumed precursor, b) of solvent of the mother solution which has not been pyrolyzed, and c) of free ligands (with optionally a chlorine-comprising or sulfur-comprising additive). A few organic compounds derived from the decomposition of the ligands may be present in very small amounts.
  • step c) of the process of the invention a daughter solution characterized by an admittedly lower precursor/solvent ratio than that of the mother solution is obtained, but virtually without other organometallic source capable of affecting the deposition mechanism.
  • organometallic compounds such as the precursors of bis(arene) type
  • all the metal originating from the decomposition of the precursor participates in the deposition of the coating, without reacting with compounds formed in the reactor. No new organometallic derivative is thus formed during the reaction.
  • the trapped daughter solution can be reused in a second deposition operation (noncontinuous mode) or in a loop recycling system which can be automated (continuous mode).
  • the daughter solution collected contains the precursor, which can be reused and recycled in the deposition process of invention, this being the case even if the final concentration of the precursor in the daughter solution is lower than its initial concentration in the mother solution.
  • a spectrocolorimetric method followed by comparison with a calibration line, can be used, optionally in the form of an in-line device incorporated in the item of CVD equipment.
  • step c) of collecting said fraction at the outlet of the reactor is thus followed by a step c1) of determination of the concentration of the precursor in the daughter solution obtained.
  • the concentration of precursor in the mother solution can be adjusted, for example in order to modify the rate of deposition of the protective layer according to step b) of the deposition process of the invention.
  • This adjustment in concentration can consist of an addition of pure precursor to the daughter solution, which solution will be introduced in order to reconstitute a mother solution, or of an addition of pure precursor directly to the feed tank in order to supplement the new mother solution.
  • the process according to the invention can comprise, in step d), an operation d0) of adjustment of the concentration of precursor, as a function of the concentration of the daughter solution poured into the feed tank.
  • the daughter solution saved is less concentrated in precursor than was the mother solution initially used, so that the amount of precursor collected is generally insufficient to carry out a new deposition operation.
  • the precursor then has to be trapped (for example by selective condensation) for at least two CVD deposition operations in order to have sufficient daughter solution for a new deposit with a similar thickness to that obtained during the use of the initial mother solution, which is generally of at least 1 ⁇ m in thickness.
  • the daughter solutions generated during different deposition operations can advantageously be saved, in order to accumulate a sufficient amount of precursor to feed the tank of mother solution for a new deposition operation.
  • steps a) to c) of the deposition process according to the invention can be repeated sequentially N times, on conclusion of which the N daughter solutions were saved, and then step d) is carried out by pouring said N daughter solutions into the feed tank in order to obtain a new mother solution capable of being used in step a).
  • steps c) and d) of the deposition process of the invention is thus to minimize the loss of organometallic precursor, which improves the environmental impact and overall decreases the cost of the DLI-MOCVD process.
  • the protective coating can be advantageously constituted of several layers of different compositions or natures, in order to form a heterogeneous multilayer protective coating.
  • This coating is then generally obtained by a process which carries out a sequenced deposition of each monolayer deposited during a cycle of the deposition process.
  • the deposition of each layer can thus be separated by a pause time, for example of between 1 minute and 10 minutes. This pause can be taken advantage of to purge the chemical vapor deposition reactor.
  • the daughter solution obtained in step c) is poured continuously into the feed tank, during the chemical vapor deposition process.
  • Steps c) and d) can be controlled by an automatic system in order to ensure a circulation loop.
  • a device makes it possible to pass from the low-pressure zone at the cryogenic trap up to the pressurized feed tank, by a pressure variation “line”.
  • the recycling is not universally applicable in a CVD deposition process as it is related to the chemical system which is employed. It has been rendered possible in the deposition process of the invention only by virtue of a specific and judicious choice of the molecular precursors which is associated with a deposition of DLI-MOCVD type.
  • the protective coating can have a mean thickness of between 1 ⁇ m and 50 ⁇ m, preferably between 10 ⁇ m and 50 ⁇ m, in order, among others, to promote the protection of the substrate.
  • a monolayer or multilayer (homogeneous or heterogeneous in composition) protective coating can be deposited with the deposition process of the invention.
  • each protective layer can have a thickness of 1 ⁇ m to 50 ⁇ m, more preferably still of 1 ⁇ m to 25 ⁇ m, indeed even of 1 ⁇ m to 15 ⁇ m.
  • at least one protective layer can have a thickness of 10 ⁇ m to 50 ⁇ m.
  • said substrate to be covered can be a part made of metal (namely, generally composed completely or essentially of native metal), of alloy, of ceramic or of silicon.
  • the substrate can also be made of another material which withstands a heat treatment at approximately 550° C.
  • FIG. 1 shows the UV/visible spectra in transmittance of deposit-free quartz slides (Blank) and after treatment at 500° C., 600° C., 750° C. and 800° C. during the injection of toluene alone (without bis(ethylbenzene)chromium precursor).
