Classifications

• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
  • B05D1/322—Removable films used as masks
• • 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
  • C03C17/001—General methods for coating; Devices therefor
  • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
• • 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
  • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
  • H05K3/046—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer
  • H05K3/048—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer using a lift-off resist pattern or a release layer pattern
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/30—Organic light-emitting transistors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/81—Anodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/81—Anodes
  • H10K50/813—Anodes characterised by their shape
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
  • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
• • 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
  • B05D3/12—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 mechanical means
• • 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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• • 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
  • C03C2218/328—Partly or completely removing a coating
• • 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
  • C03C2218/34—Masking
• • 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
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture

Definitions

• the subject of the present invention is a method for manufacturing a mask with submillimeter openings for the production of a submillimetric electroconductive grid, such a mask, and the grid thus obtained.
• Manufacturing techniques are known that make it possible to obtain metal grids of micron size. These have the advantage of achieving surface resistances less than 1 Ohm / square while maintaining a light transmission (T L ) of the order of 75 to 85%.
• T L light transmission
• their method of obtaining is based on a technique of etching a metal layer by means of a photolithographic process inducing a significant manufacturing cost incompatible with the intended applications.
• the document US7172822 describes the realization of uneven network conductor based on the use of a cracked silica gel sol mask.
• a soil based on water, alcohol and a silica precursor (TEOS) is deposited, the solvent is evaporated and annealed at 120 ° C. for 30 minutes in order to form the cracked sol-gel mask. 0.4 ⁇ m thick.
• TEOS silica precursor
• Figure 3 of this document US7172822 discloses the morphology of the sol gel silica mask. It appears as fine fracture lines oriented in a preferred direction, with bifurcations characteristic of the fracture phenomenon of elastic material. These main fracture lines are linked episodically between them by the bifurcations.
• the domains between the fracture lines are asymmetrical with two characteristic dimensions: one parallel to the direction of crack propagation between 0.8 and 1 mm, the other perpendicular between 100 and 200 ⁇ m.
• This method of manufacturing an electrode by cracking of the sol gel mask is certainly an advance for the manufacture of a network conductor by eliminating for example the use of photolithography (exposure of a resin to radiation / beam and development) , but can still be improved, in particular to be compatible with industrial requirements (reliability, simplification and / or reduction of manufacturing steps, at a lower cost, etc.). It may also be noted that this manufacturing process necessarily requires the deposition of an modifiable sub-layer (chemically or physically) at the openings in order to either allow a preferred adhesion (of metal colloids for example) or to allow catalyst grafting. for post-growth of metal, this sub-layer therefore having a functional role in the growth process of the network.
• the crack profile is V due to the fracture mechanics of the elastic material which involves using a post-masking process to grow the metal network from the colloidal particles at the base of V.
• the present invention therefore aims at overcoming the disadvantages of the processes of the prior art by proposing a method of manufacturing an electroconductive grid having at least one submillimeter characteristic dimension (width of strands A 'and / or spacing between strands B') and in electrical contact with at least one power supply element.
• This process must be simple, economical, especially devoid of step (s) of (photo) lithography, flexible (suitable for any desired connector design), achievable even on large surfaces.
• the invention firstly relates to a method for manufacturing a mask with submillimetric openings, in particular micron openings (at least for the width of the openings), for submillimetric electroconductive gate, mask on a main face of a substrate, in particular transparent and / or planar, by depositing a liquid masking layer in a given solution and drying, in which process
• a solution of colloidal nanoparticles stabilized and dispersed in a solvent is deposited, the nanoparticles having a given glass transition temperature Tg,
• the drying of the masking layer is carried out at a temperature below said temperature Tg until a mask is obtained with a two-dimensional network of submillimeter openings, called a grating mask, with edges of zones of the mask substantially right (over the entire thickness), the mask being on a so-called network mask area.
• the method further comprises forming a masking free area on said face by mechanical and / or optical shrinkage of at least one peripheral portion of the network mask area.
• a mesh of openings is formed which can be distributed over the entire masking surface and make it possible to obtain isotropic properties.
• the array of openings has significantly more interconnections than the prior art cracked silica gel ground mask.
• the grating mask has a random, aperiodic structure on at least one characteristic direction of the grating (thus parallel to the surface of the substrate), or even on two (all) directions.
• nanoparticles to promote their dispersion, preferably with at least one characteristic dimension (average), for example the average diameter, between 10 and 300 nm, or even between 50 and 150 nm, of stabilizing the nanoparticles in the solvent (in particular by treatment with surface charges, for example by a surfactant, by control of the pH), to avoid that they agglomerate with each other, that they do not precipitate and / or that they fall by gravity.
