EP2374168A1 - Procédé de dépôt de films d'oxydes minces sur des surfaces métalliques texturées courbées - Google Patents
Procédé de dépôt de films d'oxydes minces sur des surfaces métalliques texturées courbéesInfo
- Publication number
- EP2374168A1 EP2374168A1 EP09806178A EP09806178A EP2374168A1 EP 2374168 A1 EP2374168 A1 EP 2374168A1 EP 09806178 A EP09806178 A EP 09806178A EP 09806178 A EP09806178 A EP 09806178A EP 2374168 A1 EP2374168 A1 EP 2374168A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide
- substrate
- layer
- metal
- heat treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic material
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0576—Processes for depositing or forming copper oxide superconductor layers characterised by the substrate
- H10N60/0632—Intermediate layers, e.g. for growth control
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- H—ELECTRICITY
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- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0436—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD]
- H10N60/0464—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD] by metalloorganic chemical vapour deposition [MOCVD]
Definitions
- the present invention relates to the field of oxide layers, and in particular to the deposition of thin oxide layers used in electrical, electronic, magnetic, optical or optoelectronic devices.
- the present invention relates to a chemical process for the epitaxy of thin films of oxides on round textured metal substrates of millimeter small diameter, or on corrugated substrates.
- oxide layers which can fulfill different functions therein, for example: optical effect layer (for example transparent, with controlled optical index, antireflective), electrically insulating layer, electrically conductive and transparent layer, diffusion barrier, "active" layer (for example piezoelectric or superconducting layer).
- optical effect layer for example transparent, with controlled optical index, antireflective
- electrically insulating layer for example transparent, with controlled optical index, antireflective
- electrically conductive and transparent layer electrically conductive and transparent layer
- diffusion barrier for example piezoelectric or superconducting layer
- gas phase epitaxy CVD (chemical vapor deposition) techniques, which can be assisted by a plasma, sputtering techniques, possibly in a reactive medium.
- CVD chemical vapor deposition
- Gas phase epitaxy is used for the deposition of extremely thin layers; its rate of deposition is slow, and it generally requires a very high vacuum.
- it makes it possible to deposit an oxide layer with an ordered atomic structure, if the surface of the substrate also has an ordered atomic structure. This may be of interest to obtain certain properties physical or chemical that are related to this ordered structure, such as specific magnetic properties. This is also of interest for the subsequent deposition of other layers on this thin oxide layer, which will have fewer structural defects and fewer holes if the layer on which they are deposited itself has an ordered structure.
- Sputtering techniques allow for a fairly high deposition rate, but this generally leads to layers with a weak structure. They can also lead to the formation of dust; this causes the formation of small holes (pinholes in English) in the deposited thin layers.
- CVD techniques assisted or not by plasma, do not favor the direct formation of ordered layers, although a subsequent heat treatment can improve their structure. These techniques can also lead to the formation of dust and holes.
- all vacuum deposition techniques and / or from a gas phase can be adapted to allow homogeneous deposition on curved substrates, but this complicates the technology; if the substrate is for example a tube, the substrate associated with a translation is typically rotated during the deposition of the thin layer.
- This method has been used in particular to deposit layers of mixed oxide of lanthanum and zirconium (“LZO”) ordered on metal substrates biaxially textured; on these "buffer layers” can be deposited by epitaxy YBaCuO type ceramic superconductors (also called YBCO) with an ordered structure; they avoid in particular the diffusion of atoms of the metal substrate in the superconducting layer, as explained below.
- LZO mixed oxide of lanthanum and zirconium
- YBaCuO type ceramic superconductors also called YBCO
- Biaxially textured metal substrates can be obtained by a specific hardening process followed by a recrystallization annealing; these substrates of generally flat shape are known to those skilled in the art by the acronym RABiTS ("Rolling-Assisted Biaxially Textured Substrates”). They are described, for example, in the article “Deposition of Biaxially-Oriented Metal and Oxide-Buffered Layer-on-Films” by Qing He, D. K. Christen et al. (published in the journal Physica C 275 (1997), pp. 155-161), in the article "Using RABiTS to Fabricate High Temperature Superconducting Wire” by A. Goyal et al.
- biaxially textured metal sheets made of Ni-Fe alloy are also known, used in particular in electrical engineering.
- crystallographic orientation between the grains of the superconductor since these YBaCuO films must have a cristailographic structure as close as possible to that of a single crystal to avoid a decay of the critical current J c .
- Selvamanickam This compound can also be deposited in a non-stoichiometric manner (see US patent application 2008/0039330 (WoIf et al)). It is also possible to use oxides of other rare earths (samarium, gadolinium, dysprosium, erbium, ytterbium) to which are added yttrium and scandium, or several layers of different composition, for example La 2 Zr 2 O 7 / CeO 2 , see US 2007/01977045 (Trithor GmbH) and US 2007/0026247 (UT-Batelle, LLC).
- a single LZO M O D buffer layer is sufficient to ensure structural compatibility between YBaCuO and NiW, and protect the substrate from oxidation during MOCVD deposit of YBaCuO.
- the YBaCuO films grow epitaxially on the LZO and have critical current densities J c close to 1 MA.cm -2 at 77 K with a critical temperature T c of 91 K and a ⁇ 7 C ⁇ 1 K.
- a layer of YBaCuO having a thickness of between 1 ⁇ m and 5 ⁇ m is deposited from a gaseous or liquid phase followed by a heat treatment.
- a layer of a thickness of 100 nm to 200 nm of cerium oxide or lanthanum-zirconium oxide may be deposited prior to the deposition of YBaCuO 1 using the same techniques as those employed for the deposition of YBaCuO.
- this document contains no concrete example for the manufacture of such a product, and does not mention the performance of such devices.
- the patent application US 2008/0119365 Arnaud Allais and Nat Dirk describes a method of manufacturing a superconducting electrical conductor of circular section.
