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WO1994011546A1 - Preparation de pellicules de metal ou d'oxyde - Google Patents

Preparation de pellicules de metal ou d'oxyde Download PDF

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Publication number
WO1994011546A1
WO1994011546A1 PCT/GB1993/002388 GB9302388W WO9411546A1 WO 1994011546 A1 WO1994011546 A1 WO 1994011546A1 GB 9302388 W GB9302388 W GB 9302388W WO 9411546 A1 WO9411546 A1 WO 9411546A1
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WO
WIPO (PCT)
Prior art keywords
substrate
polymer
film
coating
metal
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/GB1993/002388
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English (en)
Inventor
Michael Stuart Waite
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rank Brimar Ltd
Original Assignee
Rank Brimar Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rank Brimar Ltd filed Critical Rank Brimar Ltd
Publication of WO1994011546A1 publication Critical patent/WO1994011546A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C23C18/08—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 metallic 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
    • C23C18/1204—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
    • 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
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic
    • 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
    • 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
    • C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature

Definitions

  • This invention relates to the production of oxide films, carbonate films or metal films, particularly though not exclusives for use as luminescent films.
  • it is concerned with the room temperature or low elevated temperature application of such films to substrates by techniques such as spin- or dip-coating using metal polymer precursors, in which the polymer will be a copolymer in which the units and other properties of the polymer are selected to provide suitable rheaological and viscoelastic properties.
  • Vacuum or low pressure deposition (a) can lead to differential evaporation rates in the case of mixed oxides and nonstoichiometry through oxygen deficiency.
  • CVD methods (b) require the use of volatile precursors and the relative concentrations of these must be adjusted for differential decomposition rates in order to give stoichiometric compound oxides. Furthermore the technique of CVD for complex oxides is still developing and problems such as premature homogeneous decomposition in the gas phase can produce defects and blemishes in the film.
  • the liquid phase organic precursor technique (c) can be used when the substrate is stable at the decomposition temperatures required.
  • the effective reaction temperatures for producing complex oxides by this technique are generally lower than for the equivalent reaction from the oxide powders.
  • the method is applicable to all metals for which suitable organo- metallic compounds exist which are not volatile at the decomposition temperature.
  • the systems which can be used in this technique tend to fall into two groups:
  • organometallic compound which can be a metal salt, is dissolved in a suitable solvent for spin or dip coating, with additives for viscosity control if necessary.
  • the metal is bound by M-0 bonds to a polymer which determines the rheological properties of the solution.
  • the systems which are the subject of this invention fall into this category, the bonding of the metal to the polymer chain being through acid groups.
  • a process in which metal oxides or hydroxides or other compounds are reacted with a carboxylic acid monomer containing polymerizable vinyl groups, the monomer is polymerized optionally with acrylonitrile, styrene or an ester of methacrylic acid, and the resulting polymer in DMF or DMSO is sprayed onto a substrate which is heated to decompose the polymer is disclosed in DE-A-4118749.
  • the process is used to make superconductor films, films for use in the electrical and electronics industries, refractory and/or corrosion resistant coatings and decorative coloured coatings. However the film forming material is sprayed onto a substrate which is
  • the invention provides a method for forming a film on a substrate which comprises coating a substrate with a solution of a polymer containing a metal bonded to the polymer chain through acid groups at a temperature below that at which the polymer is decomposed, allowing the coated substrate to dry, and heating the substrate to decompose the polymer and leave the metal on the substrate as such or as an oxide or carbonate.
  • the invention also provides a method for forming a film on a substrate which comprises dip- or film-coating the substrate with a solution of a polymer containing a metal bonded to the polymer chain through acid groups, allowing the coated substrate to dry, and heating the substrate to decompose the polymer and leave the metal on the substrate as such or an oxide or carbonate.
  • the polymer will normally be selected to have rheological properties suitable for spin- or dip-coating and to be sufficiently flexible to avoid a film cracking when the solvent evaporates and when the film is heated.
  • the invention further provides a method for forming a luminescent film on a substrate which comprises coating a substrate with a solution of a polymer containing metals bonded to the polymer chain through acid groups and which decompose to form a luminecsent inorganic film, the coating being carried out at a temperature below that at which the polymer is decomposed, allowing the coated substrate to dry, and heating the substrate to decompose the polymer and leave on the substrate the luminecent inorganic film.