• average for example the average diameter, between 10 and 300 nm, or even between 50 and 150 nm
• the concentration of the nanoparticles is adjusted, preferably between 5% and even 10% and 60% by weight, more preferably between 20% and 40%. It avoids the addition of binder (or in a sufficiently small quantity not to influence the mask).
• the drying causes a contraction of the masking layer and a friction of the nanoparticles at the surface inducing a tensile stress in the layer which, by relaxation, forms the openings.
• Drying can lead in one step to the removal of the solvent and the formation of the openings.
• Nanoparticles After drying, a stack of nanoparticles is thus obtained, in the form of clusters of variable size and separated by the openings themselves of variable size. Nanoparticles remain discernible even if they can aggregate. The nanoparticles are not melted to form a continuous layer.
• the drying is carried out at a temperature below the glass transition temperature for the creation of the network of openings. It has indeed been observed that above this glass transition temperature, a continuous layer was formed or at least no cracks throughout the thickness.
• a weakly adhering layer is thus deposited on the substrate, which consists simply of a stack of hard, preferably spherical, nanoparticles. These hard nanoparticles do not establish strong chemical bonds, neither with each other nor with the surface of the substrate. The cohesion of the layer is still ensured by weak forces, such as van der Waals forces or electrostatic forces.
• the resulting mask can be easily removed using pure water, cold or warm, especially with an aqueous solvent, without the need for strongly basic solutions or potentially polluting organic compounds.
• the drying step (as preferably the deposition step) can be carried out (substantially) at a temperature below 50 ° C., preferably at room temperature. typically between 20 0 C and 25 ° C.
• annealing is not necessary.
• the difference between the glass transition temperature Tg given the particles of the solution and the drying temperature is preferably greater than 10 0 C or 20 0 C.
• the drying step of the masking layer can be carried out substantially at atmospheric pressure rather than drying under vacuum for example.
• the drying parameters such as the degree of humidity, the drying speed, can be modified to adjust the average distance between openings B (in other words mask area width), the average size of apertures A (ie distance between adjacent mask area), and / or the ratio B / A. The higher the humidity (all things being equal), the lower A is.
• a solution (aqueous or non-aqueous) of colloids can be deposited by a usual liquid route technique.
• the colloid solution comprises polymeric nanoparticles and preferably with a solvent water-based or even entirely aqueous.
• acrylic copolymers for example, acrylic copolymers, polystyrenes, poly (meth) acrylates, polyesters or mixtures thereof are chosen.
• the masking layer (before drying) can thus consist essentially of a stack of colloidal particles (thus nanoparticles of a material insoluble in the solvent) which are discernable, in particular polymeric.
• the polymeric nanoparticles consist of a solid polymer and insoluble in water.
• the masking layer may optionally comprise other compounds, as traces, and which do not affect the properties of the mask (formation of the network, easy removal ).
• the aqueous colloidal solution is preferably composed of water and polymer colloidal particles, therefore excluding any other chemical agent (such as, for example, pigments, binders, plasticizers, etc.).
• the aqueous colloidal dispersion is preferably the only compound used to form the mask.
• the solution is naturally stable, with nanoparticles already formed.
• the solution preferably does not contain (or in negligible quantity) a polymer precursor type reactive element.
• the mask (after drying) can thus consist essentially of a stack of nanoparticles, preferably polymeric, discernible.
• the polymeric nanoparticles consist of a solid polymer and insoluble in water.
• the solution may comprise, alternatively or cumulatively, mineral nanoparticles, preferably silica, alumina, iron oxide.
• the masking layer it is also possible to selectively remove a part of the net mask without damaging it or damaging the underlying surface, by means of simple optical and / or mechanical means.
• the mask material has a mechanical strength sufficiently low to be removed without damaging the underlying surface but remains strong enough to support the deposition of the electroconductive material for the grid.
• Such a removal of the network mask can be carried out: by mechanical action, in particular by blowing (focused air flow, etc.), by friction with a non-abrasive element (felt-type, fabric, rubber) ), by a cut by a cutting element (a blade ..),
• a liquid deposit of the masking solution can be made on the entire face of the substrate, which is simpler to do, and partially remove the net mask, in particular:
• connection zone both a current supply area when the grid serves as an electrode or heating gate, a zone connected to a mass, when the gate serves as electromagnetic shielding.
• a marker alignment for example
• a decorative element sign, a logo, a mark
• the surface for the deposition of the masking layer is film-forming, especially preferably hydrophilic if the solvent is aqueous.
• Hydrophilic means a surface on which the contact angle of a drop of water 1 mm in diameter is less than 15 °, or even 10 °.
• This is the surface of the preferably transparent substrate: glass, plastic (polycarbonate for example), sapphire, quartz or an optionally functional added underlayer: hydrophilic layer (silica layer, for example on plastic) and / or alkali barrier layer and / or adhesion promoting layer of the gate material, and / or electroconductive layer (transparent), and / or decor layer, colored or opaque and / or, if appropriate, etching stop.