- the method consists in providing a metal support such as a wire, a rope or a tube with a diameter of between 0.5 and 3 mm, and preferably steel.
- a metal layer is then deposited on the metal support, this layer having a thickness of between 1 and 20 nm.
- the deposit is made by PVD, CVD, or CSD (deposit of a chemical solution).
- the film thus deposited is then submitted to a Texturizing treatment so that as far as possible all crystal grains are aligned (the method used for texturing is not specified).
- a buffer layer of La 2 Zr 2 O 7 is then optionally deposited by dipping in a solution of propionic acid in which lanthanum acetylacetonate and zirconia acetylacetonate are dissolved.
- the deposited liquid dries and the material is subjected to a heat treatment at 1000 0 C (the duration of treatment not being specified) to obtain an epitaxial layer of La 2 Zr 2 O 7, on which a layer of YBaCuO is then deposited by epitaxy.
- a first object of the invention is a method of depositing an oxide layer of at least one metal element on a curved surface of a textured metal substrate,
- said metal substrate advantageously being a long substrate of substantially circular or elliptical section, and still more advantageously a tubular substrate, or a corrugated, corrugated or ribbed sheet,
- said substrate being biaxially textured, and advantageously having a cube texture having grains whose direction [001] is perpendicular to the long direction of the substrate, and whose direction [100] is parallel to the long direction of the substrate, said method comprising the following steps :
- a layer of a precursor of at least one oxide of a metal element from an organic solution of at least one precursor, such as the carboxylates (and preferably propionates) of said metal, this solution preferably having a viscosity, measured at the process temperature, of between 1 mPa s and 20 mPa s, and even more preferably between 2 mPa s and 10 mPa s, (2) said oxide precursor layer is allowed to dry, preferably at a temperature of between 60 and 150 ° C., preferably between 80 ° C. and 100 ° C.,
- a heat treatment is carried out to pyrolyze said oxide precursor and to form the oxide, at least a part of said heat treatment being carried out under reducing gas purge, preferably Ar + 5% (vol) H 2 , said reducing gas preferably having a scanning speed greater than 0.005 cm / s, preferably between 0.012 cm / s and 0.1 cm / s, and even more preferably between 0.04 cm / s and 0.08 cm / s .
- the surface can be functionalized before the deposition of the precursor layer by a liquid route, advantageously by a gas phase treatment with an agent comprising sulfur.
- the thickness of the layer deposited in step (1) depends on the extraction rate of the substrate, the viscosity of the solution and the liquid-vapor surface tension.
- the substrate advantageously has a cube texture having grains whose direction [001] is perpendicular to the long direction of the substrate, and whose direction [100] is parallel to the long direction of the substrate, said long direction being typically the direction of rolling, spinning or stretching, if any.
- the heat treatment (step (3)) comprises a so-called pyrolysis phase and a so-called crystallization phase.
- the pyrolysis phase involves a heat treatment of between 150 ° C. and approximately 450 ° C., and preferably not exceeding 350 ° C., which can be carried out at least partly under reduced pressure.
- the duration of the pyrolysis phase is typically between 30 min and 180 min, preferably between 60 min and 150 min, and even more preferably between 60 min and 120 min.
- the crystallization phase involves a heat treatment at a temperature T between about 450 ° C. and about 1100 ° C., preferably between 800 ° C. and 1100 ° C., and preferably between 85 ° C. and 1000 ° C., to form the oxide.
- the crystallization phase is carried out under reducing gas purging, as indicated above.
- the heat treatment comprises a temperature rise rate of between 100 ° C./h and 2000 ° C./h, preferably between 250 ° C./h and 2000 ° C./h and even more preferentially between 500 ° C./h and 2000. ° C / h, followed by a plateau at temperature T for a period of between 1 and 120 minutes, preferably between 10 and 90 minutes, and even more preferably between 20 and 60 minutes, followed by cooling at a speed of between 100 ° C./h and 2000 ° C./h, preferably between 100 ° C./h and 1000 ° C. C / h and even more preferably between 100 ° C / h and 500 ° C / h.
- the pyrolysis phase is carried out at least in part at a reduced pressure.
- the oxide is an oxide that crystallizes in a cubic, tetragonal or orthorhombic structure.
- the mismatch (e) between the equivalent mesh of the substrate (a s ) and the equivalent mesh of the oxide (a O ⁇ ), and calculated according to the formula e
- and expressed in percent, does not exceed 15%, and preferably does not exceed 10%, and even more preferably does not exceed 5%, said parameter a O ⁇ being taken with respect to the cubic mesh parameter a of the oxide, or with respect to its multiples V (2a), 2a, or 2aV (2a),
- two of the three mesh parameters must meet the requirement under (a).
- Said oxide may be an oxide of type A 2 -X B 2 + X ⁇ 7 where A represents one or more metal elements of valence 3 (such as La or a lanthanide, such as Gd, Dy, Lu, Nd, Sa, or Sc, La being preferred) and B represents one or more metal elements of valency 4 (such as Zr, Ti, Sn, Hf, Pb, Ce, Ta, with Zr being preferred), and x is a number between -0.1 and +0.1.
- A represents one or more metal elements of valence 3 (such as La or a lanthanide, such as Gd, Dy, Lu, Nd, Sa, or Sc, La being preferred)
- B represents one or more metal elements of valency 4 (such as Zr, Ti, Sn, Hf, Pb, Ce, Ta, with Zr being preferred)
- x is a number between -0.1 and +0.1.
- Said oxide may be selected from the group consisting of: YSZ (yttrium stabilized zirconium oxide), Gd 2 Zr 2 O 7 , Sm 2 Zr 2 O 7 , Y 2 O 3 , LaAlO 3 , La 2 Zr 2 O 7 (also called LZO, in which possibly part of La is substituted by Gd), Gd 2 O 3 , CeO 2 , Sm 2 O 3 , La 07 Sr 03 MnO 3 (also called LSMO), SrTiO 3 , La 2 Mo 2 O 9 (also called LMO), BaTiO 3 , LaMnO 3 .
