Method for depositing a coating by DLI-MOCVD with direct recycling of the precursor compound

Patent metadata

Field	Value
Publication number	US-11142822-B2
Application number	US-201916669854-A
Country	US
Kind code	B2
Filing date	Oct 31, 2019
Priority date	Dec 18, 2015
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

Process for the chemical vapor deposition by DLI-MOCVD on a substrate of a protective coating composed of at least one protective layer comprising a transition metal M:a) having available, in a feed tank, a mother solution containing a hydrocarbon solvent devoid of oxygen atom and a precursor of bis(arene) type containing the transition metal M to be deposited, and, if appropriate, a carbon-incorporation inhibitor;b) vaporizing said mother solution and introducing it into a CVD reactor in order to carry out the deposition of the protective layer on said substrate;c) collecting, at the outlet of the reactor, a fraction of the gaseous effluent comprising the unconsumed precursor, the aromatic byproducts of the precursor and the solvent, these entities together forming a daughter solution, and;d) 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).

First claim

The invention claimed is:

1. 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 selected from the group consisting of a carbide, an alloy and a metal in native or virtually pure form, 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:
a) having available, in a feed tank, a mother solution containing:
a hydrocarbon solvent devoid of oxygen atom,
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
if appropriate, a carbon-incorporation inhibitor;

b) vaporizing said mother solution in an evaporator and then introducing said vaporized mother solution into a chemical vapor deposition reactor in which said substrate to be covered is found;
c) depositing the protective layer on said substrate in the chamber of the reactor, the atmosphere of which is at a deposition temperature of between 300° C. and 600° C. under reduced deposition pressure, the deposition of the protective layer on said substrate comprising consumption of the precursor which comprises the production of a gaseous effluent comprising aromatic byproducts of the precursor;
d) collecting, at an outlet of the reactor, a fraction of the gaseous effluent comprising the unconsumed precursor, the solvent and the aromatic byproducts of the precursor, the collecting step comprising an operation of selective condensation of said fraction of the gaseous effluent so as to condense the unconsumed precursor, the unconsumed solvent and the aromatic byproducts of the precursor, wherein the unconsumed precursor, the unconsumed solvent and the aromatic byproducts of the precursor together form, under standard conditions, a daughter solution; and
e) 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).

2. Process according to claim 1 , wherein step b) of vaporizing, step c) of reacting and depositing, and step d) 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 133 Pa and 6666 Pa.

3. Process according to claim 1 , wherein the transition metal M is chosen from Cr, Nb, V, W, Mo, Mn or Hf.

4. Process according to claim 3 , wherein the transition metal M is at the zero oxidation state.

5. Process according to claim 3 , wherein the protective material is a base alloy of the transition metal M.

6. Process according to claim 3 , wherein the protective material is the transition metal M in native form, or is a virtually pure composition of a single transition metal M, each of any other chemical element in said protective material being present at a level of less than 0.5 atomic %.

7. Process according to claim 1 , wherein the transition metal M is chromium.

8. Process according to claim 1 , wherein the protective material is a carbide.

9. Process according to claim 8 , wherein the carbide of the transition metal M composing the protective material is of CrC, WC, NbC, MoC, VC or HfC type, or has the stoichiometric Cr 7C 3, Cr 3C 2, Mo 2C, Mn 3C, V 2C or V 4C 3.

10. Process according to claim 1 , wherein the precursor of bis(arene) type is devoid of oxygen atom and has the general formula (Ar)(Ar′)M, where M is the transition metal 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.

11. Process according to claim 10 , wherein the aromatic groups Ar and Ar′ each 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.

12. Process according to claim 1 , wherein the solvent is 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.

13. Process according to claim 1 , wherein said mother solution further contains, as carbon-incorporation inhibitor, 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.

14. Process according to claim 13 , wherein the carbon-incorporation inhibitor is sulfur-comprising.

15. Process according to claim 1 , wherein, in step d), aliphatic byproducts of the precursor and aliphatic byproducts of the solvent which are present in the effluent at the outlet of reactor are not condensed.

16. Process according to claim 1 , wherein step d) of collecting said fraction is followed by a step d1) of determining the concentration of the precursor in the daughter solution obtained, and wherein step e) comprises an operation e0) of adjusting the concentration of the precursor, as a function of the concentration of the precursor of the daughter solution poured into the feed tank.

17. Process according to claim 1 , wherein the concentration of the precursor in the daughter solution is less than the initial concentration of the precursor in the mother solution.

18. Process according to claim 1 , wherein steps a) to d) are repeated sequentially N times and the N daughter solutions are saved, and then step e) 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).

19. Process according to claim 1 , wherein the daughter solution obtained in step d) is poured continuously into the feed tank, during the chemical vapor deposition process.

20. Process according to claim 1 , wherein the protective coating has a mean thickness of between 1 μm and 50 μm.

21. Process according to claim 1 , wherein, in step d), the operation of selective condensation is performed with a cryogenic trap at a temperature ranging between −200° C. and −50° C.

Assignees

• Commissariat Energie Atomique

Inventors

• Schuster Frédéric
• Maury Francis
• Michau Alexandre
• Pons Michel
• Boichot Raphaël
• Lomello Fernando

Classifications

• B01D5/006

  with evaporation or distillation · CPC title

• C23C16/32

  Carbides · CPC title

• C23C16/18

  from metallo-organic compounds · CPC title

• C23C16/4412

  Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps · CPC title

• C23C16/453

  passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD (C23C16/513 takes precedence; for flame or plasma spraying of coating material in the molten state C23C4/00) · CPC title