• the method of manufacturing the electrode described in US7172822 necessarily requires the deposition of an modifiable sublayer (chemically or physically) at the cracks to either allow a preferred adhesion (metal colloid for example) as already indicated , in order to allow the grafting of catalyst for a post-growth of metal, this sub-layer therefore having a functional role in the growth process of the network.
• the underlayer according to the invention is not necessarily a growth layer for electrolytic deposition of the gate material.
• the substrate according to the invention may thus comprise an underlayer which is a bottom layer, therefore the layer closest to the substrate, a continuous alkali barrier layer.
• Such a primer protects the gate material from pollution (pollutions which may cause mechanical defects such as delaminations), in the case of electroconductive deposition (to form an electrode in particular), and also preserves its electrical conductivity.
• the basecoat is robust, easy and fast to deposit according to different techniques. It can be deposited, for example by a pyrolysis technique, including chemical vapor deposition (a technique often referred to by the abbreviation of C.V. D, for "Chemical Vapor Deposition”). This technique is interesting for the invention because appropriate settings of the deposition parameters make it possible to obtain a very dense layer for a reinforced barrier.
• the primer may be optionally doped with aluminum and / boron to make its vacuum deposit more stable.
• the bottom layer (monolayer or multilayer, possibly doped) may be between 10 and 150 nm thick, more preferably between 15 and 50 nm.
• the bottom layer may preferably be: based on silicon oxide, silicon oxycarbide, layer of general formula SiOC,
• Silicon nitride is very fast to deposit and forms an excellent barrier to alkalis.
• a promoter layer for adhesion of the metal gate material (silver, gold, etc.), especially on glass, it is possible to choose a layer based on NiCr, Ti, Nb, Al, of single or mixed metal oxide, doped or not, (ITO ...), layer for example of thickness less than or equal to
• the substrate is hydrophobic, one can add a hydrophilic layer such as a silica layer.
• the chosen glass substrate is generally glazing, such as flat or curved glazing, single or multiple (double, triple ...), tempered or annealed glazing, colorless or tinted glazing, the thickness of which is in particular between 1 and 19 mm, more particularly between 2 and
• the opening network can be cleaned using a plasma source at atmospheric pressure.
• the invention also proposes a carrier substrate on a main face:
• a mask having openings submillimetre network compound (preferably consisting essentially of) a stack of detectable nanoparticles, preferably polymeric, including substantially spherical, for example glass transition temperature greater than 50 0 C, with areas mask with substantially straight edge (throughout the thickness), mask on a so-called network mask area, the network mask preferably being on a hydrophilic surface, - at least one masking free zone (for the connection ), adjacent and in contact with the net mask.
• the thickness of the masking layer (if appropriate after drying, the thickness of the net mask) is preferably between 2 and 100 microns, especially between 5 and 50 microns, or between 10 and 30 microns.
• width (mean) of the apertures of the micron or even nanometric grating A in particular between a few hundred nanometers to a few tens of micrometers, in particular between 200 nm and 50 ⁇ m,
• the open pattern ratio is less than 5%, or even less than or equal to 2%, in a given region of the mask, or even on the majority or the entire surface, so with a limited or almost zero network break, possibly reduced, and removable by etching of the network,
• the edges are of constant spacing, parallel, in particular at a scale of 10 ⁇ m (for example observed under an optical microscope with a magnification of 200).
• the width A may be for example between 1 and 20 microns, even between 1 and 10 microns, and B between 50 and 200 microns.
• the sizes of the strands A ' may preferably be between a few tens of microns to a few hundred nanometers.
• the ratio B '/ A' can be chosen between 7 and 20, or even 30 to 40.
• the patterns delimited by the openings are of various shapes, typically three, four, five sides, for example predominantly four sides, and / or of various sizes, distributed randomly, aperiodically.
• the angle between two adjacent sides of a pattern may be between 60 ° and 110 °, in particular between 80 ° and 100 °.
• a main network is obtained with openings (possibly approximately parallel) and a secondary network of openings (possibly approximately perpendicular to the parallel network), whose location and distance are random.
• the secondary openings have a width for example less than the main openings.
• control parameters chosen from the coefficient of friction between the compacted colloids can be modified, in particular by nanotexturing of the substrate and the surface of the substrate, the size of the nanoparticles, and the initial concentration of nanoparticles, the nature of the solvent, the thickness depending on the deposition technique, to adjust B, A, and / or the ratio B / A.
• the thickness of the net mask can be submicron up to several tens of microns. The greater the thickness of the masking layer, the larger A (respectively B) is.
• edges of the openings are substantially straight, that is to say in a mean plane between 80 and 100 ° with respect to the surface (if the surace is curved with respect to the tangential plane), or even between 85 ° and 95 ° .
