EP2580373A1 - Method for the low-temperature preparation of electrically conductive mesostructured coatings - Google Patents
Method for the low-temperature preparation of electrically conductive mesostructured coatingsInfo
- Publication number
- EP2580373A1 EP2580373A1 EP11726908.4A EP11726908A EP2580373A1 EP 2580373 A1 EP2580373 A1 EP 2580373A1 EP 11726908 A EP11726908 A EP 11726908A EP 2580373 A1 EP2580373 A1 EP 2580373A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mesostructured
- coating
- layer
- copolymers
- homopolymers
- 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.)
- Granted
Links
Classifications
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
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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
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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
- C23C18/1225—Deposition of multilayers of inorganic material
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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
- C23C18/1254—Sol or sol-gel processing
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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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- 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
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1667—Radiant energy, e.g. laser
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to the manufacture of a coating comprising one or more electroconductive structures consisting of metal nanoparticles.
- the metal nanoparticles are created by photoreduction catalyzed by a photocatalytic material, preferably titanium oxide.
- This manufacture does not include any heating step at a temperature greater than about 250 ° C, which allows this coating to be made on plastic substrates.
- a photocatalytic material is a semiconductor. When subjected to light radiation whose wavelength corresponds at least to the energy that separates its valence band from its conduction band, it absorbs this energy and an electron-hole pair is created. The photoelectron is then available to reduce a chemical species present on the surface of the catalyst.
- Photocatalysts are generally metal oxides or sulphides with wide bandgap. The activation of the catalyst is usually done with a radiation whose wavelength corresponds to ultra ⁇ violet.
- This publication describes in particular the production of mesoporous SiO 2 / TiO 2 bilayer coatings which are impregnated with silver nitrate and then irradiated with UV radiation through a lithographic mask.
- this mesoporous coating necessarily involves a calcination step at 350 ° C. for 2 hours of the deposited layers. This calcination is carried out in particular for the following reasons:
- the present invention is based on the rather surprising discovery that the step of calcining deposits, implemented by Martinez et al., Seems to be superfluous and that a similar method devoid of any heat treatment step at high temperature, gives conductivity results of created structures that are equivalent to, or even superior to, those obtained with a method for calcining organic components.
- the Applicant has found in particular that it is sufficient to subject the mesostructured coatings, after their sol-gel deposition, to a simple stage of maturation at moderately high temperature (less than or equal to 250 ° C.), with the purpose of consolidation of said coatings.
- the present invention relates to a method of manufacturing a mesostructured coating comprising electroconductive structures formed of metal nanoparticles consisting of a metal selected from the group consisting of Ag, Au, Pd and Pt, preferably Ag, comprising the steps of :
- step b) depositing, by the sol-gel method on the first layer, deposited during step a), a second layer of a material, mesostructured by a structuring agent, based on silica, said second layer being free of photocatalytic material; ;
- step d) contacting the consolidated coating obtained in step c) with a solution containing metal ions selected from the group consisting of silver, gold, palladium and platinum ions, preferably silver, and irradiating it with radiation enabling activation of the photocatalytic material for a time sufficient to reach the percolation threshold beyond which metal nanoparticles obtained by photocatalyzed reduction of the metal ions together form an electroconductive structure, said method being characterized in that it does not include any heat treatment at a temperature above 250 ° C.
- the present invention also relates to a mesostructured coating comprising electroconductive structures formed of metal nanoparticles, obtainable by such a method.
- the present invention also relates to the use of this mesostructured coating as an electrode, as an antistatic coating or, thanks to its reflective properties, as a heat-insulating coating.
- the present invention therefore relates to a method of manufacturing a mesostructured coating comprising electroconductive structures formed of metal nanoparticles.
- the metal is selected from the group consisting of Ag, Au, Pd and Pt.
- said metal nanoparticles are silver nanoparticles.
- the method according to the invention comprises a step a) of forming, by a sol-gel method, on a substrate, a first layer of a mesostructured material by a structuring agent.
- This material is based on silica and a photocatalytic material, in other words the silica and the photocatalytic material together represent at least 30% by weight, preferably at least 50% of said material, the remainder being formed by the agent structuring and possible impurities introduced by the sol-gel process.
- Sol-gel processes are methods, well known to those skilled in the art, which make it possible to form an amorphous three-dimensional solid network by hydrolysis and condensation of precursors in solution.
- the first layer of mesostructured material, formed in step a) of the process contains silica, a photocatalytic material and an organic structuring agent.
- the silica represents between 5% and 45% by weight of the mesostructured material.
