Classifications

• • 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
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
• • 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 
  • G02F1/13—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 liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/133345—Insulating layers
• • 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 
  • G02F1/13—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 liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1343—Electrodes
  • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
• • 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
  • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
• • 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
  • H10K50/82—Cathodes
  • H10K50/824—Cathodes combined with auxiliary electrodes

Definitions

• the present invention relates to an electroconductive support, the electrochromic device incorporating it and its manufacture.
• the lower electrode of an electrochromic glazing is a transparent layer based on indium oxide, generally tin-doped indium oxide, better known by the abbreviation ITO of thickness of l 100 to 600nm, and whose square resistance is greater than 10-15Ohm.
• the manufacturing process remains to simplify and make reliable on an industrial scale without penalizing or even improving the optical and electrical performance of the electrochromic device.
• an electroconductive support for electrochromic device comprising:
• a glass substrate transparent, possibly translucent, in particular if textured on the surface
• organic or mineral glass with a refractive index n- ⁇ in a range from 1.45 to 1.8, with a first main face, so-called first surface
• an electrode which comprises a layer arranged in a grid, referred to as a metal grid, made of metal material (pure or alloy, preferably single-layer or even multilayer) having a resistance per square of less than 10 ⁇ / D, better than 5 ⁇ , the metal gate having a thickness e2 of at least 100 nm and preferably at most 1500 nm, the metal gate being formed of strands (in other words tracks) having a width A of less than or equal to 50 ⁇ m, and being separated by a distance between strands B less than or equal to 5000 ⁇ and at least 50 ⁇ , these strands being separated by a plurality of electrically insulating non-electroconductive domains having a so-called high surface furthest from the substrate, preferably with refractive index domains greater than 1 65.
• a metal grid made of metal material (pure or alloy, preferably single-layer or even multilayer) having a resistance per square of less than 10 ⁇ / D, better than 5 ⁇
• the metal gate having
• the electroconductive support comprises on the side of the first surface a first mineral layer, preferably electrically insulating, of given composition, the first layer being directly on the first surface or on a sub-layer including barrier-mono or multilayer, mineral-barrier Moisture (if plastic substrate) or alkali (if glass), the first layer being partially or fully structured in thickness with through-holes or cavities, of width Wc to at least partially anchor the metal grid, the upper surface being the surface of the first layer or the surface of an overlay, mineral preferably of thickness less than or equal to 200 nm.
• the strands have along their length a central zone between lateral zones (planes) which are flush with the high surface and the surface roughness of the central zone is greater than the surface roughness of the lateral zones (smooth), preferably the roughness parameter.
• Rq side areas being at most 5nm.
• the electroconductive support further comprises an electroconductive coating of mineral material (mono or m ulti materials) which preferably covers directly the upper surface is above the lateral zones and in electrical connection with the lateral zones, optionally is present above the central areas and electrically connected to the central zones, having a thickness e of 5 or less than 500 nm, preferably less than or equal to 200 nm resistivity p 5 20Q.cm less than and greater than the resistivity of the metal grid, and which is of refractive index n of at least 5 1, 5 more preferably at least 1, 55 and even at least 1, 7.
• mineral material mono or m ulti materials
• the middle of the strand surface and the upper surface are spaced apart from a vertical distance H taken normal to the first surface and which is less than or equal to 500 nm, better still less than or equal to 300 nm, and even less than or equal to 100nm when the central zone is on the upper surface.
• the metal grid (its central zone) is preferably at least partially anchored in the first layer and possibly entirely anchored in the possible electrically insulating overlay (monolayer or multilayer) on the first layer.
• a high surface area of the first layer or the optional overcoat is chosen. as smooth as possible to reduce leakage currents.
• the upper surface (of the first layer or the overlayer) may preferably have a roughness Rq less than 10 nm, better 5 nm and even 2 nm.
• Rq can be defined according to IS04287 and measured by atomic force microscopy.
• H is limited to 500nm in underlaid conditions to make the profile as abrupt as possible. Surge attenuation is minimized to anchor the layer and allow passivation of the gate flanks by the non-electroconductive domains.
• the roughness parameter Rq (of the surface) of the lateral zones (planes) is at most 5 nm and even at most 3 nm and even at most 2 nm or 1 nm.