- a plurality of oxide layers are deposited one on the other, these layers possibly having the same or different chemical composition.
- the method according to the invention may further comprise a silicon deposition step above the oxide layer after the end of the crystallization phase.
- the method according to the invention may further comprise a step of depositing a superconducting oxide of the "TRBaCuO" or "YBaCuO” type above the oxide layer, knowing that these expressions "TRBaCuO” or “YBaCuO” do not do not correspond to a stoichiometry between the named elements, and TR means one or more rare earth elements.
- FIGS. 1 to 5 relate to the present invention.
- FIG. 1 shows microscopic images of the surface of a substrate coated with an LZO layer according to the invention.
- the length of the bar is 10 ⁇ m.
- Figure 2 shows a pattern of textured tube used as a substrate in the process according to the invention.
- the texture axes are indicated: the axis parallel to the long direction of the tube, and a radial axis to the tube (i.e. perpendicular to the long direction of the tube).
- FIG. 3 shows a curve of the electrical resistance as a function of temperature for a YBaCuO type superconductor deposited on a LZO type buffer layer deposited according to the method of the invention.
- the horizontal axis is graduated in Kelvin, the vertical axis in Ohm.
- FIG. 4 shows a differential suction tube used for the heat treatment of the deposited layer according to one embodiment of the invention.
- the arrows indicate a direction of gas flow.
- Figure 5 shows the shape of a curved, biaxially textured substrate. This substrate has a "curled” or “ribbed” shape.
- the present invention relates to a process for producing an oxide layer of at least one metal element on a substrate having at least one curved surface, by a process for depositing a precursor in the liquid phase, followed by the decomposition of said precursor, typically thermally, and a heat treatment of crystallization of the oxide layer.
- the method comprises, in the order indicated, the following steps:
- a metal substrate having at least one curved surface said substrate being typically a long substrate of substantially circular or elliptical section, and advantageously a tubular substrate, or a corrugated, corrugated or ribbed sheet, and said substrate being textured biaxially, and advantageously has a cube texture having grains whose direction [001] is perpendicular to the long direction of the substrate, and whose direction [100] is parallel to the long direction of the substrate, said long direction typically being the direction of rolling, spinning or drawing;
- a functionalization treatment is carried out on at least a portion of the surface of said metal substrate, preferably by H 2 S treatment;
- step (iii) depositing an epitaxial oxide layer of at least one metal element at least over a portion of the surface, this surface possibly comprising the functionalized part of said surface, from a liquid solution; said method being characterized in that: in step (iii),
- said precursor layer is allowed to dry, preferably at a temperature between 60 and 150 ° C., and preferably between 80 ° C. and 100 ° C.,
- a heat treatment is carried out at a temperature T between 800 ° C. and 1100 ° C., and preferably between 850 ° C. and 1000 ° C., to form the oxide, this heat treatment being carried out: - with a speed of temperature rise between 1OO c C / h and 2000 ° C / h, preferably between 250 ° C / h and 2000 ° C / hr and even more preferably between 500 ° C / h and 2000 ° C / h, followed by a plateau at temperature T for a period of between 1 and 120 minutes, preferably between 10 and 90 minutes, and even more preferably between 20 and 60 minutes, and followed by cooling at a speed of between 100 and 100.degree.
- ° C / h and 2000 c C / h preferably between 100 ° C / h and 1000 ° C / h and even more preferably between 100 ° C / h and 500 ° C / h; under a reduction gas purge, preferably Ar + 5% (vol) H 2 ), said reducing gas preferably having a scanning speed greater than 0.005 cm / s, preferably between 0.012 cm / s and 0.1 cm / sec s, and even more preferably between 0.04 cm / s and 0.08 cm / s.
- a functionalization treatment of the metal substrate is advantageously carried out by a process comprising the steps of: vacuum treatment (a vacuum of about 10 -3 bar is suitable) with a speed of temperature rise of 800 ° C / h, with a plateau at 600 c C for a period of at least 1 minute and preferably between 10 and 60 minutes (preferably for about 30 minutes), followed by cooling to at room temperature, - functionalization treatment, preferably by scanning inert gas (Ar) with 0.1% (vol) H 2 S at ambient temperature and at a pressure of between 10 -3 bar and 10 bar, preferably at atmospheric pressure, for a period of at least 1 minute, and advantageously of about 30 minutes, - treatment under inert gas flushing Ar + 5% (vol) H 2 with a temperature rise rate of 800 ° C. / h, with a bearing at 85O 0 C for 30 minutes, followed by cooling to room temperature.
- vacuum treatment a vacuum of about 10 -3 bar is suitable
- a speed of temperature rise of 800 ° C / h
- the method according to the invention can be applied to metal substrates biaxially textured.
- it may be for example substrates of substantially circular or elliptical cross section, and in particular tubes, or corrugated substrates or ribs, or any other shape having a curved surface.
- These substrates must be of a metal that crystallizes in a CFC (face-centered cubic) type structure and must have a ⁇ 100 ⁇ ⁇ 100> cube texture.
- They may be for example nickel, or any other alloy of CFC structure and close mesh parameter: nickel - iron, nickel - tungsten, nickel - copper.
- biaxially textured sheets made of Ni-W alloy, sold for example by the company Imphy-ArcelorMittal Stainless & Nickel Alloys, can be used. They can be shaped easily, for example to give tubular, grooved, corrugated or ribbed shapes; Figure 5 shows an example of ribbed sheet used as a substrate in the context of the present invention.
- tubular substrates which are suitable for the embodiment of the invention are manufactured by a method of welding edges in which a flat ribbon (also called flat band) is formed around a metal core disposed in its long axis split tube, the two parallel edges are then welded against each other over their entire length by a type of welding MIG or TIG. Laser welding is also possible; it does not pose any risk of pollution if it proceeds without filler metal. This tube is then stretched to reduce its diameter until the core is in contact with the entire inner wall of the tube. Other methods may be suitable for obtaining these textured substrates of substantially circular or elliptical section.