  • FIG. 2 exhibits the change in the intensity of the absorbance at the wavelength of 500 nm measured on the spectra in transmittance of FIG. 1 as a function of the pyrolysis temperature.
  • FIG. 3 represents a calibration line for BEBC in UV/visible spectrophotometry.
  • FIG. 6 exhibits a comparison of the Energy-Dispersive Spectra (EDS) of the coating obtained with fresh precursor (at the top) and recycled (at the bottom).
  • EDS Energy-Dispersive Spectra
  • FIG. 8 is a diagrammatic view of a DLI-MOCVD device suitable for the implementation of the deposition process of the invention.
  • the specific embodiments of the process of the invention relate to the deposition of coatings based on chromium (chromium carbides or chromium metal) by decomposition of the two precursors BBC or BEBC, in toluene taken as solvent.
  • the thickness of the deposit is typically 5 ⁇ m.
  • a deposit with a thickness of approximately 1.5 ⁇ m is obtained on conclusion of N3.
  • the concentration of BEBC was determined and the yield calculated for N1 and N2 (see Table 1).
  • Tests were carried out by injecting only toluene into the CVD reactor. Quartz slides are placed in the chamber of the CVD reactor on a sample holder and, after each deposition, a UV/visible transmittance spectrum was recorded. Several temperatures of the reactor were tested between 500° C. and 800° C. The spectra obtained are presented in FIG. 1 . The spectrum of a control slide, which has not been subjected to deposition of carbon, is also represented (Blank).
  • the mean transmittance at the wavelength of 500 nm was plotted for the different temperatures of the reactor. Above 600° C., it decreases because the quartz slide turns opaque following the formation of a thin film of carbon. It is justifiable to believe that toluene begins to decompose at this temperature, with an accentuation at 750° C., more marked still toward 800° C., as is shown by FIG. 2 .
  • toluene is an appropriate solvent for depositions for which the temperature does not exceed 600° C.
  • concentration of precursor of the solutions used Numerous techniques exist for determining the concentration of precursor of the solutions used, all more or less reliable and problematic to carry out.
  • concentration of precursor of the mother solution injected initially into the CVD deposition reactor is known.
  • concentration of the recycled daughter solution is to be determined.
  • the concentration of BBC and of BEBC is determined by the change in their absorption band at 315 nm in the UV range, which is monitored by spectrophotometry (Douard, A., in Institut Carnot CIRIMAT. 2006, INP Toulouse).
  • This absorption band corresponds to the M(4e2g) ⁇ L(5e2g) charge-transfer transition, brought about by the chromium-ligand bond of the precursor molecule, which bond will be cleaved in the initial phase of the mechanism of growth of the coating.
  • ⁇ the molar extinction coefficient of the precursor
  • Injection parameters which modify the proportion of injected solution with respect to the flow rate of carrier gas frequency between 1 Hz and 20 Hz; open time between 0.5 ms and 5 ms;
  • Relative amounts of precursor and of solvent concentrations of precursor of 1.0 ⁇ 10 ⁇ 2 mol.1 ⁇ 1 to 5.0 ⁇ 10 ⁇ 1 mol.1 ⁇ 1 .
  • Colorimetric assaying by spectrophotometry has made it possible to measure that the mother solution based on recycled precursor was approximately 60% less concentrated in precursor than the mother solution based on fresh precursor, without impacting the quality of the films deposited.
  • microstructures of the protective coatings obtained from fresh or recycled mother solution are in every respect similar during the observations by Scanning Electron Microscopy (SEM). Each coating is dense, compact and homogeneous in thickness over the entire surface area of the sample, as shown in FIG. 4 .
  • the interface with the Si substrate is well-defined. Furthermore, in top view (see FIG. 5 ), they have the same very smooth appearance without major heterogeneities but with a few surface contamination elements.
  • the maximum thicknesses achieved with the fresh precursor are significantly greater than those with the recycled precursor, because the concentration of the recycled solution was lower. As much precursor is consumed in the reactor, only a small part is recovered using the cryogenic trap.
  • the EDS spectra are also comparable, with slight contamination with oxygen visible in both cases, fresh precursor or recycled precursor.
  • the peaks of the chromium and the carbon have identical intensities, as is shown by the spectra in FIG. 6
  • the C/Cr ratio has the value of 0.43 for Cr 7 C 3 and 0.66 for Cr 3 C 2 .
  • the mean composition observed is thus very close to Cr 7 C 3 .
  • Examples of diffractograms obtained for a deposition starting from fresh and recycled precursor are presented in FIG. 7 .
  • the nanoindentation device is provided with an indenter of Berkovich type (triangular-based pyramid with an angle of 65.27° between the vertical and the height of one of the faces of the pyramid).
  • the measures are carried out in accordance with the rule of the tenth: the indenter drives in by less than one tenth of the thickness of the coating.