  • the polymer systems considered most suitable for this application are the vinyl acids and esters such as acrylates and methacrylates which depolymerise on heating and thus reduce the tendency to form graphitic residues. They have the additional property of acting as electron beam resists so that the electron beam lithography can be employed in device fabrication.
  • Films of complex oxides of electropositive elements may be prepared by appropriate mixture of individual metal copolymers.
  • the invention may be used to prepare luminescent rare earth doped YAG films.
  • Complex oxides incorporating acidic oxides as discrete anion units such as rare earth or indium borates can be prepared if the copolymer has a component which aids the dissolution of the acidic oxide by, for example, ester linkage or hydrogen bond formation to hydrogen substituted acrylate based units.
  • STAGE 1 Preparation of individual metal-polymer resins
  • STAGE 2 Mixing of components in ratios required for final stoichiometry where a complex and not a. simple oxide film is required
  • STAGE 3 Spin or dip coating onto chosen substrate
  • STAGE 4 Thermal decomposition of metal-polymer film
  • the polymers used are preferably co-polymers of acrylic acid (I), methacrylic acid (II) or itaconic acid (III) with methyl methacrylate (IV) or a derivative such as hydroxyethyl acrylate (V) . It was found that the metal acrylates alone, when polymerised, give films which do not adhere well to substrates and which crack on drying.
  • the film-forming resin used must bind to the metal cation, but also incorporate an effective proportion of units imparting viscoelastic behaviour so that the dried film does not develop cracks or peel.
  • ester acting as a cross-linking agent or chain extender in the polymer backbone produces films with improved adhesion to typical ceramic or glass substrates.
  • Other inert chain-extending units e.g styrene units may also be present.
  • the films containing an appropriate proportion of copolymer units can be applied to greater thickness before cracking or peeling from the substrate on drying.
  • a preferred method for the preparation of metal-polymer solutions is a two-step process: Step 1
  • Copolymers are prepared by conventional polymerisation in dimethylformamide solution with azoisobutronitrile initiator.
  • the proportion of acid to ester varies from 1:2 to 2:1 with 1:1 being the most common combination used,
  • the proportion of ester in the reaction mixture is monitored by GLC analysis and the heating is continued until the concentration of the monomeric ester falls below 5% of the starting concentration.
  • the result is a colourless, viscous liquid. It may be analysed for polymer solid content by drying in vacuum and for acid content by titration with alkali.
  • copolymers can also be prepared by emulsion polymerisation of the acid and ester in sodium lauryl
  • a metal-polymer complex is prepared by reaction of the copolymer with the metal hydroxide, carbonate or basic salt in refluxing solvent, usually DMF.
  • the metal compound is added in the calculated stoichiometric quantity depending on the acid content of the polymer and the known or assumed oxidation state of the metal.
  • the solution containing the reaction product is centrifuged or filtered to remove unreacted material.
  • the equivalent metal oxide content is adjusted to >4% by vacuum evaporation of the solvent if necessary. At this concentration the material is usually viscous enough for coating.
  • the equivalent oxide content of the resin is determined by airbake at 500°C.
  • STAGE 2 Mixing of Individual Metal-Polymer Resins
  • the individual oxide content of the required complex oxide is determined. Knowing the equivalent oxide content of each individual resin they are blended to give the required proportion of individual oxides.
  • the resin solution is applied to the substrate at a temperature below that at which the resin decomposes, usually below 140 C, preferably below 100°C and most preferably at ambient temperatures.
  • the resin solution may be dip coated onto substrates e.g using a dip method, by flowing down the internal surface of tubing or by spin coating.
  • the viscosity for each method of application is adjusted by variation of solvent concentration so that the resultant film has a thickness of ca 4 ⁇ m.
  • the coatings are dried at 120°C for half an hour prior to baking.
  • a wide variety of heat resistant inorganic substrates may be used, e.g. transparent substrates such as glass or silica, or alumina or sapphire substrates.
  • the important parameters in the decomposition are the atmosphere during firing, the temperature programming rate and the ultimate temperature. In most cases natural air firing is suitable.
  • the initial stage of decomposition of most of the metal-polymer resins is the decomposition of the acrylate based units, starting at about 150°C and complete by 400°C. Air firing or oxygen enrichment is desirable to avoid residual carbon.
  • the temperature programming rate over the initial decomposition stage is important. The rate of temperature rise should preferably be in the region 2 to 5°C/min. If the rate is too high there is possibility of nonstoichiometry in the resultant oxide, residual carbon in the film and in the case of complex oxides the formation of metastable phases. If it is too low, the processing time is unnecessarily long, although rates of
  • the ultimate temperature is determined by the nature of the substrate and the oxide film.
