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WO1992019391A1 - Method of forming metal oxide coatings - Google Patents

Method of forming metal oxide coatings Download PDF

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Publication number
WO1992019391A1
WO1992019391A1 PCT/US1992/003505 US9203505W WO9219391A1 WO 1992019391 A1 WO1992019391 A1 WO 1992019391A1 US 9203505 W US9203505 W US 9203505W WO 9219391 A1 WO9219391 A1 WO 9219391A1
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WO
WIPO (PCT)
Prior art keywords
metal
coating
substrate
metal oxide
oxide
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.)
Ceased
Application number
PCT/US1992/003505
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French (fr)
Inventor
Benmin Gong
James C. W. Chien
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Individual
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Individual
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Publication date
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Publication of WO1992019391A1 publication Critical patent/WO1992019391A1/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02244—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of a metallic layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/455—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction
    • C04B41/4554—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction the coating or impregnating material being an organic or organo-metallic precursor of an inorganic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5027—Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
    • C—CHEMISTRY; METALLURGY
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    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • 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
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    • 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
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    • 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
    • C23C18/125—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
    • H—ELECTRICITY
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition

Definitions

  • the present invention relates to methods of forming thermally stable metal oxide coatings upon substrates as of conducting, semiconducting and insulating surfaces; being more particularly directed to the formation of thin uniform and hole-free high temperature thermally stable metal oxide coatings for such purposes as (1) providing fractional to multi-micron insulating coating surfaces to conducting (and semiconducting) substrates and the like, including hard high-temperature thermally stable ceramic barrier coatings capable of resisting rust and other oxidation effects and acids, and having excellent hard wear characteristics; and (2) providing relatively conductive metal oxide coatings for
  • magnesium, lanthanum, strontium, and other metal salts to provide, as by spin coating, a coated solution upon the desired substrates ⁇ in that case, a semiconductor wafer surface.
  • the resulting micron thick film of polymer metal complex precursor thus applied to the substrate was then heated under an air atmosphere from room temperature to about 700 C for about 2 hours and then maintained at that temperature for another half hour, resulting in a smooth, continuous, pin-hole free insulating metal oxide layer of the order of 0.2
  • conductive metal oxide coatings of uniform, pinhole free properties may be desired on insulating substrates, as of glass or the like, or on semiconducting substrates as in solar cell construction.
  • An object of the invention is to provide a new and improved method of forming thin uniform and aberration-resistant and hole-free high temperature thermally stable metal oxide coatings upon substrates, including metal and other conducting
  • a further object is to provide such a novel coating method for such purposes as inhibiting rust or attack by acids or other elements upon metal and similar surfaces, providing a high temperature thermally stable ceramic barrier, providing a hard insulating thin micron range coating for conducting substrates, and/or providing a hard and excellent wear-resistant surface coating for various substrates.
  • Still an additional object is to provide novel coatings having the above-described properties that may be produced on a wide variety of substrate surfaces in accordance with the methodology underlying the
  • Another object is to provide a method of producing a conducting metal oxide coating for insulating
  • Another object is to provide a method of producing a conducting metal oxide coating for semiconducting surfaces, as of silicon or the like and novel coated products produced thereby.
  • the invention embraces a method of forming thin uniform and aberration-resistant and hole-free high- temperature thermally stable metal oxide coatings upon a substrate, that comprises, dissolving a metal salt in a polymer solution to form a polymer-metal-complex
  • precursor solution containing ions of the metal, the oxide of which is desired as a coating on the substrate; coating the precursor solution after filtration upon the surface of the substrate and insuring uniformity of application over such surface; firing the coated
  • the invention provides an entirely different and less complex and costly technique for enabling the desired types of metal oxide coatings.