• the characteristic dimensions of the grids made by pholitholithography are of regular and periodic shape (square, rectangular), constitute networks of wire strands 20 to 30 ⁇ m wide, spaced for example from 300 ⁇ m which are at the origin when illuminated by a point light source, diffraction patterns. And it would be even more difficult and expensive to make grids with random patterns. Each pattern to be made would require a specific mask.
• This technique of manufacturing the prior art also has a resolution limit of the order of a few tens of ⁇ m, leaving the reasons aesthetically visible.
• the network mask according to the invention therefore makes it possible to envisage, at lower cost, irregular grids, other shapes, of any size.
• the strand dimensions can be very small
• the grids have a low electrical resistance ( ⁇ 2 ohms) and a high light transmission (> 80%).
• the mask makes it possible to manufacture an irregular grid with a real mesh or tiling, random grid in at least one (grid) direction, and not a simple conducting network as proposed in the document US7172822.
• the invention therefore also relates to the manufacture of a submillimetric electroconductive grid on a main surface of a substrate comprising successively
• This grid can form a (semi) transparent electrode of an electrically controllable system and / or a heating grid and / or an electromagnetic shielding grid.
• the arrangement of the strands (in other words the network of strands, the strands delimiting meshes) can then be substantially the replica of that of the network of openings.
• the deposit can be made both at through openings and on the mask.
• the removal is carried out by liquid means, by an inert solvent for the grid, for example with water, acetone, alcohol, (optionally hot and / or ultrasonically assisted).
• the deposition of the electroconductive material may be a deposition at atmospheric pressure, in particular by plasma, vacuum deposition, sputtering, or evaporation.
• Electrically conductive material can be deposited on the electroconductive material by electrolysis.
• the deposit is thus possibly supplemented by an electrolytic recharge by using an electrode made of Ag, Cu, Gold, or another metal of high conductivity that can be used.
• electrolytic deposition can be carried out indifferently before or after removal of the mask.
• fuzziness values of between 1 and 20% are obtained for the grid.
• the invention also relates to a substrate, in particular transparent, carrying on a main surface of an irregular submillimetric grid, that is to say a network of two-dimensional and meshed strands with mesh (closed), in particular random in at least one grid direction (so parallel to the substrate).
• the gate is made of an electroconductive material and the face also carries a solid electroconductive zone adjacent and in contact with the gate and said electroconductive material.
• This grid and the solid zone may in particular be formed from the manufacturing method already defined above.
• the solid electroconductive zone may be a wide band, in particular rectangular.
• the grid may have one and / or the following characteristics: a space (average) ratio between the strands B 'over the (mean) submillimetric width of the strands A' of between 7 and 40,
• the patterns of the grid are random (aperiodic), of various shape and / or size, - the cells delimited by the strands are of three and / or four and / or five sides, for example mostly four sides,
• the grid has an aperiodic (or random) structure in at least one direction, preferably in two directions,
• the angle between two adjacent sides of a mesh may be between 60 ° and 110 °, in particular between 80 ° and 100 °,
• the difference between the maximum width of the strands and the minimum width of the strands is less than 4, or even less than or equal to 2, in a given region of the grid, or even on the majority or the entire surface,
• the difference between the maximum mesh size (space between strands forming a mesh) and the minimum mesh size is less than 4, or even less than or equal to 2, in a given grid region, or even the majority or even all the surface,
• blind the rate of non-closed mesh and / or cut strand segment
• edges of strands are constant spacing, including substantially linear, parallel to the scale of 10 microns (for example observed under an optical microscope with a magnification of 200).
• the grid according to the invention may have isotropic electrical properties.
• the irregular electro-conductive grid according to the invention may not diffract a punctual light.
• the thickness of the strands may be substantially constant in the thickness, or be wider at the base.
• the electro-conductive grid according to the invention may comprise a main network with strands (possibly approximately parallel) and a secondary network of strands (possibly approximately perpendicular to the parallel network).
• the electro-conductive grid according to the invention may be deposited on at least one surface portion of the substrate, in particular with a glass function, made of plastic or mineral material, as already indicated.
• the electro-conductive grid according to the invention may be deposited on a hydrophilic and / or adhesion promoter and / or barrier and / or decorative undercoat as already indicated.
• the electro-conductive grid according to the invention may have a square resistance of between 0.1 and 30 Ohm / square.
• the electro-conductive grid according to the invention may have a resistance per square of less than or equal to 5 Ohm / square, or even less than or equal to
• the ratio B '/ A' may be different, for example at least double, in a first gate region and in a second gate region.
• the first and second regions may be of a distinct or equal shape and / or of a distinct or equal size.