  • the minimum ultimate temperature for formation of an oxide phase is 400°C, for transition metal oxide films for example.
  • transition metal oxide films for example.
  • complex oxides such a yttrium aluminium garnet the crystalline oxide phase is established at 900°C but crystallinity is improved by further annealing up to 1400°C (on sapphire substrates) .
  • the resulting films typically have thickness about 0.3 ⁇ m per coating or layer.
  • the invention will be further illustrated by reference to the following Examples.
  • Acrylic acid (72g), methyl, methacrylate (lOOg) and dimethylformamide (lOOg) are refluxed with 0.5g AIBN until GLC analysis of the MMA/DMF ratio indicates that the MMA content is ⁇ 5% of starting value.
  • the residual MMA and excess solvent are removed by rotary evaporation.
  • the solvent content is adjusted to a known value in the range 15 to 30 weight percent as determined by drying samples at 100°C.
  • the acid content is determined by titration in alcohol solution with sodium hydroxide.
  • Nickel carbonate is heated with the copolymer in stoichiometric quantity based on the acid content of the polymer until the carbonate has dissolved.
  • the solution is centrifuged or filtered to remove residual powder.
  • the solvent content is adjusted to give a Ni content of 2.5-4%.
  • the preferred solvents are DMF or acetylacetone. DMF solutions are brown ,solutions containing acetyl ⁇ acetone are green.
  • Acrylic acid and methyl methacrylate are copolymerised as in Example 1.
  • the resin solution is applied to the substrate by spin coating or flow methods as appropriate and decomposed by heating to > 400°C for a minimum of 1 hour in air or oxygen to give an indium tin oxide film.
  • STAGE 1 Preparation of Individual Metal-Polymer Solutions.
  • the individual hydroxides of yttrium, aluminium and terbium are prepared as dried amorphous powders by ammoniacal hydrolysis of the corresponding nitrates.
  • the hydroxides are reacted with acid-methyl methacrylate copolymer prepared as in Example 1 above.
  • a proportion of the methyl meth ⁇ acrylate may be replaced by 2-hydroxyethyl methacrylate.
  • the equivalent oxide content of the individual metal- polymer solutions is determined by pyrolysis.
  • the individual metal-polymer solutions are hence combined in the proportions appropriate to give a Tb:Y molar ratio of 1:30 and a Y:A1 molar ratio of 3:5.
  • STAGE 2 Preparation of Oxide Films
  • the resin solution is applied to the substrate by spin coating or flow methods as appropriate.
  • the heating rate for successful decomposition to give a transparent YAG layer must be controlled at ⁇ 4°C/min to temperatures of
  • the resulting layer forms a YAG:Tb luminescent film.
  • the Ni containing polymer can be used to deposit a high resistivity (lOM ⁇ .cm) film on the internal surface of a
  • the coating is applied by drawing the resin up the tube by suction and allowing to drain back.
  • Indium tin oxide containing films The internal surface of a miniature CRT was provided with a wall electrode by flow coating with the indium tin containing resin and decomposition of the polymer at 420°C.
  • Green emitting cathodoluminescent YAG:Tb films, annealed on sapphire substrates at 1400°C, can be prepared by spin coating of the mixed metal polymer resin with subsequent decomposition, (see Fig 1). Multiple layers can be built up to increase thickness. With other activators e.g Eu, Nd other emission bands are available. The other activators are incorporated as the Tb by preparation of the corresponding polymer.
  • Fig 2 illustrates the cathodoluminescent spectrum of a Y203:Eu film prepared by decomposition at 900°C of a layer spin-coated onto sapphire from a methyl methacrylate-itaconic acid copolymer containing Y and Eu.
  • a luminescent film is as the phosphor of a microtips fluorescent display (R Meyer et al, Japan Display, 88, 512) which is a flat panel display based on an array of field emission cathodes. Normal phosphor screens are based on powder layers and therefore could generate particles which would destroy the cathodes. Hence the interest in a simply produced thin film luminescent screen.
  • Another possible application is for a high luminance light source achieved by electron beam or other high energy excitation.
  • the layers could be deposited on substrates of complex geometry and would be well heat sinked to avoid excessive temperatures.
  • the layers could be transparent or granular to assist with light extraction (light trapping due to total internal reflection is well known in thin transparent films resulting in only 10-20% of the generated light being emitted). Possible fields of use include both displays and illumination systems.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un procédé servant à déposer une pellicule sur un substrat en revêtant ce dernier à température ambiante avec une solution d'un polymère contenant un métal fixé à la chaîne polymère par l'intermédiaire de groupes acides et en réchauffant le substrat, de façon à décomposer le polymère. On laisse le métal sur le substrat en tant que tel ou en tant qu'oxyde ou carbonate. Des systèmes appropriés comprennent des esters et des acides de vinyle, tels que des acrylates ou des méthacrylates se décomposant à la chaleur. On peut utiliser le procédé pour fabriquer des pellicules de phosphore GYA dopé aux terres rares ou des pellicules de phosphore de borate.
PCT/GB1993/002388 1992-11-19 1993-11-19 Preparation de pellicules de metal ou d'oxyde Ceased WO1994011546A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9224242.9 1992-11-19
GB929224242A GB9224242D0 (en) 1992-11-19 1992-11-19 Preparation of metal or oxide films