  • Prior techniques have involved, for example, sputtering or chemical vapor deposition to deposit coatings having some of the properties above described.
  • the before-described methacrylic acid-vinyl acetate copolymer was dissolved in N,N-dimethylformarnide in the ratio of about fifty percent copolymer and fifty percent dimethylformarnide.
  • the resulting copolymer solution then received a metal salt in the form of indium nitrate pentahydrate in the proportion of 75% cop ⁇ lymer and 25% ⁇ f.etal salt to form a p ⁇ lymer-metal-complex precursor solution wherein indium oxide was desired as the
  • the precursor solution was filtered with 0.4 micron filtering to remove foreign particles and then to enable spin coating on an acetone-cleaned silicon substrate surface. This resulted in a coating of about 2 microns thinness, as measured by interferometer measurements, producing uniformity over the surface.
  • the coated substrate was then introduced into an air (or oxygen) oven with the temperature increased from room temperature to 400 C for about 40 minutes, resulting in substantially complete burn-off of the polymer
  • Example 1 The experiment of Example 1 was repeated and the amount of indium nitrate compound relative to the amountof polymer solution was varied from the 25 grams of the metal salt and 75 grams of the copolymer of Example 1. It was noted that control of the concentration could be effected by increasing the amount of the copolymer, resulting in thinning of the coating,
  • Example 1 of metal oxide salt and the copolymer were repeated for zirconium acetyl acetonate with about 3% yittrium nitrate added, instead of indium nitrate pentahydrate. The same process was effected, this time on a conducting
  • Example 1 The process and proportions set forth in Example 1 was repeated on a steel plate for an aluminum nitrate salt, producing an excellent insulating coating of aluminum oxide of the order of a few tenths of a micron.
  • Example 1 The building up of this layer to the order of amicron and higher was then effected by recycling or repeating the steps of Example 1 (namely the spinning and heating) five times, each time adding 0.2 micron thickness to the coating.
  • Example 2 The same process as in Example 1 was repeated on a steel plate with a chromium nitrate metal salt,
  • Example 1 The steps of Example 1 were also repeated for a titanium nitrate salt providing an excellent titanium dioxide film, again on a steel substrate.
  • the color of coatings is distinctly related to the coating thickness, which not only enables verification of thickness and uniformity of coating, but also enables a selection of a desired color of the coating surface. It has been found that all metal oxides tested produce the same color for the same thickness; namely, at 1 micron thickness, the coating is clear and has no color; at 0.2 micron
  • metal oxides can, with a further modification of the method, be rendered substantially conducting, and well adapted for providing a conducting metal oxide coating on insulation substrates, such as glass or a ceramic, such as alumina, ZrO 2 or YSZ, a high temperature polymer, such as a polyimide or polysulfone and the like.
  • the substrates may be flat surfaces, wafers or fibers such as glass or alumina fibers. This technique has been found to be effectable through the adding in the polymer metal complex precursor solution containing the dissolved metal salt, the oxide of which metal it is desired to use as the coating, an
  • the indium oxide-to-tin oxide ratio was about 10:1.
  • the resulting polymer metal complex precursor solution was spin coated upon the surface of a glass substrate, insuring uniformity of application over the whole surface, and the coated glass was then fired in an air or oxygen furnace at a temperature of about 400 C for about 40 minutes, raising the temperature from about room temperature about 5 degrees per minute. At about 300 C the polymer substantially completely burned off with no residue, leaving the oxidized doped indium oxide.
  • the glass coated element was then kept in the oven at the 400 C temperature for about 10 to 20 minutes and then it was removed and cooled, providing a coating, that was found to be conducting, of about 91% indium oxide and 9% tin oxide.
  • Example 7 The same technique of Example 7 was repeated with the process of coating and firing recycled five times, producing a one micron thick conducting indium oxide film.
  • Example 7 The process of Example 7 was repeated, but instead of spin-coating the glass, it was dip-coated again, producing a uniform, aberration-resistant and hole-free high temperature thermally stable conducting metal oxide coating of the order of 0.2 mircon.
  • the metal or other substrate surface may be dipped or sprayed with the polymer metal complex, again, however, enduring uniformity of application over the entire surface.
  • the polymer metal complex may, if desired, be drawn into a fiber or other shape as before stated.
  • metal oxides such as Al 2 O 3 , TiO 2 , ZrO 2 , MgO and Cr 2 O 3 ; and mixed metal oxides such as ZrO 2 ⁇ Y 2 O 3 (YSZ), SrTiO 3 , LaAlO 3 ,
  • the polymer of the polymer metal complex precursors used in the methods of the invention may as explained in part in said copending application, be a carboxly, amide, amic acid, ester, anhydride, nitrile or amine-containing homopolymer, copolymer or terpolymer or the like.