• Rmax (maximum height) in each lateral zone (plane) is at most 20nm and even at most 10nm.
• the roughness of the central zone greater than the surface roughness of the lateral zones is obtained in particular for depositing the gate material by a liquid route such as electroless plating (by silvering, etc.).
• the roughness of the central zone increases with the thickness of the metal grid (the smooth character of the lateral zones is independent of the thickness).
• the roughness parameter Rq (or rms) in the central zone may be at least 10 nm and even at least 20 nm and preferably at most 60 nm. And even the roughness parameter Rmax (maximum height) in the central zone can be at least 100 nm and even at least 150 nm and preferably at most 500 nm.
• Rmax and Rq of the metal grid can be defined according to IS04287 and measured by atomic force microscopy.
• a lateral zone flush with the upper surface may be strictly on the same plane as the upper surface or deviate from it by at most 10 nm and better by at most 5 nm.
• each lateral zone (plane) is flush with the upper surface also comes from the liquid deposition of the metal, such as electroless deposition ("electroless" in English) based on the reduction of a metal salt in solution, deposit made through the openings of a masking layer on a layer (partially or entirely) structured by wet etching. This phenomenon of outcropping is independent of the thickness of metal.
• the metal such as silver is deposited in the holes of a layer (partially or entirely) structured (overlayer only, or overlay and first layer).
• the holes are wider than the openings of the masking layer due to lateral etching which occurs during the formation of the structured layer by wet etching.
• the silver is deposited on the flanks and on the so-called internal surface of the masking layer which is located above each hole, inner surface in the plane of the upper surface and therefore protruding from the flanks of each hole.
• the lateral areas flush with the high surface are flat, smooth because of their contact with the masking layer itself smooth internal surface.
• the internal surface reproduces the smoothness, the plane of the upper surface. Wet etching does not generate significant roughness on the inner surface and smooth sidewalls and cavity bottoms (these potentially generated roughnesses do not increase the roughness of the gate surface with respect to smooth surface deposition).
• PVD physical vapor deposition
• a masking layer such as a (photo) resin
• the lateral zones of the strands are in a bowl, forming a rupture of morphology of depth equivalent to the height of cavities of the layer (partially or entirely) structured capable of generating short circuits when the electrochromic device is manufactured thereafter.
• the strand has no smooth side area and flush with the upper surface for a grid under flush or flush.
• the silvering is simple, less complex (no vacuum installations, etc.) than the "PVD" physical vapor deposition, and is suitable for any size of metal grid.
• the electrical conductivity of the silver-deposited silver is sufficient (typically 30% to 40% less than that of a silver grid made by PVD).
• the central area under the upper surface is flush and H is greater than 100 nm, even greater than 150 nm.
• the Applicant has found the interest of a sufficient gap between the surface of the metal grid in the central zone and the high surface. Indeed, in the case of overlying grates, or under flush with lower values of H, the Applicant has observed the appearance of metal protuberances of height H1 of the order of 20 nm to 200 nm and width W1 at mid-height of the order of 20 to 500 nm along the inner edges of the lateral zones. These protuberances are continuous or discontinuous. These protuberances are harmful because they may increase the leakage currents.
• the difference H greater than 100 nm, even greater than 150 nm according to the invention can significantly reduce these protuberances and their height or even to remove them.
• the metal grid when the metal grid is flush with the upper surface, with H greater than 100 nm, better than 150 nm, the majority of metal strands and even each metal strand according to the invention is devoid of these protuberances.
• the metal strand surface preferably silver, is considered to be devoid of protuberances when these protuberances along the inner edges of the lateral zones have a height of less than 10 nm.
• H is less than or equal to 100 nm and even preferably the central zone below the upper surface, preferably the metal strand surface is devoid of protuberances (metal) of height greater than 10 nm along the inner edges (central zone side) of the lateral zones.
• the protuberances are generated during removal of the masking layer. It is assumed that when the gap H is small (near flush strands) the break between the gate metal (silver) deposited in the hole of the layer (partially or completely) structured and that on the flanks of the masking layer is more difficult to achieve because of a contact zone between the gate metal and that on a larger masking layer. However these protuberances can be removed by etching.