- the metal substrate Prior to the functionalization of the substrate for the deposition of the oxide layer, the metal substrate must be degreased.
- this is done in two stages: first with acetone (preferably in a bath subjected to ultrasound), then with the aid of an alcohol, such as methanol, ethanol, butanols or hexanols (methanol being preferred because its evaporation leaves no trace).
- an alcohol such as methanol, ethanol, butanols or hexanols (methanol being preferred because its evaporation leaves no trace).
- Functionalization of the substrate In some cases, it is advantageous to functionalize the substrate prior to depositing the metal-organic precursor of the oxide layer.
- Functionalization of the metal substrate has two objectives: a first object is to provide an adaptation layer for the binding of the oxide to the metal: it is to create crystallographic sites on the metal that can bind to those oxide. Thus a layer is obtained which reproduces the atomic structure of the substrate (i.e. epitaxy).
- Functionalization also aims to create a chemically stable surface, because this surface will necessarily be exposed to ambient pressure when the substrate is soaked in the solution to deposit the precursor layer.
- this step is essential to allow a chemical bond of the atoms of the oxide to those of the metal. This is particularly the case when it is desired to create an LZO type oxide layer which acts as a buffer layer for the subsequent deposition of a YBaCuO-type ceramic.
- the functionalization of the substrate is preferably carried out by a surface treatment, consisting of a deposit of one or more monolayers of sulfur.
- Sulfur is known to form an ordered chemisorbed layer on metals with a CFC (face-centered cubic) crystallographic structure generally used as substrates.
- This sulfur layer may be obtained by a suitable heat treatment, and advantageously by a process comprising the steps of: vacuum treatment (a primary vacuum, ie of the order of 10 -3 bar, is sufficient) with a rate of rise to temperature between 600 ° C / h and 1000 ° C / hr (preferably about 800 ° C / h), followed by a plateau at a temperature of between 550 c C and 650 0 C (preferably at about 600 0 C) for about 30 minutes, then cooling to room temperature, inert gas (Ar) sweep with about 0.1% (vol) H 2 S at room temperature for about 30 minutes, at atmospheric pressure;
- vacuum treatment a primary vacuum, ie of the order of 10 -3 bar, is sufficient
- a rate of rise to temperature between 600 ° C / h and 1000 ° C / hr preferably about 800 ° C / h
- a plateau at a temperature of between 550 c C and 650 0 C (preferably at about 600 0 C) for
- the control of this layer can be done by surface analysis techniques known to those skilled in the art for this purpose, such as Auger, RHEED.
- Auger RHEED
- the sulfurization treatment by ultraviolet application of a monolayer of sulfur is suggested in the article "RHEED Studies of Epitaxial Oxide Seed-Layer Growth on RABiTS Ni (OOI): The RoIe of Surface Structure and Chemistry", by C. Cantoni et al., (available on the internet server [cond-mat.supr.con], arXiv: cond-mat / 0106254v1).
- a process for deposition of sulfur on the substrate before deposition of the atmospheric pressure YBaCuO layer is also described in the patent applications of American Superconductor Corp., US 2007/0197395 (but in this document, a metal or oxidic buffer layer other than LZO is deposited on top of this sulfur layer, before deposition of the YBaCuO layer) and US 2007/0179063.
- a sulfur compound such as an organic sulfide
- carbon may interfere with surface functionalization.
- the surface can also be treated with sulfur vapors, but it is difficult to determine. Given the availability and simplicity of the H 2 S molecule, this treatment is preferred.
- the surface can also be functionalized by the creation of an oxygen monolayer, or by adsorption of a controlled quantity of water vapor.
- the result of the functionalization process is an air stable functionalization layer for the time necessary to transfer the substrate into the epitaxial liquid phase.
- the metal substrate contains sulfur
- the surface layer which is formed by segregation following certain heat treatments of the metal, which then take the place of functionalization treatment.
- the segregation taking place during cooling is the cooling that must be carefully controlled.
- texturizing annealing may thus include functionalization annealing.
- (Ni) Deposition of the precursor layer and formation of the oxide layer First, a precursor layer is deposited by a liquid route and then a heat treatment is carried out to form the oxide layer.
- An oxide layer of good quality reproduces the texture of the substrate on the one hand and on the other hand constitutes an effective barrier to the diffusion of the atoms of the biaxially textured metal substrate.
- the oxide layer formed in the context of the present invention must have a crystallographic structure compatible with that of the biaxially textured metal substrate.
- the following oxides can be deposited on a substrate of
- YSZ yttrium stabilized zirconium oxide
- Gd 2 Zr 2 O 7 Sm 2 Zr 2 O 7 , Y 2 O 3 , LaAlO 3 , La 2 Zr 2 O 7 , Gd 2 O 3 , CeO 2 , Sm 2 O 3, La 07 Sr 03 MnO 3 (referred to as LSMO), SrTiO 3, La 2 Mo 2 O 9 (called LMO) 1 BaTiO 3, LaMnO 3.
- the oxide layer formed in the context of the present invention may be an oxide of type A 2 .
- X B 2 + X O 7 where A represents one or more metal elements of valence 3 (such as La or a lanthanide, such as Gd, Dy, Lu, Nd, Sa, or Sc, with La being preferred) and B represents one or more metal elements of valency 4 (such as Zr, Ti, Sn, Hf, Pb, Ce, Ta, Zr being preferred), such as La 2 Zr 2 O 7 , and x is a number between -0.1 and +0.1.
- LZO La 2 Zr 2 O 7
- oxides of an even more complex formula for example with three different metallic elements, or non-stoichiometric oxides, but always provided that their crystallographic structure is compatible with that of the biaxially textured metal substrate.
- a second thin oxide layer of identical or different composition over a first thin oxide layer.
- a second layer of GZO may be deposited on a first LZO layer.