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Abstract

A method is disclosed of forming thin uniform micron range and submicron range aberration-resistant and hole-free high-temperature thermally stable metal oxide coatings upon metal, insulating and other substrates, involving the application of a polymer metal complex precursor solution to the substrate and appropriate firing for oxidation of the metal and the coating while burning off all traces of the polymer. Insulating metal oxide coatings on conducting and semiconducting substrates are produced, and, if desired, conducting metal oxide coatings on insulating or semiconducting substrates.

Description

Method of Forming Metal Oxide Coatings
The present invention relates to methods of forming thermally stable metal oxide coatings upon substrates as of conducting, semiconducting and insulating surfaces; being more particularly directed to the formation of thin uniform and hole-free high temperature thermally stable metal oxide coatings for such purposes as (1) providing fractional to multi-micron insulating coating surfaces to conducting (and semiconducting) substrates and the like, including hard high-temperature thermally stable ceramic barrier coatings capable of resisting rust and other oxidation effects and acids, and having excellent hard wear characteristics; and (2) providing relatively conductive metal oxide coatings for
insulating surfaces and the like.
BACKGROUND
In copending application Serial No. 407312, of which the present application is partially a
continuat ion-in-part, filed September 15, 1989, by co-inventor James C. Chien, and of common assignee, there is disclosed a novel method of applying to semiconductor wafer surfaces and the like a coating of a polymer metal complex to form thereon a corresponding insulating barrier metal oxide thin layer adhered to the wafer surface and non-reactive therewith. The layer is formed by firing at elevated temperatures in an air atmosphere to result in a smooth continuous uniform insulating coating or layer well-adhered to the substrate. The use of a dimethylformamide solvent for a copolymer of methacrylic acid and vinyl acetate was therein described as dissolving a metal salt, such as a nitrate of
magnesium, lanthanum, strontium, and other metal salts to provide, as by spin coating, a coated solution upon the desired substrates ╌ in that case, a semiconductor wafer surface. The resulting micron thick film of polymer metal complex precursor thus applied to the substrate was then heated under an air atmosphere from room temperature to about 700 C for about 2 hours and then maintained at that temperature for another half hour, resulting in a smooth, continuous, pin-hole free insulating metal oxide layer of the order of 0.2
micron. Such a technique has been found admirably suited to the coating of such semiconductor surfaces and the like as for buffer or similar purposes.
There are occasions, however, where the forming of similar high-temperature thermally stable metal oxide coatings on other types of substrates, including metal or other conducting substrate surfaces may be desired not only for some of the same reasons as described in said copending application, but also for very different functions and reasons. These include, for example, providing a hard and excellent wear-resistant coating, and/or strongly insulating coating, and/or a high temperature thermally stable ceramic barrier, and/or for preventing rusting or other oxidation' processes or attack by acids, while preventing the lifting of the coating that could otherwise permit attack of the substrate surface.
There are also instances where relatively
conductive metal oxide coatings of uniform, pinhole free properties may be desired on insulating substrates, as of glass or the like, or on semiconducting substrates as in solar cell construction. Underlying the present invention, indeed is a discovery that rather critical modifications of the process described In said copending application may be instituted particularly to solve the above problems and it is to these purposes that the present invention is primarily directed.
OBJECTS OF INVENTION
An object of the invention, therefore, is to provide a new and improved method of forming thin uniform and aberration-resistant and hole-free high temperature thermally stable metal oxide coatings upon substrates, including metal and other conducting
surfaces, semiconducting surfaces, as well as insulating surfaces, and to provide for control of the micron range thinness of the resulting metal oxide coating.
A further object is to provide such a novel coating method for such purposes as inhibiting rust or attack by acids or other elements upon metal and similar surfaces, providing a high temperature thermally stable ceramic barrier, providing a hard insulating thin micron range coating for conducting substrates, and/or providing a hard and excellent wear-resistant surface coating for various substrates.
Still an additional object is to provide novel coatings having the above-described properties that may be produced on a wide variety of substrate surfaces in accordance with the methodology underlying the
invention.
Another object is to provide a method of producing a conducting metal oxide coating for insulating
substrate surfaces, as of glass or the like, and novel coated products produced thereby.
Another object is to provide a method of producing a conducting metal oxide coating for semiconducting surfaces, as of silicon or the like and novel coated products produced thereby.