• the light transmission of the network depends on the ratio B '/ A' between the average distance between the strands B 'on the average width of the strands A'.
• the ratio B '/ A' is between 5 and even more preferably of the order of 10 to easily retain the transparency and facilitate manufacture, for example B 'and A' being respectively about 50 microns and 5 microns. .mu.m.
• an average width of strands A ' is chosen between 100 nm and 30 ⁇ m, preferably less than or equal to 10 ⁇ m, or even 5 ⁇ m to limit their visibility and greater than or equal to 1 ⁇ m to facilitate manufacture and to easily maintain a high conductivity and transparency.
• an average distance between strands B 'greater than A' between 5 microns and 300 microns, and even between 20 and 100 microns, in order to easily retain transparency.
• the thickness of the strands can be between 100 nm and 5 ⁇ m, especially micron, more preferably from 0.5 to 3 ⁇ m to easily maintain transparency and high conductivity.
• the grid according to the invention may be over a large area, for example an area greater than or equal to 0.02 m 2 or even greater than or equal to 0.5 m 2 or 1 m 2 .
• the substrate may be flat or curved, (for example a tube for a coaxial lamp, etc.) and furthermore rigid, flexible or semi-flexible.
• the main faces of the planar substrate may be rectangular, square or even any other shape (round, oval, polygonal ).
• the substrate may be large, for example, top surface to 0.02 m 2, or even 0.5 m 2 or 1 m 2.
• the substrate may be preferably substantially transparent, mineral or plastic such as polycarbonate PC or polymethyl methacrylate PMMA or PET, polyvinyl butyral PVB, polyurethane PU, polytetrafluoroethylene PTFE etc.
• the substrate is preferably glass, in particular in silicosodocalcic glass.
• the substrate can be tinted.
• the substrate may have a glass function when it is substantially transparent, and whether it is based on minerals (a soda-lime glass, for example) or is based on a plastic material (such as polycarbonate PC or polymethyl methacrylate PMMA).
• minerals a soda-lime glass, for example
• plastic material such as polycarbonate PC or polymethyl methacrylate PMMA
• the substrate may be chosen preferably from quartz, silica, magnesium fluoride (MgF 2 ) or calcium fluoride (CaF 2 ), a borosilicate glass, a glass with less than 0.05% of Fe 2 O 3 .
• MgF 2 magnesium fluoride
• CaF 2 calcium fluoride
• borosilicate glass a glass with less than 0.05% of Fe 2 O 3 .
• magnesium or calcium fluorides transmit more than 80% or even 90% over the entire range of UVs, ie UVA (between 315 and 380 nm), UVB (between 280 and 315 nm), the UVC (between 200 and 280 nm), or the VUV (between about 10 and 200 nm), quartz and certain high-purity silicas transmit more than 80% or even 90% over the entire range of UVA, UVB and UVC,
• Borosilicate glass like Schott borofloat, transmits more than 70% over the entire range of UVA, - Silicone-calcium glasses with less than 0.05% Fe III or
• Fe 2 O 3 notably Saint-Gobain's Diamant glass, Pilkington's Optiwhite glass, and Schott's B270 glass, transmit more than 70% or even 80% over the entire range of UVA.
• a silica-based glass such as Planilux glass sold by Saint-Gobain, has a transmission greater than 80% beyond 360 nm, which may be sufficient for certain embodiments and applications.
• the substrate may also be chosen to be transparent in a given infrared range, for example between 1 ⁇ m and 5 ⁇ m. This is for example sapphire.
• the light transmission (overall) of the substrate coated with the grid may be greater than or equal to 50%, even more preferably greater than or equal to 70%, in particular between 70% to 86%.
• the (overall) transmission in a given IR range for example between 1 and 5 ⁇ m, of the substrate coated with the grid greater than or equal to 50%, more preferably still greater than or equal to 70%, in particular is between 70% at 86%.
• the targeted applications are for example heated windows with infrared vision system, especially for night vision.
• the (overall) transmission in a given UV range, of the substrate coated with the grid may be greater than or equal to 50%, even more preferably greater than or equal to 70%, in particular is between 70% to 86%.
• the gate according to the invention can be used in particular as a lower electrode (closest to the substrate) for an organic electroluminescent device (OLED in English) in particular at the rear emission ("bottom emission” in English) or emission by the back and front.
• OLED organic electroluminescent device
• Multiple glazing, laminated (laminating interlayer type EVA, PU, PVB ”) can incorporate a carrier substrate of the grid according to the invention with the adjacent connector area and in contact with the gate.
• active layer in an electrochemical device, and / or electrically controllable and with variable optical and / or energy properties, for example a liquid crystal device or a photovoltaic device, or an organic or inorganic electroluminescent device ("TFEL "etc.), a particularly flat lamp, a UV lamp possibly flat,
• TFEL organic or inorganic electroluminescent device
• a heating grid of a heating device a vehicle, (windshield, rear window, porthole ..), household electrical equipment, radiator type, towel dryer, refrigerated enclosure, for a defrosting action, anti-condensation , antifog, ....
