Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • 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
• • 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
  • C03C4/00—Compositions for glass with special properties
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
  • H10K10/80—Constructional details
  • H10K10/82—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
• • 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
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/251—Al, Cu, Mg or noble metals
  • C03C2217/252—Al
• • 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
  • C03C2218/10—Deposition methods
  • C03C2218/11—Deposition methods from solutions or suspensions
  • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
  • G02F1/153—Constructional details
  • G02F1/155—Electrodes
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
  • G02F1/153—Constructional details
  • G02F1/155—Electrodes
  • G02F2001/1555—Counter electrode
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
  • H10K2102/301—Details of OLEDs
  • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
• • 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.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• • 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.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer

Definitions

• the subject of the present invention is a method for producing a mask with submillimeter openings with a view to producing a grid, possibly electroconductive, in particular for an electrochemical device, and / or electrically controllable of the glazing type and having optical properties and / or variable energy, or a photovoltaic device, or a light emitting device, or even a heating device, or possibly a flat lamp device.
• 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 (TL) of the order of 75 to 85%.
• TL light transmission
• these grids have a certain number of disadvantages: their method of obtaining is based on a technique of etching a metal layer or by means of a photolithographic process associated with a chemical etching process by a liquid route, either by a laser ablation technique.
• a soil based on water, alcohol and a silica precursor 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.
• 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 crack propagation direction 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 constitutes an advance for the manufacture of a network conductor by eliminating for example the use of photolithography (exposure of a resin to a radiation / beam and development), but can still be improved, especially to be compatible with industrial requirements (reliability, simplification and / or reduction of manufacturing steps, at a lower cost, etc.).
• this irregular array electrode can be improved.
• the manufacturing process necessarily requires the deposition of an modifiable sub-layer (chemically or physically) at the interstices to either allow a preferred adhesion (of metal colloids for example) or allow the grafting of catalyst for a post-growth of metal, this sub-layer thus having a functional role in the growth process of the network.
• the crack profile is in fact V fracture mechanics of the elastic material which involves using a post-mask process to grow the metal network from the colloidal particles at the base of V.
• the present invention therefore aims at overcoming the drawbacks of the processes of the prior art by proposing a method of manufacturing a submillimeter and irregular network, in particular electroconductive, economical, reproducible, controlled, and whose optical properties and / or properties of electrical conductivity are at least comparable to those of the prior art.
• the subject of the invention is firstly a method for manufacturing a mask with submillimeter openings on a surface portion of a substrate, especially with a glass function, comprising the following steps:
• a mask layer is deposited on the substrate or on a sub-layer from a solution of colloidal particles stabilized and dispersed in a solvent,
• the mask layer is dried until a two-dimensional network of interstices with a substantially straight edge is formed, forming the mask with a random interstice mesh, aperiodic in at least one direction.
• the average width A is submillimetric
• the gap network has significantly more interconnections than the fissured silica gel ground mask.
• the width (average) of the micron or even nanometric network A in particular between a few hundred nanometers to a few tens of micrometers, in particular between 200 nm and 50 ⁇ m,
• - size (average) pattern B millimeter or submillimeter, in particular between 5 to 500 microns, or even 100 to 250 microns,
• the open mesh rate (non-emerging gap, "blind"), 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, therefore with a rupture limited network see almost zero, possibly reduced, and deleted by burning 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 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 meshes delimited by the openings are of various shapes, typically three, four, five sides, for example mainly four sides, and / or of various sizes, randomly distributed, aperiodic.
• the angle between two adjacent sides of a mesh can be between 60 ° and 1 10 °, in particular between 80 ° and 100 °.
• a main network is obtained with gaps (possibly approximately parallel) and a secondary network of interstices (possibly approximately perpendicular to the parallel network), the location and distance of which are random.
• the secondary interstices have a width for example less than the main interstices.
• the solution is naturally stable, with nanoparticles already formed, and preferably does not contain (or in negligible amount) polymer-precursor type reactive element.
• Drying leads in one step to the removal of the solvent and the formation of the interstices. After drying, clusters of nanoparticles, clusters of variable size and separated by the interstices of variable size, are thus obtained. To obtain the openings over the entire depth, it is necessary at a time:
• particles of limited size nanoparticles
• dispersion with preferably a characteristic (average) dimension between 10 and 300 nm, or even 50 and 150 nm
• the concentration of particles is adjusted, preferably between 5% and even 10% and 60% by weight, more preferably between 20% and 40%. The addition of binder is avoided.