- the structuring agent preferably represents between 5% and 60% by weight of the mesostructured material.
- This structuring agent has the role of forming in this material mesopores.
- the term "mesopores" refers to pores with a diameter of between 2 and 50 nm (nanometers).
- the mesoporous materials are obtained by removal of the structuring agent, for example by calcination. As long as the structuring agent has not been eliminated, the mesopores are occupied by it, and the material is said to be "mesostructured", that is to say that it has mesopores filled with structuring agent. .
- the structuring agent may be a polymer or a surfactant.
- the structuring agent is chosen from nonionic surfactants.
- Block copolymers preferably block copolymers based on ethylene oxide and propylene oxide, are advantageously used.
- nonionic structuring agent preferred in the present invention are poloxamers sold under the name Pluronic ®.
- the photocatalytic material is preferably a metal oxide. It is preferably selected from the group consisting of titanium oxide, zinc oxide, bismuth oxide and vanadium oxide, or a mixture thereof. In a particularly preferred manner, the photocatalytic material is TiC 2 titanium oxide.
- the mass ratio of the photocatalytic material to the silica in the first layer is between 0.05 and 2.7.
- the Ti / Si atomic ratio is preferably between 0.05 and 2, in particular between 0.5 and 1.5, and more preferably between 0.8 and 1 2.
- the photocatalytic material according to the invention is in the physical form which is necessary for it to have photocatalytic properties.
- the 10 2 must be at least partially crystallized, preferably in anatase form.
- the photocatalytic material is present in the first layer in the form of particles in a silica matrix, for example nanoparticles with a diameter of between 0.5 and 300 nm, in particular between 1 and 80 nm. .
- These nanoparticles may themselves consist of grains or smaller elemental crystallites. These particles can also be agglomerated or aggregated to each other.
- Step a) of the process according to the invention may comprise the following substeps:
- a sol containing at least one silica precursor preferably a tetraalkoxysilane, such as tetraethoxysilane, dissolved in an organoskeletal solvent containing a catalyst acid or basic hydrolysis and the structuring agent;
- the organo-aqueous solvent is an alcohol / water mixture, the alcohol typically being methanol or ethanol.
- the application of the soil to the substrate can be done according to the techniques known to those skilled in the art, for example by centrifugation (in English spin coating), by dip-coating or by laminar coating (in English). English roll coating).
- the substrate may be any suitable solid material.
- the substrate is preferably a non-conductive substrate. It may be for example traditional substrates glass, Pyrex ® , silica etc.
- the substrate is an organic polymer.
- suitable organic polymers are poly (ethylene terephthalate), polycarbonate, polyamides, polyimides, polysulfones, poly (methyl methacrylate), copolymers of ethylene terephthalate and carbonate, polyolefins, especially polynorbornenes, homopolymers and copolymers of diethylene glycol bis (allyl carbonate), (meth) acrylic homopolymers and copolymers, especially (meth) acrylic homopolymers and copolymers derived from bisphenol A, thio (meth) acrylic homopolymers and copolymers, homopolymers and copolymers urethane and thiourethane, epoxy homopolymers and copolymers and episulfide homopolymers and copolymers, cotton in the form of solid material, film or wire.
- suitable organic polymers are poly (ethylene terephthalate), polycarbonate, polyamides, polyimides, polysulfones, poly (methyl methacrylate), copolymers of
- the method according to the invention has the advantage of not including any heat treatment at a temperature above 250 ° C.
- this method is particularly recommended for use on a polymeric support that does not withstand prolonged exposure to temperatures above 250 ° C.
- a transparent polymeric support In the perspective of an application in the field of optics or glazings, use will in particular be made of a transparent polymeric support.
- Step b) of the process according to the invention consists in depositing, by the sol-gel method on the first layer, deposited during step a), a second layer of a mesostructured material with a structuring agent, based on silica. said second layer being free of photocatalytic material.
- the first coating is advantageously subjected to no intermediate heating between step a) and step b). Indeed, as will be demonstrated below with the aid of a comparative example, the Applicant has found that the conductivity of the metal structures formed was significantly less good when the first layer was subjected to a heat treatment before the deposition of the second layer.
- the first coating may advantageously be subjected to a maturation treatment before the deposition of the second layer, said maturation treatment consisting in keeping the first layer in a humid atmosphere at room temperature for a period of between 15 minutes and 2 hours.
- humidity relative (HR) of this atmosphere is preferably between 60 and 80%.
- the deposition of this second layer is done in the same way as the deposition of the first layer, the only difference being the absence of the photocatalytic material.
- the silica precursor tetraalkoxysilane
- the catalyst the solvent and the structuring agent may be the same as those used for the first layer.