- Ni5W / LZO / YBaCuO / protection (Ag) deposited on a flat substrate makes it possible to pass about 1 MA / cm 2 at 77 ° K while the solutions of the state of the art propose up to 10 buffer layers to achieve the same result.
- the method according to the invention makes it possible in particular to use a single type of buffer layer, and therefore it is simpler than the known methods.
- the method according to the invention makes it possible to deposit such a layer on a curved substrate, for example on a tube, so as to subsequently obtain a superconducting layer at the temperature of the liquid nitrogen, which does not seem be possible with the methods according to the state of the art.
- obtaining an oxide layer of good quality involves multiple factors.
- the decomposition of the precursor must give an oxide.
- carboxylates in which the cation is coordinated to oxygen. They therefore allow the formation of oxides, even under reducing conditions avoiding oxidation of the substrate metal.
- the advantage of the carboxylates is their stability with respect to the humidity of the atmosphere.
- the precursor is deposited by liquid, and in particular by dipping.
- propionates are preferred.
- they are commercially available for many metal elements, or can be prepared quite easily.
- LaZr (prop) 7 is preferably prepared by etching in propionic acid La (acac) 3 x 3 H 2 O and Zr (acac) 4 (where "acac” refers to acetylacetonate) separately, heating slightly (typically to about 60 c C) without evaporating a significant amount of propionic acid.
- the maximum concentration of LaZr (prop) 7 usable appears to be 0.9 mol / l.
- the carboxylates are advantageously used, and even more preferably the propionates of metals A and B.
- gadolinium propionate is advantageously used.
- the viscosity ⁇ of the solution is a very important parameter because it conditions the thickness deposited after soaking.
- the viscosity of metal carboxylate solutions for example that of LZO propionate solutions (LaZr (prop) 7), in an acid, such as propionic acid, depends on the concentration of the solution. It is known (see, for example, Knoth et al., Sup Sci.Technol 18 (2005), pp. 334-339) that the viscosity of a solution of 0.05 mol / l of LaZr (prop) 7 in the propionic acid, is 1.5 mPas, 2.5 for 0.15 mol / l, and 6.5 mPas for a concentration of 0.3 mol / l.
- the thickness of precursor solution deposited after quenching d is given by the Landau - Levich equation: where ⁇ is the liquid-vapor surface tension, p the liquid density and v the withdrawal rate out of the bath, and a is a numerical parameter which is about 0.94.
- Adjuvants such as plurifunctionalized compounds selected for example from polyamines, polyamides, polyethers, amino alcohols, or true polymers, for example polymethyl methacrylate (PMMA), polyethylene glycol (PEG) 1 alcohol
- PMMA polymethyl methacrylate
- PEG polyethylene glycol
- PVA polyvinyl
- the thickness of the precursor deposit also depends on the temperature of the bath.
- the elevation of the temperature by a few degrees can change by several tens of% the final thickness of oxide obtained after heat treatment. It is preferred not to exceed 40 ° C., and even more preferably not to exceed 30 ° C. Above 40 ° C., the composition of the solution is modified due to the evaporation of solvent (typically propionic acid if uses propionates). Too low a bath temperature is likely to lead to the beginning of crystallization of one of the species present in the bath. Therefore, a temperature of between 20 ° C. and 30 ° C. is preferred.
- the viscosity of the precursor solution at the temperature of the process is preferably between 1 mPa s and 20 mPa s, and even more preferably between 2 mPa s and 10 mPa s.
- This measurement is carried out conventionally by a ball viscometer.
- the method according to the invention involves a curved surface substrate, for example of cylindrical shape, such as a tube. The deposit is done by dipping. When the substrate is removed from the liquid, it flows out but a film remains deposited, the thickness of which is governed by the law written above.
- the cylindrical geometry of the substrate modifies the flows with respect to the planar geometry, in particular because of the different edge effects.
- the precursor layer deposited by the liquid route is dried, preferably at a temperature between 60 ° C. and 150 ° C., and preferably between 80 ° C. and 100 ° C., advantageously by infra-red heating. .
- This drying leads to the at least partial polymerization of the layer, attested by the fact that the precursor becomes rigid and only partially soluble in the usual solvents.
- this layer is also dried by a stream of hot neutral gas (argon or nitrogen, for example), preferably at a temperature of between 80 ° C. and 100 ° C.
- the quenching and drying / polymerization steps are done in a controlled atmosphere. This implies, on the one hand, the protection against dust that would make "straws" in the film. This also implies a careful control of the moisture content, so that the process is reproducible. A relative humidity of 20% is suitable. A lower rate may also be appropriate.
- the thickness will be chosen according to the intended application. It depends on the extraction rate, the viscosity and the liquid vapor surface tension.
- the optimum thickness range of LZO considering the properties of the superconductor which then covers it, is between 30 nm and 250 nm.
- the inventors have been able to deposit on curved surfaces, and in particular on tubes with a diameter of a few millimeters, up to 250 nm of LZO, in several successive depositions, without cracks and with correct textural qualities, although these layers are not always crystallized on the surface as required.
- a buffer layer whose density, but also the thickness, is high, within the limits indicated above.
- the inventors have found that the properties of the superconductive layer TRBaCuO or YBaCuO are better for the thicker LZO thicknesses.
- One explanation could be that the surface defects of the substrate are further masked with thick buffer layers.
- a thickness of between 60 nm and 250 nm is preferred, and even more preferably between 80 nm and 250 nm.
- the method according to the invention makes it possible to deposit a thickness of between 30 nm and about 120 nm in one go, without formation of cracks.
- a typical thickness deposited at one time is 80 nm.
- the deposition of several layers one on the other, these layers being of identical composition gives a better densification of the buffer layer obtained.
- the deposited layer in a single deposit or in several successive deposits, is bi-axially textured.
- the thickness of the deposited layer depends on the rate with which the substrate is extracted from the liquid. This rate is advantageously between 1 mm / min and 100 mm / min, and is preferably at least 10 mm / min.