• the solvent is preferably water-based or even entirely aqueous.
• the colloid solution comprises polymeric nanoparticles (and preferably with a water-based or even entirely aqueous solvent)
• the solution comprises inorganic nanoparticles, preferably silica, alumina, iron oxide.
• the particles having a given glass transition temperature Tg, the deposition and the drying can preferably be carried out at a temperature below said temperature Tg for a better control of the morphology of the grid mask,
• the deposition and drying steps of the process may in particular be carried out (substantially) at room temperature, typically between 20 ° and 25 ° C. Annealing is not necessary.
• the difference between the given glass transition temperature Tg of the particles and the drying temperature is preferably greater than
• the deposition and drying steps of the process can be carried out substantially at atmospheric pressure rather than vacuum drying for example.
• a solution (aqueous or non-aqueous) of colloids can be deposited by a usual liquid route technique.
• drying parameters such as the degree of humidity, the drying speed, can be modified to adjust B, A, and / or the B / A ratio.
• 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 particles, the nature of the solvent, the thickness depending on the deposition technique, to adjust B, A, and / or ratio B / A.
• the thickness of the mask can be submicron up to several tens of microns. The greater the thickness of the mask layer, the larger A (respectively B) is.
• edges of the mask are substantially straight, that is to say in a mean plane between 80 and 100 ° relative to the surface, or even between 85 ° and 95 °.
• the discontinuous layer is deposited (no or little deposit along the edges) and the coated mask can be removed. without damaging the grid.
• the deposit can be made both through the interstices and on the mask.
• the interstitial network can be cleaned using a plasma source at atmospheric pressure.
• a plasma source at atmospheric pressure.
• a heat treatment (local or otherwise) at a temperature above Tg, in particular 3 times at 5 times Tg, and naturally below the melting temperature Tf, or a differential drying of the mask, for example by modifying locally the degree of humidity and / or the temperature.
• the pads consist of a mass of nanoparticles: under the action of temperature, these pads are likely to become denser. After densification the size of the pads (B) is decreased: their surface and the thickness are reduced. There is thus by this heat treatment modification in the characteristic dimensions of the mask: ratio between the opening of the stitches and the width of the stitches.
• the compaction of the mask in the second advantage, causes an improvement in the adhesion thereof on the substrate which makes it more manipulable (it avoids chipping) while keeping the steps of lift-off possible (simple washing at the same time). water if the colloid was deposited from an aqueous solution).
• the heating time is adjusted according to the temperature of the treatment. Typically the duration is less than 1 h, preferably 1 min to 20 min.
• the modified zone or zones may be peripheral or central, of any form.
• the surface for the deposition of the mask layer is film-forming, in particular hydrophilic if the solvent is aqueous.
• This is the surface of the substrate: glass, plastic (polycarbonate for example) or an optionally added underlayer: hydrophilic layer (silica layer, for example on plastic) and / or alkali barrier layer and / or or adhesion promoting layer of the gate material, and / or electroconductive layer (transparent), and / or decor layer, colored or opaque.
• This underlayer is not necessarily a growth layer for electrolytic deposition of the gate material.
• the substrate according to the invention may thus comprise an underlayer (in particular as a base layer, the closest to the substrate), which is continuous and may be an alkaline barrier. It protects the grid material (pollution that can cause mechanical defects such as delamination) 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, especially in the gas phase (technique often referred to by the abbreviation of C. V. D, for "Chemical Vapor
• the primer may be optionally doped with aluminum and / boron to make its vacuum deposit more stable.
• the layer of background (monolayer or multilayer, possibly doped) may be of thickness between 10 and 150 nm, 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 Si3N 4 doped or not. Silicon nitride is very fast to deposit and forms an excellent barrier to alkalis.
• the metal grid material silver, gold
• the substrate is hydrophobic, one can add a hydrophilic layer such as a silica layer.
• the mask according to the invention therefore makes it possible to envisage, at a lower cost, other shapes, other grid sizes than regular grids with a geometric pattern and while keeping the irregular nature of the conducting network already known but which does not form a grid. wire rack.
• the deposition, (in particular) through the interstices of said mask of a so-called grid material to fill a fraction of the depth of the interstices.
• the masking layer (which is optionally a first layer) is removed until the grid is revealed based on said gate material (one or more layers).
• the arrangement of the strands can then be substantially the replica of that of the network of openings.