  • a measurement cycle is carried out in three steps:
  • the nanoindentation measurements were carried out on samples coated starting from fresh precursor (thickness of 3.5 ⁇ m) and recycled precursor (thickness of 1 ⁇ m).
  • the calculations made by the measurement and analysis software take into account a Poisson coefficient of the coating of 0.2.
  • the measurements of hardnesses and of Young's modulus are presented in Table 2.
  • a device for deposition by DLI-MOCVD which may be suitable for the implementation of the deposition steps a) and b) of the process of the invention is, for example, described in its main characteristics in the document WO 2008009714.
  • the DLI-MOCVD device which can be used for the deposition of the protective coating with the deposition process of the invention according to steps a) to d) comprises mainly a feed tank, an evaporator, an injector, a CVD reactor and a unit for collecting the daughter solution for the purpose of the recycling thereof in the device.
  • This DLI-MOCVD device is described more specifically with reference to FIG. 8 .
  • a pressurized feed tank 1 feeds the injector 2 with mother solution.
  • the injector 2 is generally constituted of a commercial pulsed injection system, for example a diesel automobile injector.
  • the opening and the closing of the injector 2 can be computer-controlled, which makes possible the injection of the mother solution into the evaporator 3 .
  • the evaporator 3 is positioned coaxially above the generally vertical CVD deposition chamber 10 into which it emerges.
  • a carrier gas feed line 4 emerges in the evaporator 3 next to the outlet of the injector 2 .
  • the stream of carrier gas entrains the vaporized mother solution from the evaporator 3 toward the CVD deposition chamber 10 .
  • a baffle 8 stops the possible unvaporized droplets at the outlet of the evaporator 3 and a screen 9 pierced with holes uniformly dispenses the gas stream.
  • This screen 9 makes possible good distribution of the gas stream in the CVD deposition chamber 10 , which contributes to a good surface state of the coatings and a uniformity in thickness being obtained.
  • a slide valve 5 can isolate the evaporator 3 from the remainder of the CVD deposition chamber 10 : the volume thus delimited below the slide valve 5 comprises the CVD reactor proper in which is found the susceptor 13 on which the substrate to be covered is placed.
  • the additional pipe 6 above the slide valve 5 makes possible the arrival of a reactive gas, such as, for example, a carbon-incorporation inhibitor.
  • the additional pipe 7 above the slide valve 5 makes it possible for the evaporator 3 to be pumped out during the cycles of purging or cleaning the latter.
  • the collar 14 on which the connections of the additional pipes 6 and 7 are made, and also the slide valve 5 at the inlet of the CVD reactor, are heated to a temperature close to that of the evaporator 3 .
  • a protective layer is deposited on the substrate starting from the vaporized mother solution in the CVD reactor.
  • an outlet pipe 12 at the outlet of the CVD deposition chamber 10 collects a fraction of the gaseous effluent produced during the reaction.
  • This fraction comprises the unconsumed precursor of bis(arene) type, the aromatic byproducts of the precursor and the solvent, indeed even, if appropriate, the carbon-incorporation inhibitor.
  • the outlet pipe 12 emerges on a selective condensation unit 14 (such as, for example, a cryogenic trap), in which the main undesirable compounds (in particular the light hydrocarbons) of the fraction of the gaseous effluent are removed, in order to produce a daughter solution.
  • a selective condensation unit 14 such as, for example, a cryogenic trap
  • a pipe 15 continuously dispatches the daughter solution thus produced in order to recycle it in the feed tank 1 .
  • a new mother solution is then formed for the purpose of the use thereof in a new cycle of the deposition process of the invention.
  • a backing pump 11 can be used to purge the whole of the DLI-MOCVD device, for example before a new deposition.

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US11634810B2 (en) 2016-09-28 2023-04-25 Commissariat A L'energie Atomique Et Aux Energies Alternatives Process of manufacture a nuclear component with metal substrate by DLI-MOCVD and method against oxidation/hydriding of nuclear component
US11715572B2 (en) 2016-09-28 2023-08-01 Commissariat A L'energie Atomique Et Aux Energies Alternatives Composite nuclear component, DLI-MOCVD method for producing same, and uses for controlling oxidation/hydridation
US12354757B2 (en) 2016-09-28 2025-07-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Composite nuclear component, DLI-MOCVD method for producing same, and uses for controlling oxidation/hydridation
US12437885B2 (en) 2016-09-28 2025-10-07 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nuclear reactor component having a coating of partially metastable chromium
US11976355B2 (en) * 2020-09-29 2024-05-07 Centre National De La Recherche Scientifique Method for manufacturing an environmental barrier

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RU2699126C1 (ru) 2019-09-03
JP6997711B2 (ja) 2022-02-04
US20200123655A1 (en) 2020-04-23
EP3390686B1 (fr) 2019-11-20
JP2019502023A (ja) 2019-01-24
FR3045673B1 (fr) 2020-02-28
US11142822B2 (en) 2021-10-12

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