- the process according to the invention differs from the flat substrate processes by the texture of the substrate.
- the texture In flat ribbons, the texture is three-dimensional and has two preferred orthogonal directions. This means that the grains are oriented relative to each other in the plane and perpendicular to the plane. If we roll this tape to make a tube, we will mechanically introduce radial disorientations between grains, and create surface stresses. The average radial disorientation between grains can be calculated if the number of grains is known over 360 °.
- a substrate in the form of a tube typically has a mean grain size of 50 ⁇ m, observed over an area with a diameter of 2 mm, which leads to a average radial disorientation between grain about 3 °; this is acceptable.
- Such a substrate has a bidirectional texture with a radial axis and an axial axis.
- Its oxide layer typically has a grain size between 50 nm and 80 nm.
- This step is particularly critical for the process according to the invention.
- the residual solvents can be evaporated under primary vacuum, and the oxide precursor is converted to oxide, typically by pyrolysis.
- a crystallization treatment is carried out: the film is brought to a temperature of between 850 and 1100 ° C. with a rate of rise in temperature of between 100 and 2000 ° C./h under a reduction gas sweep, preferably a mixture argon containing 5 vol-% H 2 .
- a reduction gas sweep preferably a mixture argon containing 5 vol-% H 2 .
- the use of such a gas avoids the oxidation of the substrate. It can be useful to carry out a bearing at high temperature.
- the gas flow and flow rate, the rate of rise in temperature and the treatment temperature are essential parameters of the heat treatment phase.
- the gas velocity must be as high as possible, without the risk of cooling the sample, and it conditions the progress of the pyrolysis of the precursors, in particular the advancement of the pyrolysis front, and the advancement of the crystallization front of the textured part. in the movie.
- the temperature of the heat treatment is advantageously between 800 ° C. and
- the recrystallization temperature is advantageously close to 1100 ° C. Too high a temperature, and a treatment too long at high temperature, can promote the interdiffusion between the metal substrate and the buffer layer. In particular, the tungsten of the nickel-tungsten substrate can diffuse into the buffer layer, and the lanthanum of the buffer layer can diffuse into the metal substrate. There may also be reactions to the interface.
- the optimum crystallization temperature depends slightly on the metal element composition of the layer.
- the values given above are optimal for the LZO. Gd doping may induce a slight drop in this temperature.
- the heat treatment is advantageously carried out with a temperature rise rate of between 100 ° C./h and 2000 ° C./h, preferably between 250 ° C./h and 2000 ° C./h and even more preferentially.
- the heat treatment can be carried out in two parts or phases distinguished by their temperature range: a first part or so-called pyrolysis phase, ranging from about 150 ° C. to about 450 ° C., and preferably not exceeding 350 0 C, and a second part or so-called phase of crystallization, ranging from about 450 ° C to about 1000 0 C or 1100 ° C.
- the rates of rise in temperature within these two regimes may be different, for example slow in the pyrolysis phase and fast in the crystallization phase.
- the heat treatment involves a passage under vacuum in the pyrolysis field, preferably of a duration of between 30 min and 180 min, and more preferably between 60 min and 120 min. At the end of the pyrolysis phase, it is allowed to cool to room temperature, or the heat treatment can be continued by increasing the temperature to reach the crystallization phase.
- the heat treatment during the crystallization phase must be carried out under reducing gas purge, preferably Ar + 5% (vol) H 2 ), said reducing gas preferably having a scanning speed greater than 0.005 cm / s, preferably between 0.012 cm / s and 0.1 cm / s, and even more preferably between 0.04 cm / s and 0.08 cm / s. It is also possible to use a mixture of N 2 + H 2 (typically 5% by volume H 2 ) which is less expensive than an Ar + H 2 mixture.
- this gas sweep is performed by injecting the preheated gas against the current in a so-called differential suction tube, which is shown schematically in FIG. 4. It comprises a heating wall (7). ) and perforated inner walls (3) which delimit an interior space (2) and an outer space (1).
- the product to be treated (6) is in the interior space (2).
- the gas enters (4) into the tube, entrains the gaseous products of the pyrolysis reaction and is extracted outside the tube by suction (4) through the perforated walls
- the gas sweep may also be applied during the pyrolysis phase, if one does not choose to carry out the pyrolysis, as indicated above, under vacuum.
- the pyrolysis phase is carried out at 350 ° C. under primary vacuum for 1 hour (minimum 30 minutes), in order to eliminate the residues of propionic acid, and the crystallization phase is carried out under a purge.
- argon / H 2 as described above.
- the decomposition of the oxide precursor can also, at least partially, be carried out by means other than heat.
- the epitaxial portion that starts from the interface by heterogeneous nucleation on the substrate must extend to the surface to allow epitaxial uptake for the subsequent deposition of other layers, for example a layer of TRBaCuO, YBaCuO or silicon, good quality.
- the properties of chemically obtained oxide films mean that nucleation can also occur by nucleation in the homogeneous phase, the seeds then germinating in random directions and creating a non-epitaxial surface part. It is essential to avoid this nucleation in homogeneous phase so that the film is texture throughout its thickness, to the surface.
- nucleation is by epitaxy on the grains of the metal substrate, resulting in an epitaxial layer of excellent quality, that is to say crystallized, textured in surface and dense, which allows to deposit then layers of oxide, for example TRBaCuO or YBaCuO, of very good quality.
- oxide for example TRBaCuO or YBaCuO
- the oxide layer for example the LZO layer
- the subsequently deposited layers such as at the TRBaCuO, YBaCuO or silicon layer
- the subsequently deposited layers such as at the TRBaCuO, YBaCuO or silicon layer
- the subsequently deposited layers such as at the TRBaCuO, YBaCuO or silicon layer
- the process according to the invention is particularly advantageous compared with known methods.
- the process according to the invention involves the deposition of the oxide layer on a curved surface. It may be for example a tube.