- the sol-gel process can also be implemented in the same way. However, this is not essential.
- Step b) of the method according to the invention may comprise the substeps consisting of:
- a sol containing at least one silica precursor preferably a tetraalkoxysilane, such as tetraethoxysilane, dissolved in an organosilic solvent containing an acidic or basic hydrolysis catalyst and the structuring agent;
- Step c) of the process according to the invention consists of consolidating the first and second layers by subjecting them together to a maturation treatment.
- This maturation treatment consists of exposing the substrate and the two layers at a temperature of between 50 ° C. and 250 ° C. for a period of between 10 minutes and 200 hours.
- the treatment is carried out at a temperature between 70 ° C and 140 ° C, more preferably between 80 ° C and 125 ° C, and even more preferably between 100 ° C and 120 ° C.
- the duration of this treatment is between 10 minutes and 200 hours, preferably between 2 and 36 hours, more preferably between 8 and 24 hours, and even more preferably between 10 and 16 hours.
- the duration of this maturation step is advantageously shorter as the temperature of the heat treatment is high.
- the following conditions can be applied: a time of between 11 and 13 hours at a temperature of between 100 ° C. and 120 ° C.
- step c) The consolidation treatment of step c) can be carried out according to the appropriate techniques known to those skilled in the art, for example in an oven, in the open air ...
- the temperature of this treatment carried out during this step c) being less than or equal to 250 ° C., the mesostructuring agent present in the pores of the deposited materials is not eliminated.
- step d) of the process according to the invention consists in bringing the consolidated coating, obtained in step c), into contact with a solution containing metal ions, the metal being chosen from the group consisting of Ag, Au , Pd and Pt, preferably Ag, and irradiating it with a radiation capable of activating the photocatalytic material, for a time sufficient to reach the percolation threshold beyond which metallic nanoparticles obtained by photocatalyzed reduction of the metal ions, together form an electroconductive structure.
- a solution containing metal ions the metal being chosen from the group consisting of Ag, Au , Pd and Pt, preferably Ag, and irradiating it with a radiation capable of activating the photocatalytic material, for a time sufficient to reach the percolation threshold beyond which metallic nanoparticles obtained by photocatalyzed reduction of the metal ions, together form an electroconductive structure.
- the solution containing metal ions may be chosen from a saline solution such for example based on nitrate, chloride, acetate or tetrafluoroborate.
- it is: a solution of silver nitrate (for Ag), or
- the solvent may be a water / isopropanol mixture.
- the coating obtained in step c) is immersed in the solution containing the metal ions.
- the contacting of the solution with the coating can also be carried out by spraying, spin coating, jet of material, inkjet type, or coating.
- the activating radiation of the photo-catalytic material is preferably UV radiation, preferably near UV radiation.
- UV radiation generally means a radiation whose wavelength is between 10 and 400 nm, and "near UV radiation", a radiation whose wavelength is between 200 and 400 nm.
- the photocatalytic material is T1O 2
- the irradiation can typically be performed with a commercial UV lamp.
- the coating formed by the superposition of the first and second layers, consolidated together is brought into contact with the solution of metal ions, in particular by immersion, while the irradiation is carried out. In this way, a constant supply of metal ions is ensured.
- the coating is first impregnated with the metal ion solution, then it is rinsed and / or dried, and then irradiated, ie the coating is not in contact with the solution of metal ions during the irradiation.
- This embodiment has the advantage of being easier to achieve because the irradiation can take place distinctly in the time and space of the contact with the coating. However, it is necessary that sufficient metal ions are introduced into the coating, prior to the irradiation step, so that the percolation threshold can be reached.
- the irradiation carried out in step d) takes place with the aid of a radiation source emitting in the wavelength range considered, in particular in the UV. It may be for example a mercury vapor lamp, a laser or a diode.
- a radiation source emitting in the wavelength range considered, in particular in the UV. It may be for example a mercury vapor lamp, a laser or a diode.
- the irradiation can be done through a mask, preferably a photolithography mask, so as to inscribe a conductive pattern on the substrate.
- the process according to the present invention is characterized in that it does not comprise any heat treatment at a temperature above 250 ° C., more preferably at 200 ° C., even more preferably at 140 ° C. .
- the method according to the invention makes it possible to manufacture mesostructured coatings with electroconductive structures having a conductivity greater than 20 S / cm.
- Such "high" conductivities had already been obtained by Martinez et al. on mesoporous materials, that is to say materials whose structuring agent had been removed by calcination, but never on mesostructured materials still containing the organic structuring agent.