Other and further objects will be explained hereinafter and are more particularly delineated in the appended claims.
SUMMARY
In summary, however, from one of its important aspects, the invention embraces a method of forming thin uniform and aberration-resistant and hole-free high- temperature thermally stable metal oxide coatings upon a substrate, that comprises, dissolving a metal salt in a polymer solution to form a polymer-metal-complex
precursor solution, containing ions of the metal, the oxide of which is desired as a coating on the substrate; coating the precursor solution after filtration upon the surface of the substrate and insuring uniformity of application over such surface; firing the coated
substrate in an air or oxygen furnace to oxidize the said metal in the coating while burning off all traces of the polymer; and cooling the coated substrate to produce a hard, high temperature thermally stable metal oxide coating of submicron or micron range thinness adhered to the substrate surface.
Preferred and best mode formulations and details are hereinafter set forth, including novel coated products attainable by the technique of the invention.
DESCRIPTION OF INVENTION
As will be evident hereinafter, the invention provides an entirely different and less complex and costly technique for enabling the desired types of metal oxide coatings. Prior techniques have involved, for example, sputtering or chemical vapor deposition to deposit coatings having some of the properties above described.
Other techniques for applying wear-resistant surfaces or enameling for wire or other surface
insulation, or anodizing metal surfaces to protect the same, all appear to be more complex and costly than the techniques of the present invention; and in any event, the invention is particularly suited to the deposit of fractional or micron-range thin coatings which cannot readily be attained by such prior techniques.
It is in order to describe the fabrication method underlying the invention by way of several examples of successful tests.
Turning first to metal oxide coatings for
semiconductor surfaces, similar to those of said
copending application, as for solar cell construction of the like, reference is made to the following example. Example 1
The before-described methacrylic acid-vinyl acetate copolymer was dissolved in N,N-dimethylformarnide in the ratio of about fifty percent copolymer and fifty percent dimethylformarnide. The resulting copolymer solution then received a metal salt in the form of indium nitrate pentahydrate in the proportion of 75% copυlymer and 25% ϊf.etal salt to form a pυlymer-metal-complex precursor solution wherein indium oxide was desired as the
insulating coating on a semiconductor silicon
substrate. The precursor solution was filtered with 0.4 micron filtering to remove foreign particles and then to enable spin coating on an acetone-cleaned silicon substrate surface. This resulted in a coating of about 2 microns thinness, as measured by interferometer measurements, producing uniformity over the surface.
The coated substrate was then introduced into an air (or oxygen) oven with the temperature increased from room temperature to 400 C for about 40 minutes, resulting in substantially complete burn-off of the polymer
(commencing at about 300 C), with no carbon or other polymer residue remaining, and with the indium metal oxidized as the coating on the silicon surface. The oxide coated substrate was then kept in the oven for another 10 to 20 minutes at substantially the same 400 C, resulting in an 0.2 micron thin indium oxide coating, strongly adhered to the substrate upon the cooling of the same. This coating was found to be totally aberration-resistant and hole-free and extremely uniform over the complete surface. Such uniformity, indeed, is demonstrated by the continuity of the
characteristic blue color of such a thin film oxide coating, as viewed in daylight.
Example 2
The experiment of Example 1 was repeated and the amount of indium nitrate compound relative to the amountof polymer solution was varied from the 25 grams of the metal salt and 75 grams of the copolymer of Example 1. It was noted that control of the concentration could be effected by increasing the amount of the copolymer, resulting in thinning of the coating,
Application of the technique of the invention to conducting substrates was also successfully implemented. Example 3
The relative proportions of Example 1 of metal oxide salt and the copolymer were repeated for zirconium acetyl acetonate with about 3% yittrium nitrate added, instead of indium nitrate pentahydrate. The same process was effected, this time on a conducting
stainless steel plate, forming a 0.2 mircon thick yittrium oxide-stabilized zirconium oxide film which was uniform and showed high-temperature thermally stable ceramic barrier properties.
Example 4
The process and proportions set forth in Example 1 was repeated on a steel plate for an aluminum nitrate salt, producing an excellent insulating coating of aluminum oxide of the order of a few tenths of a micron.
The building up of this layer to the order of amicron and higher was then effected by recycling or repeating the steps of Example 1 (namely the spinning and heating) five times, each time adding 0.2 micron thickness to the coating.
Example 5
The same process as in Example 1 was repeated on a steel plate with a chromium nitrate metal salt,