• the "all solid” (the “all solid” are defined, within the meaning of the invention, for stacks of layers for which all the layers are of inorganic nature) or “all “(the” all polymers “are defined, within the meaning of the invention for stacks of layers for which all the layers are of organic nature), or alternatively mixed or hybrid electrochromes (the layers of the stack are of organic nature and of inorganic nature) or to liquid crystal or viologen systems.
• the discharge lamps include with phosphor (s) as active element.
• the flat lamps in particular comprise two glass substrates maintained with a small spacing relative to each other, generally less than a few millimeters, and hermetically sealed so as to enclose a gas under reduced pressure in which an electrical discharge produces a radiation generally in the ultraviolet range which excites a phosphor then emitting visible light.
• the UV flat lamps can have the same structure, one naturally chooses for at least one of the walls a material transmitting UV (as already described).
• the UV radiation is directly produced by the plasma gas and / or by a suitable additional phosphor.
• UV flat lamps As examples of UV flat lamps, one can refer to the patents WO2006 / 090086, WO2007 / 042689, WO2007 / 023237 WO2008 / 023124 incorporated by reference.
• the discharge between the electrodes may be non-coplanar ("plane plane"), with anode and cathode respectively associated with the substrates, by one face or in the thickness, (both internal or external, the internal one and the other external, at least one in the substrate .7) for example as described in WO2004 / 015739, WO2006 / 090086, WO2008 / 023124 incorporated by reference.
• the discharge between the electrodes can be coplanar (anode and cathode in the same plane, on the same substrate) as described in patent WO2007 / 023237 incorporated by reference.
• This layer is preferably separated from the electrodes by insulating layers. Examples of such glazings are described in EP1 553 153 A (with the materials for example in Table 6).
• a liquid crystal glazing can be used as glazing with variable light diffusion. It is based on the use of a film placed between two conducting layers and based on a polymeric material in which droplets of liquid crystals, in particular nematic with positive dielectric anisotropy, are dispersed.
• the liquid crystals when the film is turned on, are oriented along a preferred axis, which allows vision. When the crystals are not aligned, the film becomes diffused and prevents vision. Examples of such films are described in particular in European Patent EP0238164 and US Patents US4435047, US4806922, US4732456. This type of film, once laminated and incorporated between two glass substrates, is marketed by SAINT-GOBAIN GLASS under the trade name Privalite.
• NCAP Nematic Curvilinearly Aligned Phases in English
• PDLC Polymer Dispersed Liquid Crystal in English
• CLC Cholesteric Liquid Crystal in English
• These may further contain dichroic dyes, especially in solution in the liquid crystal droplets. It is then possible to modulate the light scattering and the light absorption of the systems.
• cholesteric liquid crystal-based gels containing a small amount of crosslinked polymer such as those described in patent WO-92/19695.
• the invention also relates to the incorporation of grid as obtained from the development of the mask previously described in windows, operating in transmission.
• Glazing is to be understood in a broad sense and encompasses any essentially transparent, glass-function, glass and / or polymeric material (such as polycarbonate PC or polymethyl methacrylate PMMA).
• the carrier substrates and / or counter-substrates that is to say the substrates surrounding the active system, can be rigid, flexible or semi-flexible.
• the invention also relates to the various applications that can be found in these devices, glazing or mirrors: it may be to make glazing for building, including external glazing, internal partitions or glass doors. It can also be windows, roofs or internal partitions of means of transport such as trains, planes, cars, boats, construction equipment. It can also be display or display screens, such as projection screens, television or computer, touch screens, illuminated surfaces, heated windows.
• FIGS. 1 to 2d show masks used in the process according to the invention
• FIG. 3a is an SEM view illustrating the profile of the opening of the mask
• FIG. 3b schematically represents a front view of the network mask according to the invention with two free zones of masking according to the invention
• FIG. 3c schematically represents a front view of the network mask according to the invention with a free masking zone according to the invention
• FIG. 3d schematically represents a front view of the network mask according to FIG. invention with zones of free masking according to the invention
• FIG. 4 represents a grid in plan view
• FIGS. 5 and 6 show masks with different drying fronts
• FIGS. 7 and 8 show partial views SEM of grid
• a substrate with a glass function 1 for example planar and mineral
• a glass function 1 for example planar and mineral
• spin coating a single emulsion of colloidal particles based on acrylic copolymer stabilized in the water in a mass concentration of 40%, a pH of 5.1, with a viscosity of 15 mPa.s.