- the method according to the present invention makes it possible to produce coatings comprising electroconductive structures formed of metal nanoparticles chosen from the ions of Ag, Au, Pd and Pt, preferably Ag.
- electroconductive is meant a material capable of conducting electrical current, as opposed to a semiconductor or insulator.
- the electroconductive structures which are included in the coating according to the invention have a conductivity greater than 20 S / cm, preferably greater than 70 S / cm, and even more preferably greater than 90 S / cm, the conductivity being measured according to the Van der Pauw method.
- the first method allows rapid measurement and thus to monitor the conductivity as a function of the irradiation time and therefore the amount of metal nanoparticles, in particular silver, formed on the same film.
- This measurement is made by a Microworld brand surface resistivity meter, using the four-point method (or Van der Pauw method).
- the surface of the coating is brought into manual contact with a "4-point head”.
- the 4 points are each separated by one millimeter.
- the value given is an average of 10 measurements made at 10 different places on the coating. This measurement is made through the first layer which is insulating.
- the second method is to position two silver lacquer pads on the coating, separated by one centimeter from each other, and to measure the resistivity of the coating using an ohmmeter between these two points.
- the given value is obtained from a single measurement.
- the silver lacquer penetrates the porous coating to come into contact with the conductive layer. This measurement can only be done after the end of the irradiation and therefore does not allow real-time monitoring.
- the thickness of the various layers constituting the coating according to the present invention depends on the deposition parameters of these layers during step a) and step b) of the process according to the present invention, and the consolidation treatment of step c) of the process according to the present invention.
- the first layer of mesostructured material of the coating according to the invention has a thickness, after consolidation, of between 200 and 2000 nm, more preferably between 400 and 800 nm.
- the second layer of mesostructured material of the coating according to the present invention has a thickness, after consolidation, of between 50 and 1000 nm, more preferably between 100 and 300 nm.
- the total thickness of the mesostructured coating, after consolidation, according to the present invention is preferably between 250 and 3000 nm, more preferably between 500 and 1100 nm,
- This coating meets a real need. Indeed, thanks to the use of photolithography masks, the electroconductive structures they contain are extremely thin and can be positioned with great precision.
- the method according to the invention has the advantage of not including any heat treatment at a temperature above 250 ° C.
- this method is particularly recommended for use on a polymeric support which has various properties, in particular on a transparent and / or flexible polymeric support.
- the film then undergoes a heat treatment of 12 hours at 110 ° C.
- Three comparative coatings B, C and D were prepared according to the protocol described for the coating A, except that: - The coating B was subjected to two anneals at 110 ° C: Once the first layer is deposited, it is first heat treated at 110 ° C for 12 hours before receiving the second layer, all of the two The layers are then annealed for 12 hours at 110 ° C. In this case the two layers are mesostructured, that is to say they still contain the structuring agent.
- Coating C was annealed at 450 ° C: The two layers were deposited successively and calcined together at 450 ° C. In this case, these two layers are mesoporous, that is to say that the pores of the structure are empty, the structuring agent having been removed by calcination.
- the coating D was subjected to two anneals at 450 ° C: Once the first layer is deposited, it is first calcined at 450 ° C before receiving the second layer, all of the two layers then being subjected calcination at 450 ° C. In this case, the calcination resulting in the decomposition of the structuring agent, the two layers are mesoporous, as in the coating C.