• the removal is carried out by liquid means, by an inert solvent for the grid, for example with water, acetone, alcohol,
• the deposition of the gate material fills both a fraction of the openings of the mask and also covering the surface of the mask,
• the deposition of the gate material is a deposition at atmospheric pressure, in particular by plasma, vacuum deposition, sputtering, evaporation.
• the material deposited in the interstices may be chosen from electrically conductive materials.
• the gate material may be electrically conductive and is deposited on the gate material electrically conductive 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.
• the invention also relates to a substrate carrying a grid irregular, that is to say a network of two-dimensional and meshed strands, with meshes (closed patterns), random, aperiodic.
• This grid may in particular be formed from the mask already defined above.
• the grid may have one and / or the following characteristics:
• the grid patterns are random (aperiodic), of various shape and / or size,
• - meshes delimited by the strands are 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, for most or all meshes, in a given region or over the entire surface, the gap between the largest dimension mesh characteristic and the smallest characteristic dimension of mesh less than 2,
• 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 strands and the minimum width of 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 whole surface, the distance 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 on the majority or even the entire surface,
• the rate of non-closed mesh and / or cut strand segment is less than 5%, or even less than or equal to 2%, in a given grid region, or even on the majority or the entire surface area , or a limited network break, see almost zero, -
• the 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 grid according to the invention can not diffract a point light.
• the thickness of the strands may be substantially constant in the thickness, or be wider at the base.
• the grid may comprise a main network with strands (possibly approximately parallel) and a secondary network of strands (possibly approximately perpendicular to the parallel network).
• the grid may be deposited on at least one surface portion of the substrate, in particular with a glass function, plastic or mineral, as already indicated.
• the grid may be deposited on a sub-layer, hydrophilic and / or promoter adhesion and / or barrier and / or decor as already indicated.
• the electro-conductive grid 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 which is less than or equal to 5 Ohm / square, or even less than or equal to 1 Ohm / square, or even 0.5 Ohm / square, in particular for an upper gate thickness or equal to 1 micron, and preferably less than 10 microns or even less than or equal to 5 microns.
• the light transmission of the substrate coated with the grid greater than or equal to 50%, even more preferably greater than or equal to 70%, in particular is between 70% to 86%.
• the B / A ratio 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.
• a gradient of electrical power (application to heating, defrosting, achieving homogeneous heat flow on non-rectangular surfaces.
• 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 transparency and facilitate manufacture.
• B and A are respectively about 50 microns and 5 microns.
• 100 nra and 30 microns preferably less than or equal to 10 microns, or even 5 microns to limit their visibility and greater than or equal to 1 micron to facilitate manufacture and to easily maintain high conductivity and transparency.
• an average distance between strands B greater than A between 5 ⁇ m and 300 ⁇ m, or even between 20 and 100 ⁇ m, to easily retain transparency.
• the thickness of the strands may be between 100 nm and 5 ⁇ m, especially micron, more preferably 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, and further rigid, flexible or semi-flexible.
• This substrate may be large, for example, top surface to 0.02 m 2, or even 0.5 m 2 or I m 2 and with a lower electrode substantially occupying the surface (the structuring zones)
• the substrate may be substantially transparent, mineral or in 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 of silicosodocalcic glass.
• a substrate has a glass function when it is substantially transparent, and is based on minerals (a soda-lime glass, for example) or is based on plastic (like polycarbonate PC or polymethyl methacrylate PMMA),
• 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
• a multiple glazing, laminated may incorporate a carrier substrate of the grid according to the invention.
• 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 electroluminescent device, a device for flat lamp,
• heating of a heating device, an electromagnetic shielding device, or any other device requiring a layer (optionally
• FIGS. 1 to 2e represent examples of masks obtained by the method according to the invention.
• FIG. 3 is an SEM view illustrating the profile of the crack
• FIG. 4 represents a grid in plan view - FIGS. 5 and 6 show masks with different drying fronts
• FIGS. 7 and 8 represent partial views SEM of gate
• FIGS. 9 and 10 show grids in plan view.
• a spin coating emulsion of a single emulsion of acrylic-based copolymer-based particles stabilized in water at a mass concentration of 40% is deposited. of 5, 1, of viscosity equal to 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 1 15 ° C.
• the layer incorporating the colloidal particles is then dried so as to evaporate the solvent and form the interstices.