• the colloidal particles have a characteristic dimension of 80 to 100 nm and are marketed under the company DSM under the trademark Neocryl XK 52® and have a Tg equal to 115 ° C.
• the drying layer incorporating the particles is then dried. colloidal so as to evaporate the solvent and to form the openings.
• This drying can be carried out by any suitable method and at a temperature below Tg (hot air drying, etc.), for example at room temperature.
• Tg hot air drying, etc.
• the system self-arranges, forms a network mask 1 having an array of openings 10. It describes patterns, examples of which are shown in FIGS. 1 and 2 (views (400 ⁇ m x 500 ⁇ m)).
• a stable network mask 1 is obtained without resorting to an annealing with a structure characterized by the opening width (average) subsequently denoted by A (in fact the size of the A 'strand) and the (middle) space between the openings subsequently designated B.
• This stabilized mask will subsequently be defined by the ratio B / A.
• the layer based on XK52 is this time deposited by flow coating, which gives a variation in thickness between the bottom and the top of the sample (from 10 ⁇ m to 20 ⁇ m) leading to a variation in mesh size. .
• This ratio B / A is also modified by adapting, for example, the coefficient of friction between the compacted colloids and the surface of the substrate, or the size of the nanoparticles, or even the rate of evaporation, or the initial concentration of particles, or the nature of the solvent, or the thickness depending on the deposition technique.
• the surface roughness of the substrate was finally modified by atmospheric plasma etching of the glass surface via a mask of Ag nodules. This roughness is of the order of magnitude of the size of the areas of contact with the colloids which increases the coefficient of friction of these colloids with the substrate.
• the following table shows the effect of the change of coefficient of friction on the ratio B / A and the morphology of the mask. It appears that we obtain smaller mesh sizes with identical initial thickness and an increasing ratio B / A.
• the dimensional parameters of the network of openings obtained by spin coating of the same emulsion containing colloidal particles previously described are given below.
• the different rotational speeds of the "spin coating" apparatus modify the structure of the mask.
• a network mask 1 is obtained.
• FIG. 3a is a partial transverse view of the mask 1, obtained by SEM.
• the profile shown in FIG. 3a presents a definite advantage for:
• the network mask 1 thus obtained can be used as modified or modified by different post treatments.
• the inventors have furthermore discovered that the use of a plasma source as a cleaning source for the organic particles located at the bottom of the opening subsequently makes it possible to improve the adhesion of the material used for the grid. If there are no colloidal particles in the bottom of the openings, there will be a maximum adhesion of the material that is expected to be provided to fill the opening (this will be described in detail later in the text) with the glass-function substrate.
• a cleaning using a plasma source at atmospheric pressure, plasma blown based on a mixture of oxygen and helium allows both the improvement of the adhesion deposited material at the bottom of the openings and widening of the openings. It will be possible to use a plasma source of "ATOMFLOW" brand marketed by the company Surfx.
• a plasma source of "ATOMFLOW" brand marketed by the company Surfx In another embodiment, a single emulsion of colloidal particles based on acrylic copolymer stabilized in water is deposited in a mass concentration of 50%, a pH of 3, with a viscosity equal to 200 mPa.s.
• the colloidal particles have a characteristic dimension of about 118 nm and are marketed by DSM under the trade name Neocryl XK 38® and have a Tg equal to 71 ° C.
• the resulting network is shown in Figure 2c.
• the space between strands openings is between 50 and 100 100 microns and the range of widths of the strand openings is between 3 and 10 microns.
• a 40% silica colloid solution with a characteristic dimension of about 10 to 20 nm, is deposited, for example the LUDOX® AS 40 product sold by Sigma Aldrich.
• the B / A ratio is about 30 or so, as shown in Figure 2d.
• silica colloids typically, it is possible to deposit, for example, between 15% and 50% of silica colloids in an organic solvent (in particular aqueous).
• the mask occupies the entire face of the substrate.
• This elimination can consist of: in the removal of one or more peripheral strips of the mask, for example two parallel rectangular lateral strips 21, 22 (or longitudinal strips) as shown in FIG. 3b,
• Figure 3d schematically shows a front view of the network mask according to the invention with free zones of masking according to the invention.
• the network mask area 1 is divided into four disjoint regions 11 to 14, round. Each of the regions is surrounded by an annular free zone 21 to 24 ring, made by removing the net mask before deposition of the gate material.
• Each annular free mask area is connected by free masking tracks 31 to 34, opening to a peripheral common track 35.
• a solid mask is used for the other zones 40, intended to be electrically insulating.
• an electrically conductive deposit is made of a grid connected to the connection zone (s).
• the material chosen is from electrically conductive materials such as aluminum, silver, copper, nickel, chromium, alloys of these metals, conductive oxides chosen especially from ITO, IZO, ZnO: Al; ZnO: Ga ZnO: B; SnO2: F; SnO2: Sb.