- Graphs A, B, C and D represent the respective evolution of the conductivity of coatings A, B, C and D (measured by the four-point method), as a function of the time of irradiation (UV lamp at 312 nm) in the presence of a solution of AgNC> 3 at 0.05 M in a 50:50 mixture of water and isopropanol.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1054532A FR2961219B1 (en) | 2010-06-09 | 2010-06-09 | PROCESS FOR THE LOW TEMPERATURE PREPARATION OF ELECTROCONDUCTIVE MESOSTRUCTURE COATINGS |
PCT/FR2011/051205 WO2011154637A1 (en) | 2010-06-09 | 2011-05-26 | Method for the low-temperature preparation of electrically conductive mesostructured coatings |
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EP2580373A1 true EP2580373A1 (en) | 2013-04-17 |
EP2580373B1 EP2580373B1 (en) | 2015-07-08 |
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EP11726908.4A Active EP2580373B1 (en) | 2010-06-09 | 2011-05-26 | Procedure for preparing a mesostructured electrically conductive coating at low temperature |
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US (1) | US20130078458A1 (en) |
EP (1) | EP2580373B1 (en) |
JP (1) | JP5908463B2 (en) |
KR (1) | KR101782927B1 (en) |
CN (1) | CN102933744B (en) |
AU (1) | AU2011263565B2 (en) |
BR (1) | BR112012031291B1 (en) |
FR (1) | FR2961219B1 (en) |
WO (1) | WO2011154637A1 (en) |
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US20140262806A1 (en) * | 2013-03-15 | 2014-09-18 | Sunpower Technologies Llc | Method for Increasing Efficiency of Semiconductor Photocatalysts |
EP2829857A1 (en) * | 2013-07-24 | 2015-01-28 | Ecole Polytechnique | Piezoresistive material exhibiting an optimal gauge factor |
CN104934330A (en) * | 2015-05-08 | 2015-09-23 | 京东方科技集团股份有限公司 | Film transistor and preparation method thereof, array substrate and display panel |
US10604442B2 (en) | 2016-11-17 | 2020-03-31 | Cardinal Cg Company | Static-dissipative coating technology |
CN108754460A (en) * | 2018-05-18 | 2018-11-06 | 蚌埠心里程电子科技有限公司 | A kind of Metal surface anti-corrosion automatically cleaning processing method |
US11938469B1 (en) * | 2020-06-08 | 2024-03-26 | National Technology & Engineering Solutions Of Sandia, Llc | Ultrathin layer photocatalysts |
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JP3464590B2 (en) * | 1997-06-06 | 2003-11-10 | 住友大阪セメント株式会社 | Substrate with transparent conductive film and method for manufacturing the same |
FR2800731B1 (en) * | 1999-11-05 | 2002-01-18 | Saint Gobain Vitrage | TRANSPARENT SUBSTRATE HAVING A SILICON-DERIVED LAYER |
JP3530896B2 (en) * | 2000-02-21 | 2004-05-24 | 独立行政法人産業技術総合研究所 | Mesoporous TiO2 thin film having three-dimensional structure and method for producing the same |
JP2001246261A (en) * | 2000-03-08 | 2001-09-11 | Mitsubishi Heavy Ind Ltd | Photocatalyst |
AU2002239008A1 (en) * | 2001-03-21 | 2002-10-03 | Nippon Sheet Glass Co., Ltd. | Coated article, coating liquid composition, and method for producing coated article |
JP4672233B2 (en) * | 2001-11-06 | 2011-04-20 | 大日本印刷株式会社 | Method for manufacturing conductive pattern forming body |
FR2838734B1 (en) * | 2002-04-17 | 2005-04-15 | Saint Gobain | SELF-CLEANING COATING SUBSTRATE |
FR2874007B1 (en) * | 2004-08-03 | 2007-11-23 | Essilor Int | PROCESS FOR PRODUCING A SUBSTRATE COATED WITH A MESOPOROUS LAYER AND ITS OPTICAL APPLICATION |
ES2296533B1 (en) * | 2006-09-22 | 2009-04-01 | Consejo Superior Investig. Cientificas | MULTI-PAPER PREPARATION PROCEDURE WITH ORDERLY MESOPOROUS STRUCTURE, MATERIAL AS OBTAINED AND USED. |
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2010
- 2010-06-09 FR FR1054532A patent/FR2961219B1/en not_active Expired - Fee Related
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- 2011-05-26 AU AU2011263565A patent/AU2011263565B2/en active Active
- 2011-05-26 CN CN201180028111.8A patent/CN102933744B/en active Active
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- 2011-05-26 KR KR1020127030756A patent/KR101782927B1/en active IP Right Grant
- 2011-05-26 JP JP2013513731A patent/JP5908463B2/en active Active
- 2011-05-26 US US13/702,043 patent/US20130078458A1/en not_active Abandoned
- 2011-05-26 WO PCT/FR2011/051205 patent/WO2011154637A1/en active Application Filing
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WO2011154637A1 (en) | 2011-12-15 |
AU2011263565B2 (en) | 2016-06-30 |
JP2013529256A (en) | 2013-07-18 |
US20130078458A1 (en) | 2013-03-28 |
EP2580373B1 (en) | 2015-07-08 |
KR20130095644A (en) | 2013-08-28 |
BR112012031291A8 (en) | 2018-08-14 |
JP5908463B2 (en) | 2016-04-26 |
FR2961219B1 (en) | 2012-07-13 |
CN102933744A (en) | 2013-02-13 |
BR112012031291B1 (en) | 2019-12-24 |
KR101782927B1 (en) | 2017-09-28 |
CN102933744B (en) | 2014-11-26 |
BR112012031291A2 (en) | 2016-11-01 |
FR2961219A1 (en) | 2011-12-16 |
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