Publications (1)

Publication Number Publication Date
WO1994011546A1 true WO1994011546A1 (fr) 1994-05-26

Family

ID=10725340

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1993/002388 Ceased WO1994011546A1 (fr) 1992-11-19 1993-11-19 Preparation de pellicules de metal ou d'oxyde

Country Status (2)

Country Link
GB (1) GB9224242D0 (fr)
WO (1) WO1994011546A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002061791A3 (fr) * 2001-01-29 2003-11-27 Du Pont Fibres et rubans contenant du phosphore, des metaux conducteurs ou des particules dielectriques se pretant a la fabrication d'ecrans plats
US7163596B2 (en) 2002-06-07 2007-01-16 E. I. Du Pont Nemours And Company Fibers and ribbons for use in the manufacture of solar cells
US7282106B2 (en) 2003-05-02 2007-10-16 E. I. Du Pont De Nemours And Company Fibers and ribbons for use in the manufacture of solar cells
US11047747B2 (en) 2017-03-27 2021-06-29 Firouzeh Sabri Light weight flexible temperature sensor kit

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808653A (en) * 1986-12-04 1989-02-28 Dow Corning Corporation Coating composition containing hydrogen silsesquioxane resin and other metal oxide precursors
EP0431999A1 (fr) * 1989-11-20 1991-06-12 Thomson-Csf Procédé de dépôt d'une composition céramique en couche mince, et produit obtenu par ce procédé
DE4118749A1 (de) * 1990-06-11 1991-12-12 Freiberg Bergakademie Verfahren zur herstellung von duennen homogenen auftragsschichten aus oxidischen materialien
GB2253635A (en) * 1991-01-25 1992-09-16 Amp Akzo Corp Heat decomposable compositions containing organogold compound and glass forming resinate
GB2253636A (en) * 1991-01-25 1992-09-16 Amp Akzo Corp Heat decomposable compositions containing organogold compound and resin binder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808653A (en) * 1986-12-04 1989-02-28 Dow Corning Corporation Coating composition containing hydrogen silsesquioxane resin and other metal oxide precursors
EP0431999A1 (fr) * 1989-11-20 1991-06-12 Thomson-Csf Procédé de dépôt d'une composition céramique en couche mince, et produit obtenu par ce procédé
DE4118749A1 (de) * 1990-06-11 1991-12-12 Freiberg Bergakademie Verfahren zur herstellung von duennen homogenen auftragsschichten aus oxidischen materialien
GB2253635A (en) * 1991-01-25 1992-09-16 Amp Akzo Corp Heat decomposable compositions containing organogold compound and glass forming resinate
GB2253636A (en) * 1991-01-25 1992-09-16 Amp Akzo Corp Heat decomposable compositions containing organogold compound and resin binder

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002061791A3 (fr) * 2001-01-29 2003-11-27 Du Pont Fibres et rubans contenant du phosphore, des metaux conducteurs ou des particules dielectriques se pretant a la fabrication d'ecrans plats
US7201814B2 (en) 2001-01-29 2007-04-10 E. I. Du Pont De Nemours And Company Fibers and ribbons containing phosphor, conductive metals or dielectric particles for use in the manufacture of flat panel displays
US7163596B2 (en) 2002-06-07 2007-01-16 E. I. Du Pont Nemours And Company Fibers and ribbons for use in the manufacture of solar cells
US7282106B2 (en) 2003-05-02 2007-10-16 E. I. Du Pont De Nemours And Company Fibers and ribbons for use in the manufacture of solar cells
US7491442B2 (en) 2003-05-02 2009-02-17 E. I. Du Pont De Nemours And Company Fibers and ribbons for use in the manufacture of solar cells
US11047747B2 (en) 2017-03-27 2021-06-29 Firouzeh Sabri Light weight flexible temperature sensor kit

Also Published As

Publication number Publication date
GB9224242D0 (en) 1993-01-06

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