• the electroconductive support may comprise a so-called discontinuous passivation layer of electrically material, forming a grid of insulating tracks located above the central zones and possibly above the lateral zones of the strands, entirely covering the central zones and possibly partially or entirely covering the lateral areas and not exceeding laterally from the outer edges of the strands (above the upper surface) or protruding laterally from the outer edges of the strands by at most 1 ⁇ , even not more than 500 nm, or at most 200nm (above the high surface), or even not exceeding central areas.
• the insulating gate according to the invention can potentially limit the leakage currents and therefore the degradation of the lifetime of the electrochromic device. If in addition the surface of the insulating gate is smooth (for example a layer obtained by sol-gel or other liquid-channel method), it can planarize large faults source of leakage currents.
• the metal grid has strands of small width A that can even be invisible and is preferably irregular and better random to suppress possible diffraction phenomena. And passivation is localized above the strands. Since the insulating tracks do not extend laterally beyond the metal strands (or little, exceeding less than 1 ⁇ m), the insulating tracks do not induce active surface loss (or little, in terms of the ratio between the widths of the strands and the lateral extension possible according to the invention). The presence of the lateral zones smoother than the central zone also provides a major advantage of the support according to the invention. The lateral zones do not need to be passivated in themselves (since smooth).
• the manufacturing method according to the invention makes it possible to locate the insulating tracks partially or entirely on the lateral zones, and thus to completely cover the rough central zones. Since the lateral zones are smooth and do not generate leakage currents, their overlap, which may be only partial, is not a problem. The possibility of a partial recovery also provides an advantage in terms of manufacturing process, giving a tolerance in the choice of process parameters.
• the insulating tracks may therefore cover all or part of the lateral areas indifferently as long as the central zones are completely covered.
• the width of the central zone may be greater than, equal to or less than that of each lateral zone (defined at the level of the high surface). It depends on e 2 , H and the width of the holes hosting the metal grid.
• the passivation layer has above the central zone a so-called upper surface which has a roughness parameter Rq of less than 10 nm, better still 5 nm and even 2 nm and even a roughness parameter Rmax of less than 100 nm, better still 50nm and even at 20nm.
• the passivation layer preferably has flanks which have a roughness parameter Rq of less than 10 nm even at 5 nm and better at 2 nm and even a roughness parameter R max of less than 100 nm better at 50 nm and even at 20 nm.
• the passivation layer may be monolayer or multilayer, transparent or opaque (more or less absorbent) and any refractive index.
• the passivation layer may be organic, in particular polymeric.
• the electrically insulating material is a positive photosensitive material (annealing), of thickness e 6 less than 1000 nm, even at most 600 nm and even at most 300 nm on the electroconductive coating
• the photosensitive material is conventionally used in photolithography for masking layers and called photoresist in English. It is usually a photoresist.
• a "positive" photosensitive material is typically a type of photosensitive material for which the portion exposed to UV light becomes developer-soluble (developer solution) and the unexposed portion of unexposed photosensitive material remains insoluble.
• a "negative" photosensitive material is typically a type of photosensitive material for which the exposed portion becomes insoluble to the developer and the unexposed portion of the photosensitive material remains soluble.
• the passivation layer may be monolayer or multilayer, transparent or opaque (more or less absorbent) and any refractive index.
• the insulating tracks have oblique flanks induced by the development of the positive photosensitive material.
• the base of the insulating tracks may be of angle ⁇ of at most 60 °, even between 40 and 50 °, with the upper surface such that the insulating tracks are of decreasing width while moving away from the first surface.
• the section of the passivation layer is typically dome-shaped, with no sharp angles.
• the positive photosensitive material is compatible with the subsequent steps of manufacturing the electrochromic device.
• planarizing material thickness is preferably of the order of magnitude of the value of Rmax of the metal gate.
• the passivation layer is a layer based on at least one of the following materials: polyimide, polysiloxane, phenolformaldehyde (known under the name of novolac resin or novolac in English), polymethylmethacrylate (PMMA) ).