• This deposition phase may be carried out for example by magnetron sputtering or by gas phase deposition.
• the material is deposited inside the network of openings so as to fill the openings, the filling taking place in a thickness, for example of the order of 1/2 mask height.
• the net mask is then immersed in a solution containing water and acetone (the cleaning solution is chosen according to the nature of the nanoparticles), then rinsed so as to remove all the parts coated with nanoparticles.
• the cleaning solution is chosen according to the nature of the nanoparticles
• FIG. 4 shows a photograph obtained at the SEM of a grid 5 with its strands 50 thus obtained (without showing the connection zone).
• Figures 7 and 8 show SEM views from above (in perspective) and detail of the strands of an aluminum grid 5. It is observed that the strands 50 have relatively smooth and parallel edges.
• the electrode incorporating the gate 5 according to the invention has a electrical resistivity between 0.1 and 30 Ohm / square and a TL of 70 to 86%, which makes its use as a transparent electrode perfectly satisfactory.
• the metal gate has a total thickness of between 100 nm and 5 ⁇ m.
• the electrode remains transparent, that is to say that it has a low light absorption in the visible even in the presence of the grid (its network is almost invisible given its dimensions).
• the grid has an aperiodic or random structure in at least one direction to avoid diffractive phenomena and induces a shadowing of 15 to 25% of the light.
• a network as shown in Figure 4 having metal strands 50 700 nm wide spaced 10 microns gives a bare substrate of light transmission 92% 80% light transmission.
• Another advantage of this embodiment method is that it is possible to modulate the blur value in reflection of the grids.
• the fuzziness value is of the order of 4 to 5%.
• the blur value is less than 1%, with B / A being constant.
• a promoter-adhesion sub-layer of the gate material For example, nickel is deposited and aluminum as the gate material. This grid is shown in Figure 9.
• ITO, NiCr or Ti is deposited and as silver gate material.
• the glass coated with the adhesion promoting sublayer and the magnetron sputtering silver grid constitutes the cathode of the experimental device; the anode consists of a copper plate. Its role in dissolving, to maintain constant throughout the deposition process concentration of Cu 2+ ions and thus the deposition rate.
• the temperature of the solution during the electrolysis is 23 ⁇ 20 ° C.
• the deposition conditions are: voltage ⁇ . 1.5 V and current ⁇ . 1 A.
• the anode and the cathode are positioned parallel to obtain lines of perpendicular fields.
• the copper layers are homogeneous on the silver grids.
• the thickness of the deposit increases with the duration of the electrolysis and the density of the current as well as the morphology of the deposit. The results are reported in the table below and in Figure 10.
• the SEM observations (carried out on these grids) show that the mesh size is 30 ⁇ m ⁇ 10 ⁇ m and the size of the strands is between 2 and 5 ⁇ m.
• the invention can be applied to various types of electrically controllable systems, in particular electrochemical systems, in which the electroconductive grid with its connections can be integrated as an active layer (as electrode, heating layer or electromagnetic shielding layer) connected.
• active layer as electrode, heating layer or electromagnetic shielding layer
• a first category of system includes electrochromic systems, especially "all solid” (the “all solid” being defined, within the meaning of the invention for stacks of layers for which all the layers are of inorganic nature) or “all solid” polymer “(the” all-polymer “being defined, within the meaning of the invention for stacks of layers for which all the layers are of organic nature), or for mixed or hybrid electrochromes
• the layers of the stack are of an organic nature and of an inorganic nature) or else to liquid crystal or viologen systems.
• a single zone of connectivity can suffice, one can for example choose a lateral or longitudinal rectangular band or frame.
• lamps flat and / or UV with phosphor discharge (s) as active element.
• the electroconductive grid thus produced can also constitute an electromagnetic shielding, a single zone of connectivity can then be sufficient, one can for example choose a rectangular lateral or longitudinal band or the frame. For example, the mask described in FIG. 3c is chosen.
• the electroconductive grid thus produced can also also constitute a heating grid, in particular in a windshield, two zones of connections are then necessary, one can for example choose two rectangular strips on two opposite edges (lateral, longitudinal ....) .
• the mask described in FIG. 3c is chosen.
• electroconductive grid can also serve as a lower electrode of a light emitting system, in particular organic (OLED). Two areas of electrically isolated connections between them are then necessary, the first being in electrical contact with the grid the second being also electrically insulated from the grid and used to the upper electrode.
• OLED organic
• peripheral bands For example four peripheral bands are formed, two lateral peripheral bands for the lower electrode (closer to the substrate), two longitudinal peripheral bands for the upper electrode.
• the second connection zone (the two longitudinal peripheral bands in this case) is separated, for example by selective chemical etching (screen printing paste for example) or by laser of the grid.

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