producing a hard and excellent rust and wear-resistant 0.2 micron thick film of chromium oxide.
Example 6
The steps of Example 1 were also repeated for a titanium nitrate salt providing an excellent titanium dioxide film, again on a steel substrate.
Underlying all of the above examples is the generic concept of providing a polymer metal complex solution filtered as a clear liquid with no precipitations and then depositing it as a uniform coating over the surface-to-be-coated by spin coating, controlled dipping, or spraying. These steps are followed by heating to remove the polymer complex and solvent and oxidizing, resulting in a smooth and uniform, pure metal oxide film of the order of submicron thickness, which is free
It is observed, moreover, that the color of coatings is distinctly related to the coating thickness, which not only enables verification of thickness and uniformity of coating, but also enables a selection of a desired color of the coating surface. It has been found that all metal oxides tested produce the same color for the same thickness; namely, at 1 micron thickness, the coating is clear and has no color; at 0.2 micron
thickness, there is a blue tint; 0.3-0.4 micron thick films appear yellow; 0.5 micron, green; 0.5 micron, violet; and 0.8 micron, pink.
Further underlying the present invention, as previously stated, is the rather startling discovery that such metal oxides can, with a further modification of the method, be rendered substantially conducting, and well adapted for providing a conducting metal oxide coating on insulation substrates, such as glass or a ceramic, such as alumina, ZrO2 or YSZ, a high temperature polymer, such as a polyimide or polysulfone and the like. The substrates may be flat surfaces, wafers or fibers such as glass or alumina fibers. This technique has been found to be effectable through the adding in the polymer metal complex precursor solution containing the dissolved metal salt, the oxide of which metal it is desired to use as the coating, an
appropriate metal dopant salt that renders the metal oxide coating conductive.
Example 7
A copolymer of methacrylic acid and vinyl acetate, both relatively low temperature decomposing polymers, was combined with a solvent of N-N-dimethylformamide in about equal proportions to provide a copolymer solution into which was dissolved a mixture of indium nitrate and a small amount of tin bromide dopant. The indium oxide-to-tin oxide ratio was about 10:1.
The resulting polymer metal complex precursor solution was spin coated upon the surface of a glass substrate, insuring uniformity of application over the whole surface, and the coated glass was then fired in an air or oxygen furnace at a temperature of about 400 C for about 40 minutes, raising the temperature from about room temperature about 5 degrees per minute. At about 300 C the polymer substantially completely burned off with no residue, leaving the oxidized doped indium oxide. The glass coated element was then kept in the oven at the 400 C temperature for about 10 to 20 minutes and then it was removed and cooled, providing a coating, that was found to be conducting, of about 91% indium oxide and 9% tin oxide.
Example 8
The same technique of Example 7 was repeated with the process of coating and firing recycled five times, producing a one micron thick conducting indium oxide film.
Example 9
3.5g of indium nitrate pentahydrate and 0.379g of tin (II) bromide (or alternatively, 0.25g of tin (II) chloride) and 15g of 1:1 vinyl acetate and methacrylic acid copolymer was co-dissolved, and the solution concentrated to a viscosity of 20-30 centipoise. This solution was applied to a glass substrate by spin- coating and then calcined in a furnace under flowing oxygen at 350-400 C for 10 minutes. A uniform f i lm of In 0 SnO of 0.2 to 0.3 microns thickness was formed without pinholes, and was highly conductive. Thicker films were produced by repeating the above process.
Example 10
The process of Example 7 was repeated, but instead of spin-coating the glass, it was dip-coated again, producing a uniform, aberration-resistant and hole-free high temperature thermally stable conducting metal oxide coating of the order of 0.2 mircon.
While the invention has been described in
connection with spin coating, it has been verified in tests similar to Example 1, that, as before stated, the metal or other substrate surface may be dipped or sprayed with the polymer metal complex, again, however, enduring uniformity of application over the entire surface. Instead of a coating, moreover, the polymer metal complex may, if desired, be drawn into a fiber or other shape as before stated. The production of thin films of metal oxides and mixed metal oxides on substrates in accordance with the invention (using corresponding metal nitrates in the polymer-metal complex solutions), embraces metal oxides such as Al2O3, TiO2, ZrO2, MgO and Cr2O3; and mixed metal oxides such as ZrO2· Y2O3 (YSZ), SrTiO3, LaAlO3,
In2O3· SnO2 and the metal oxide superconductors of said copending application. The polymer of the polymer metal complex precursors used in the methods of the invention, moreover, may as explained in part in said copending application, be a carboxly, amide, amic acid, ester, anhydride, nitrile or amine-containing homopolymer, copolymer or terpolymer or the like.
Further modifications will also occur to those skilled in this art, and such are considered to fall within the spirit and scope of the invention as defined in the appended claims.