• the passivation layer is inorganic, and more particularly an oxide layer preferably by sol-gel and / or nitride of a material that is a metal and / or silicon and preferably a layer of silicon nitride, or titanium, or titanium oxide, zirconium, silicon, niobium and mixtures thereof.
• the material of the insulating tracks can be deposited by different methods (for example sputtering, sol-gel).
• sol-gel A sol-gel process is favored because of its lower cost and the planarizing nature of sol-gel materials.
• the passivation layer is on the electro-conductive coating, preferably mineral.
• the passivation layer is between the electro-conductive coating, preferably mineral, and the central zone (and even the lateral zones).
• the electroconductive coating preferably an indium-based layer, is discontinuous, absent from the central zones.
• the electroconductive coating may be discontinuous, absent from the central zones and H is then defined between the middle of the strand surface and the surface of the electroconductive coating.
• the first layer may be an oxide layer preferably sol-gel and / or nitride of a material which is a metal and / or silicon and preferably a layer of silicon nitride, titanium, or titanium oxide, zirconium, silicon, and mixtures thereof or else transparent conductive oxide, in particular based on zinc.
• the first optionally partially structured layer according to the invention may be over a large surface, for example an upper surface or equal to 0.005 m 2 or even greater than or equal to 0.5 m 2 or 1 m 2.
• the grid according to the invention may be over a large surface, for example an upper surface or equal to 0.02 m 2, or even greater than or equal to 0.5 m 2 or 1 m 2.
• the barrier layer may be based on silicon nitride, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, or silica, alumina, titanium oxide, tin oxide, of aluminum nitride, of titanium nitride, for example of thickness less than or equal to 10 nm and preferably greater than or equal to 3 nm even at 5 nm. It can be a multilayer.
• all refractive indices are defined at 550 nm.
• the strands are elongate - disjoint or preferably interconnected (at least in the active region) in particular mesh -. Insulating tracks have the same architecture.
• the metal grid is obtained by autocatalytic deposition and preferably by silvering.
• the metal grid according to the invention may have a square resistance of less than 10 ohm / square, preferably less than or equal to 50 Hz / square, and even 10 oh / square.
• the material or materials of the metal grid are selected from the group consisting of silver, copper, nickel, especially pure material or may be an alloy based on these metals.
• the grid is preferably based on silver.
• the metal grid may preferably be monolayer (silver) or even multilayer (preferably with at least 80% even 90% silver).
• the metal grid can be multilayer, especially multilayer silver, and understand
• a first metal layer (directly on the bottom of the cavities or metal layer closest to the bottom of the cavities), preferably in a first metallic material, which is preferably based on silver or even made of silver, forming less 15% and even 10% of the total thickness e 2 of the gate and / or of at least 3 nm, 5 nm or even at least 10 nm, and preferably less than 100 nm or even 50 nm,
• a second metal layer (on the first layer, away from the substrate), in particular with a discernable interface with the first layer, based on a second metal material which is preferably chosen from silver, aluminum or copper , forming at least 70%, 80% and even 90% of the total thickness e 2 of the second layer grid which is preferably based on silver or even made of silver, especially as the first layer.
• first silver-based metal layer according to a first deposition method, for example deposited by silvering, preferably with a thickness of at least 20 nm and even at least 30 nm, or by vacuum deposition (spraying). and a second silver-based metal layer having a thickness of at least 3 nm or even 5 nm, according to a second deposition method which is preferably electroplating.
• a first deposition method for example deposited by silvering, preferably with a thickness of at least 20 nm and even at least 30 nm, or by vacuum deposition (spraying).
• second silver-based metal layer having a thickness of at least 3 nm or even 5 nm, according to a second deposition method which is preferably electroplating.
• the advantage of electroplating is a higher silver utilization rate than silvering and a less expensive method of spraying.
• the metal grid may be multilayered with layers of different materials, for example with a final layer of protection against corrosion (water and / or air), for example metallic, in a material distinct from the underlying metallic layer, in particular distinct silver, less than 10nm thick better than 5nm or even 3nm. This layer is useful in particular for a silver-based grid.
• a final layer of protection against corrosion water and / or air
• metallic in a material distinct from the underlying metallic layer, in particular distinct silver, less than 10nm thick better than 5nm or even 3nm. This layer is useful in particular for a silver-based grid.