- a textured metal substrate is used which has grooves. It is possible, for example, to use a corrugated substrate or rib, which has been prepared from a flat sheet by a mechanical deformation process, for example by the application of rollers. These grooves or ribs are advantageously arranged in a direction other than orthogonal to the long direction of the substrate; they do not need to be parallel to each other, or parallel to the long axis of the substrate.
- TRBaCuO may be deposited in the spaces (recesses) between the grooves, ribs or corrugations, which generates veins of superconducting material; thus, the AC losses are reduced by splitting the section where the current flows.
- the method according to the invention is particularly well suited for depositing a homogeneous buffer layer of the type A 2 - x B 2+ ⁇ O 7 on such a grooved substrate (such as a corrugated substrate or rib), whereas the vacuum processes on Such a substrate generally leads to layers having an inhomogeneous thickness.
- a corrugated, ribbed or grooved sheet may also be a substrate for photovoltaic devices.
- the deposited layer is a LZO type layer of suitable thickness (typically between 30 nm and 250 nm, one can then deposit on this layer one or more superconducting layers of the type TRBaCuO or YBaCuO, on the last of these superconducting layers on depositing a thin protective layer by spraying Ag.
- the cumulative thickness of the superconducting layers is between 200 nm and 500 nm.
- the deposition of the TRBaCuO or YBaCuO layer is preferably by the technique of MOCVD (metal-organic Chemical vapor deposition), which the skilled person knows as such.
- MOCVD metal-organic Chemical vapor deposition
- a suitable technique for depositing YBaCuO with MOCVD is described, for example, in patent application WO 93/08838 and in the article published by Donet et al. in J. Phys IV Pr 11 AA 319 in 2001.
- a gas stream transports the precursors into the reaction zone where CVD growth takes place on a heated substrate. It is thus possible to inject either droplets consisting of mixtures of several precursors, or successively droplets consisting of a single precursor. This technique allows the deposition of layers of complex chemical composition.
- nozzles distributed around the cylinder may be used, or the cylindrical substrate may be rotated about its long axis in front of a plurality of nozzles.
- 16 nozzles distributed over a length of 30 cm can be used.
- a metal layer is then deposited.
- This layer is preferably permeable to oxygen, allowing its diffusion. Money gives the best result.
- This layer may be deposited with any known technique, but deposition under conditions allowing the absence of interface contaminations preventing current transfer between the silver protective layer and the superconducting layer is preferred. The cleaning of the interface can be done for example by an argon-oxygen plasma.
- a silver layer having a thickness of between 250 nm and 450 nm is deposited.
- the method according to the invention also makes it possible to prepare substrates for photovoltaic devices.
- a layer of epitaxial LZO may be deposited on a corrugated sheet.
- LZO formed and crystallized as described above can be deposited by any suitable method (such as CVD or gas phase epitaxy), crystalline silicon. Due to the ordered nature of the LZO surface, the silicon thus deposited will be, from the first atomic layers, a highly ordered solid having good electronic characteristics.
- the method according to the invention has many advantages.
- the oxide layers are dense and have only a small porosity of small, non-interconnected holes (probably at grain boundaries), virtually free of holes through holes (pin holes).
- the very low density of pin holes gives a low probability of short circuits between the underlying metal and a metal layer deposited above the oxide layer.
- These layers also provide an effective barrier to diffusion between the underlying substrate and the exterior (which may be another layer deposited on the oxide layer).
- These layers can serve as substrates for the deposition of other layers, thin or thick.
- the ordered crystallographic structure of the oxide layers obtained according to the invention promotes the growth of layers of ordered crystallographic structure, and promotes the quality of the interfaces between the layers, at the atomic scale.
- Example 1 A high temperature ceramic superconductor device was manufactured on an oxide layer deposited by the method according to the invention. This device has the following characteristics:
- the substrate was a tube made by welding the edges of a biaxially textured Ni sheet; this tube had been functionalized with H 2 S.
- the metal oxide buffer layer, deposited by the process according to the invention is a layer of LZO, which typically has a thickness of between 80 nm and 210 nm.
- the layer of TRBaCuO or YBaCuO, deposited above the LZO layer, is advantageously a YBaCuO layer having a thickness of between 200 nm and 500 nm, and typically of the order of 350 nm.
- the protective metal layer deposited above the layer of TRBaCuO or YBaCuO, is a silver layer, which typically has a thickness between 250 nm and 450 nm, and typically of the order of 350 nm.
- Such yarn of YBaCuO deposited on a textured yarn of Ni has a temperature T c of at least 83 K, preferably at least 85 K, and even more preferentially from minus 93 K.
- the current density, measured at 4 K, is greater than 3 A per centimeter of perimeter.
- FIG. 1 shows three micrographs, obtained by different techniques, of the same tube coated with a LZO layer deposited by the process according to the invention.
- the LZO layer with a thickness of 110 nm was deposited on a bi-axial textured Ni-5at% W flat substrate, which was converted into a tube by a rolling-welding process.
- Figure 1 (b) shows a micrograph obtained by scanning electron microscopy (20 kV acceleration voltage) on the rolled-welded tube. During the stretching phase, the LZO layer is fractured according to the L ⁇ ders bands generated by the deformation of the metal substrate. The micrograph shows the fractures of the LZO layer induced by this deformation.
- Figure 1 (a) shows a micrograph obtained by backscattered electron diffraction (EBSD) electron microscopy of the same tube.
- EBSD backscattered electron diffraction
- FIG. 1 (c) shows a micrograph obtained by scanning electron microscopy in backscattered electron diffraction mode under conditions identical to those used for FIG. 1 (b), on a tube whose LZO layer has been repaired by deposition of a second layer of LZO by the process according to the invention. It is observed that this second deposit blocks the empty zones caused by the process of forming the tube, which are visible in Figures 1 (a) and 1 (b).
- FIG. 3 shows that a deposit of YBaCuO on such a substrate can have a resistivity of less than 0.10 ⁇ at 80 K, and a resistivity at 60 K where it becomes superconducting.