Claims

What is claimed is:
1. A method of forming thin, uniform,
aberration-resistant and hole-free high-temperature thermally stable metal oxide coatings upon a substrate, that comprises, dissolving a metal salt in a polymer solution to form a polymer-metal-complex precursor solution, containing the ions of the metal the oxide of which is desired as a coating on the substrate; coating the precursor solution after filtration upon the surface of the substrate and insuring uniformity of application over such surface; firing the coated substrate in an air or oxygen furnace to oxidize the said metal in the coating while burning off all traces of the polymer; and cooling the coated substrate to produce a hard, high temperature thermally stable metal oxide coating of submicron or micron range thinness adhered to the substrate surface.
2. A method as claimed in claim 1 and in which the substrate is one of a conducting, semiconducting and an insulating substrate.
3. A method as claimed in claim 1 and in which the substrate is a metal surface, and the metal oxide coating serves to provide one or more of insulation, wear surfacing, thermal barrier, and rust and other oxidation resistance.
4. A method as claimed in claim 1 and in which the thinness of the coating is controlled by varying the amount of metal salt in the polymer-metal-complex solution.
5. A method as claimed in claim 1 and in which the polymer solution comprises methacrylic acid and vinyl acetate dissolved in
dimethlyformamide.
6. A method as claimed in claim 5 and in which the metal salt is selected from the group consisting of titanium nitrate, zirconium acetylacetonate, aluminum nitrate, indium nitrate, magnesium nitrate and chromium
nitrate, providing respective oxide coatings of Ti, Zr, Al, In, Mg, and Cr.
7. A method as claimed in claim 5 and in which the dimethylformamide is approximately 50% of the polymer solution.
8. A method as claimed in claim 7 and in which the metal salt is of the order of about 25% of the polymer-metal-complex precursor.
9. A method as claimed in claim 5 and in which the firing is effected at about 400 C for about 40 minutes, followed by continuing heating at about 400 C for about 10-20 minutes, resulting in a coating of the order of 0.2 u.
10. A method as claimed in claim 9 and in which the coating and firing process is repeated to increase the coating th ickness .
11 . A method as claimed in claim 1 and in which the polymer solution comprises polymethacrylic acid.
12. A method as claimed in claim 1 and in which the polymer is selected from the group consisting of carboxyl, amide, amic acid, ester, anhydride, nitrile, amine-containing polymers.
13. A micron-thin, uniform, and aberration-resistant and hole-free, hard, high-temperature thermally stable metal oxide-coated substrate formed by the method of claim 1.
14. A micron-thin, uniform, aberration-resistant and hole-free, hard, high-temperature thermally stable metal oxide-coated surface as claimed in claim 13 and in which the metal oxide is selected from the group consisting of oxides of Ti, Zr, Sr, Sn, Y, In, Al, Mg, and Cr.
15. A method as claimed in claim 1 and in which a metal dopant salt is mixed in the polymer solution to produce with the metal oxide coating an oxide of the metal dopant that renders the coating conductive.