• the metal grid may be further multilayered with two layers of different materials, for example bilayer, and composed of:
• a (single) metal layer made of the abovementioned materials, preferably based on, or even in silver, with a thickness of at least 100 nm preferably, for example deposited by silver plating or vacuum deposition (spraying),
• an overcoat of protection against corrosion for example metallic, made of a material distinct from the metallic layer, in particular distinct from silver, with a thickness of less than 10 nm, better than 5 nm or even 3nm
• the metal grid may be a metal layer such as silver and be coated with a protective overcoat, especially temporary, especially polymeric.
• the metal grid may preferably be deposited directly on the first layer selected partially structured or on a dielectric underlayer, in particular hooked (function hooked to facilitate the deposition of gate material).
• the underlayer is directly on the cavities (the bottom and preferably all or part of the flanks of the cavities) of the partially structured layer and is preferably absent from the surface of the partially structured layer, which is a preferably mineral layer, in particular oxide (s), for example a transparent conductive oxide.
• the dielectric underlayer is of thickness e A less than 30 nm even at 10 nm. This hooked layer is easily deposited by magnetron sputtering.
• the metal grid is directly in contact with a structured layer (no layer between the grid and the bottom of the cavities).
• the metal strands are interconnected in the active area of the electrochromic device or connected (only) via their ends to electrical contacts.
• the metal grid may be in the form of strands in the form of closed patterns or meshes (interconnected strands between them defining closed patterns), of irregular shape and / or of irregular size and better even random.
• the thickness e 2 is not necessarily constant in a cavity along the width of a strand. Preferably it is defined at the center of the strand surface.
• the width A is not necessarily constant in a given cavity.
• the thickness e 2 (defined at the center of the strand surface) may be less than 1500 nm, better at 1000 nm, especially in a range from 100 nm to 1000 nm, or less than 800 nm and in particular in a range from 200 nm to 800 nm. , especially from 100 to 500 nm or even 100 to 300 nm if the structured layer is sol-gel.
• the width A is preferably less than 30 ⁇ m to further limit the visibility of the strands with the naked eye.
• A is preferably in a range from 1 to 20 ⁇ , more preferably from 1, 5 ⁇ to 20 ⁇ or even from 3 ⁇ to 15 ⁇ .
• B is at least 50 ⁇ and even at least 200 ⁇ and B is less than 5000 ⁇ , better still less than 2000 ⁇ even at 1000 ⁇ .
• Another characteristic of the metal grid according to the invention is a coverage ratio T which is preferably less than 25% and more preferably 10%, and even 6% or 2%. And preferably the insulating grid has a coverage ratio T 'less than or equal to T, less than 25% or less than 10%, and even 6%.
• a B between 2000 and 5000 ⁇ when e 2 is between 800 and 1500nm and A is between 10 and 50 ⁇ . This corresponds to a coverage rate of between 0.4 and 6.0%.
• a B may be desired between 200 and 1000 ⁇ when e 2 is less than 500 nm and A is between 3 and 20 ⁇ m or 3 to 10 ⁇ m. This corresponds to a coverage rate of between 0.5 and 22% or 0.5 to 1 1%.
• the first layer preferably electrically insulating, and even preferably a gel sol, is entirely structured in thickness with through holes Wc width and preferably the optional barrier sub-layer is not structured.
• the first preferably electrically insulating layer, and even preferably a gel sol, is partially structured in thickness, electrically insulating, being formed:
• the lateral zones are contiguous with the first layer and are of width L1, L1 being greater than the height e c cavities and L1 ⁇ 2e c and even L1 ⁇ 1, 4e c .
• the overlayer (monolayer or multilayer), of electrically insulating material, preferably mineral, discontinuous defining through holes, overlayer being part of the non-electroconductive domains, the upper surface being the surface of the overcoat, of thickness e z of at most 500 nm and even 300 nm or not more than 100 nm and preferably at least 20 nm
• the first electrically insulating layer preferably mineral, which is:
• a structured region under the overlay (and on the lower region), region with cavities (thus blind openings) of width Wc facing the through holes, in particular cavities accommodating at least the lower part (of the central zone) of the metal grid, (the upper part of the central zone of the metal grid possibly extending into the through openings of the overlay or even beyond the upper surface).