- This example describes the deposition of an epitaxial layer of La 2 Zr 2 O 7 on corrugated sheet.
- the substrate was a biaxially textured Ni ribbed sheet, 80 ⁇ m thick, 4 cm long, and 1 cm wide; its shape is shown schematically in FIG. 5.
- This sheet was obtained from a flat sheet by pressing on two rods of alumina 1 mm in diameter, arranged parallel to the length of the sample and separated from 7 mm approx. After pressing the shape of the rods is embedded in the sheet by giving an undulating shape with slightly angular projections. There is a significant increase in the stiffness of the sheet facilitating its handling.
- This sheet was then dipped in a propionate solution of a metal of adequate viscosity, then extracted at a speed of 66 mm / min to cover a uniform deposit.
- the thickness of this deposit is determined by the flow of the liquid downwards, the critical parameters being the viscosity and the surface tension.
- the concave parts serve as drains and the thickness of the layer is lower in these parts, as evidenced by the final color of the film after crystallization. Conversely, the protruding parts are thicker.
- the sample was crystallized in an oven following the treatment already described.
- the result was a sample covered with a glossy enamel whose color reflects its thickness.
- the flat parts are sky blue, corresponding to a thickness of 80-100 nm.
- the crystal structure was observed by X-ray diffraction with a beam of 2 mm x 1 mm, sized to probe the flat part. This is well crystallized with the expected texture (direction [001] // at the normal of the surface and the direction [100] parallel to the direction ⁇ 110> of Ni), indicating that the undulation has not induced disturbance on this area.
- the structural characterization of the corrugated part can be done conventionally only by flattening it in a press. (On the other hand, the technique of microdiffraction makes it possible to avoid this difficulty which can introduce artifacts during flattening; however, this has not been done in the context of this example).
- the observation of the flattened sheet reveals a cube texture of good quality (equivalent to that of the flat part) demonstrating that the undulation created had no influence on the scale of the measurement, that is on a surface of some 2x1 mm 2 . This does not exclude that distortions may exist on a micron scale at the peaks of the projections, but their contribution to the mean is indistinguishable.
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Abstract
Description
Claims
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FR0807113A FR2940323B1 (fr) | 2008-12-18 | 2008-12-18 | Procede de depot de films d'oxydes sur tubes metalliques textures |
PCT/FR2009/001449 WO2010076429A1 (fr) | 2008-12-18 | 2009-12-18 | Procédé de dépôt de films d'oxydes minces sur des surfaces métalliques texturées courbées |
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EP2374168A1 true EP2374168A1 (fr) | 2011-10-12 |
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EP09804275.7A Revoked EP2374167B1 (fr) | 2008-12-18 | 2009-12-18 | Procédé de dépôt de films d'oxydes sur tubes métalliques texturés |
EP09806178A Withdrawn EP2374168A1 (fr) | 2008-12-18 | 2009-12-18 | Procédé de dépôt de films d'oxydes minces sur des surfaces métalliques texturées courbées |
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EP (2) | EP2374167B1 (fr) |
JP (2) | JP2012512803A (fr) |
KR (2) | KR20110112365A (fr) |
ES (1) | ES2495342T3 (fr) |
FR (1) | FR2940323B1 (fr) |
WO (2) | WO2010076429A1 (fr) |
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JP5606226B2 (ja) * | 2009-11-30 | 2014-10-15 | キヤノン株式会社 | X線モノクロメータ及びx線分光装置 |
FR2981952B1 (fr) | 2011-11-02 | 2015-01-02 | Fabien Gaben | Procede de realisation de couches minces denses par electrophorese |
EP2785470A4 (fr) * | 2011-12-01 | 2015-08-19 | Univ Utah Res Found | Dispositifs photoniques sur des substrats plans et courbés et leurs procédés de fabrication |
CN106105010B (zh) * | 2014-03-18 | 2018-10-09 | 意大利学院科技基金会 | 用于机械能量收集和感应的摩擦生电复合物 |
EP2960954A1 (fr) * | 2014-06-24 | 2015-12-30 | Basf Se | Procédé de fabrication d'un composite constitué d'une couche à supraconducteur haute température (HTS) |
FR3080957B1 (fr) | 2018-05-07 | 2020-07-10 | I-Ten | Electrodes mesoporeuses pour dispositifs electrochimiques en couches minces |
CN109273255B (zh) * | 2018-09-18 | 2021-04-23 | 陕西科技大学 | 一种高铁磁性的lsmo薄膜及其制备方法 |
WO2021063723A1 (fr) * | 2019-09-30 | 2021-04-08 | Basf Se | Ruban supraconductrice à haute température avec tampon à teneur en carbone contrôlée |
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2009
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- 2009-12-18 WO PCT/FR2009/001449 patent/WO2010076429A1/fr active Application Filing
- 2009-12-18 JP JP2011541538A patent/JP2012512803A/ja active Pending
- 2009-12-18 EP EP09806178A patent/EP2374168A1/fr not_active Withdrawn
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ES2495342T3 (es) | 2014-09-17 |
FR2940323B1 (fr) | 2011-02-11 |
JP2012512803A (ja) | 2012-06-07 |
EP2374167A1 (fr) | 2011-10-12 |
WO2010076428A8 (fr) | 2010-11-18 |
WO2010076428A1 (fr) | 2010-07-08 |
US8642511B2 (en) | 2014-02-04 |
FR2940323A1 (fr) | 2010-06-25 |
US20110312500A1 (en) | 2011-12-22 |
WO2010076429A1 (fr) | 2010-07-08 |
US20120028810A1 (en) | 2012-02-02 |
EP2374167B1 (fr) | 2014-06-11 |
JP2012512802A (ja) | 2012-06-07 |
KR20110125209A (ko) | 2011-11-18 |
KR20110112365A (ko) | 2011-10-12 |
US8633138B2 (en) | 2014-01-21 |
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