• This drying can be carried out by any suitable method and preferably at a temperature below Tg (hot air drying, etc.), for example at room temperature.
• 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 contact areas 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 interstitial network obtained by spin coating of the same emulsion containing colloidal particles are given below. previously described.
• the different rotational speeds of the "spin coating" apparatus modify the structure of the mask.
• the crack profile shown in FIG. 3 has a certain advantage for: depositing, in particular in a single step, a large thickness of material,
• the mask thus obtained can be used as modified or modified by different post treatments.
• there is no no colloidal particles in the bottom of cracks so there will be a maximum adhesion of the material that is expected to provide so as to fill the crack (this will be described in detail later in the text) with the substrate glass function.
• the inventors have furthermore discovered that the use of a plasma source as a cleaning source for organic particles situated at the bottom of the crack subsequently makes it possible to improve the adhesion of the material used for the grid.
• 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 of the material deposited at the bottom of the interstices and widening of the interstices.
• a plasma source of "ATOMFLOW" brand marketed by the company Surfx it will be possible to use a plasma source of "ATOMFLOW" brand marketed by the company Surfx.
• 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, of viscosity equal to 200 mPa.s.
• the colloidal particles have a characteristic dimension of about 18 nm and are marketed under the company DSM under the trademark Neocryl XK 38® and have a Tg equal to 71 ° C.
• the resulting network is shown in Figure 2c.
• 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 FIG.
• silica colloids typically, it is possible to deposit, for example, between 15% and 50% of silica colloids in an organic solvent (in particular aqueous).
• a grid is produced. To do this, we proceed to deposit, through the mask, a material to fill the interstices.
• the material chosen is preferably from electrically conductive materials such as aluminum, silver, copper, nickel, chromium, the alloys of these metals, conductive oxides chosen in particular from HTO, IZO, ZnO: Al; ZnO: Ga ZnO: B; SnO2: F; SnO2: Sb; nitrides such as titanium nitride, carbides such as silicon carbide ...
• 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 interstices so as to fill the cracks, the filling taking place in a thickness for example of the order of 1/2 mask height.
• a "lift off” operation is performed. This operation is facilitated by the fact that the cohesion of the colloids results from weak forces VanderWaals type (no binder, or bonding resulting by annealing).
• the colloidal mask is then immersed in a solution containing water and acetone (the cleaning solution is chosen according to the nature of the colloidal particles) and then rinsed so as to remove all the parts coated with colloids.
• FIG. 4 shows a photograph obtained by SEM of a grid thus obtained.
• Figures 7 and 8 show SEM views from above (in perspective) and detail of the strands of an aluminum grid. It is observed that the strands have relatively smooth and parallel edges.
• the electrode incorporating the gate according to the invention has an electrical resistivity of 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 FIG. 4 having metal wires 700 nm wide spaced apart by 10 ⁇ m, gives a bare light transmission substrate 92% an 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.
• B strand spacing
• a blur of the order of 20% is obtained. Beyond a fuzziness value of 5%, this phenomenon can be used as a means light extraction at the interfaces or means for trapping light.
• a promoter-adhesion sub-layer of the gate material Prior to the deposition of the mask material, it is possible to deposit, in particular by vacuum deposition, a promoter-adhesion sub-layer of the gate material.
• 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.
• a copper overcoat on the silver gate 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 deposition conditions are as follows: voltage ⁇ 1, 5 V and current £ 1 A.
• the anode and cathode spaced 3 to 5 cm apart and of the same size, are positioned parallel to obtain perpendicular line lines
• the copper layers are homogeneous on the silver grids.
• the thickness of the deposit increases with the duration of the electrolysis and the current density as well as the morphology of the deposit. The results are reported in the table below and in Figure 10.
• the SEM observations (performed 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 different types of electrochemical or electrically controllable systems in which the grid can be integrated as an active layer (as an electrode for example). It is more particularly interested in electrochromic systems, especially the "all solid” ones (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 the “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 electrochromic or hybrid (the layers of the stack are of organic nature and inorganic nature) or to liquid crystal or viologen systems, or electroluminescent systems, flat lamps.
• the metal grid thus produced may also constitute a heating element in a windshield, or an electromagnetic shield.
• the invention also relates to the incorporation of grid as obtained from the development of the mask previously described in windows, operating in transmission.
• the term "glazing” is to be understood in the broad sense and encompasses all material 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 screens, touch screens, illuminating surfaces, heated windows.

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• 2007
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• 2008
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