16. A method as claimed in claim 15 and in which the polymer solution comprises copolymers of methacrylic acid and vinyl acetate dissolved in N-N-dimethylformamide.
17. A method as claimed in claim 15 and in which the metal salt is an indium salt and the dopant is a tin salt.
18. A method as claimed in claim 17 and in which the indium salt is indium nitrate pentahydrate and the tin salt is one of tin bromide and tin chloride.
19. A method as claimed in claim 18 and in which the indium-to-tin salt ratio is of the order of about 10:1.
20. A method as claimed in claim 15 and in which the substrate is an insulating surface.
21. A micron-thin, uniform, aberration-resistant and hole-free, hard, high temperature stable conductive metal oxide-coated surface substrate formed by the method of claim 1.
22. A conductive metal oxide-coated insulating
substrate as claimed in claim 21 and in which the metal oxide coating is on indium oxide and tin oxide.
23. A conductive metal oxide-coated insulating
substrate as claimed in claim 22 wherein the ratio of indium oxide to tin oxide is of the order of about 10:1.
24. A micron-thin, uniform, aberration-resistant and hole-free, hard, high-temperature thermally stable conducting metal oxide-coated substrate in which the metal oxide coating is of indium and tin oxide.
PCT/US1992/003505 1991-04-29 1992-04-28 Method of forming metal oxide coatings Ceased WO1992019391A1 (en)

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Cited By (2)

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WO2012024019A1 (en) * 2010-08-19 2012-02-23 Caterpillar Inc. Pre-oxidation of engine valves and seat inserts for improved life
CN115125596A (en) * 2021-03-24 2022-09-30 中国科学院苏州纳米技术与纳米仿生研究所 Surface treatment method and application

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US4636440A (en) * 1985-10-28 1987-01-13 Manville Corporation Novel process for coating substrates with glass-like films and coated substrates
US4666742A (en) * 1983-05-11 1987-05-19 Nissan Chemical Industries Ltd. Polymer composition containing an organic metal complex and method for producing a metallized polymer from the polymer composition
US4946710A (en) * 1987-06-02 1990-08-07 National Semiconductor Corporation Method for preparing PLZT, PZT and PLT sol-gels and fabricating ferroelectric thin films

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US4666742A (en) * 1983-05-11 1987-05-19 Nissan Chemical Industries Ltd. Polymer composition containing an organic metal complex and method for producing a metallized polymer from the polymer composition
US4636440A (en) * 1985-10-28 1987-01-13 Manville Corporation Novel process for coating substrates with glass-like films and coated substrates
US4946710A (en) * 1987-06-02 1990-08-07 National Semiconductor Corporation Method for preparing PLZT, PZT and PLT sol-gels and fabricating ferroelectric thin films

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012024019A1 (en) * 2010-08-19 2012-02-23 Caterpillar Inc. Pre-oxidation of engine valves and seat inserts for improved life
CN115125596A (en) * 2021-03-24 2022-09-30 中国科学院苏州纳米技术与纳米仿生研究所 Surface treatment method and application

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