• the through holes being W1 width, the cavities being Wc width with preferably Wc ⁇ W1 even Wc> W1.
• edge zone strand zones are contiguous to the lateral zones, are more peripheral than the lateral zones and are in the cavities under the overlay - thus flush with the surface of the first layer (the lateral zones forming a recess of edge areas of the thickness e z ).
• the lateral areas are of width L1 defined as the distance between points X "and Y ', the edge areas of width L2 defined as the distance between points X' and Y, Y" is the orthogonal projection of Y in the plane of the surface of the lateral zones, L3 is the distance between X "and Y", L3 being greater than the total height e c + e ' c and L3 ⁇ 2 (e c + e' c ) and even L3 ⁇ 1, 4 (e c + e ' c ) where e c is the height of the cavities (taken in the middle) and e' c is the height of the holes.
• A is defined at the high surface if W1> Wc and at the surface of the first layer if W1 ⁇ Wc.
• B is defined at the high surface if W1> Wc and at the surface of the first layer if W1 ⁇ Wc
• the cavities are preferably defined by flanks flared, the cavities widening away from the plastic substrate.
• L is between points X and Y such that X is the highest point of the sidewall and Y is the point at the end of the bottom of the cavity.
• the holes of the overlay may be delimited by flanks flaring, widening away from the plastic substrate, with a horizontal distance L' greater than e ' c and with L' ⁇ 2e' c
• the first layer is a layer partially structured in thickness whose upper surface possibly forms the upper surface, the deeper the cavities are, the greater the lateral zones are.
• the overlay is transparent with the lowest possible absorption.
• the overlay is inorganic, in particular comprises a layer of a metal oxide and / or silicon, a metal nitride and / or silicon, a metal oxynitride and / or silicon (SiON).
• Its thickness z may be less than 200 nm, 150 nm, 100 nm and even 5 or 20 nm to 80 nm. It may be a monolayer or a multilayer, in particular of metal oxides or of metal oxides and of metal nitrides (such as Si0 2 / Si 3 N 4 ).
• the overlayer is for example a barrier layer (protection) or stop acid etching, for example aqua regia which is the usual de etching solution used for the electroconductive coating.
• the overcoat comprises at least one layer of a Ti oxide, Zr, Al and mixtures thereof, or Sn, and optionally containing silicon.
• the overlayer is of refractive index greater than 1, 7.
• an average refractive index of preferably greater than 1.7 is defined.
• any layer of refractive index less than 1.7 be less than 50 nm thick.
• the overlay has blind or preferably through holes.
• the holes can be of height e ' c greater than 20nm, and even of at least 50nm or
• e 'c is taken at the center of the hole.
• the holes may form grooves (one-dimensional), regularly spaced or not particularly disjoint (at least in the active zone) of any shape for example straight or sinuous.
• the holes can form a mesh, that is to say a network of interconnected openings
• the mesh can be defined by a maximum width between two points of a mesh.
• the cavities or through holes of the first layer are preferably partially filled by the metal grid.
• the cavities are delimited by a bottom and flanks most often forming a bowl.
• the cavities or through holes of the first layer separating the non-electroconductive domains may be of height e c greater than 200 nm, and even at least 250 nm or 500 nm and preferably smaller than 1500 nm or 1200 nm and of width A c less than or equal to 30 ⁇ m. . e c is taken from the center of the cavity. A c is preferably taken at the bottom of the cavity.
• the cavities or through holes of the first layer may form grooves (one-dimensional) regularly spaced or not particularly disjoint (at least in the active zone) of any shape for example straight or sinuous.
• the cavities or through holes of the first layer may form a mesh, that is to say a network of interconnected openings (two-dimensional), periodic or aperiodic, of regular or irregular mesh, of any shape: geometric in particular (square, rectangle , Honeycomb).
• the mesh can be defined by a maximum width between two points of a mesh B c .
• e c is greater than 200 nm, even greater than 250 nm or 500 nm.
• e c is preferably submicron.
• e ' c is greater than 100 nm, even greater than 250 nm and less than or equal to 500 nm.
• e ' c is preferably submicron.
• a layer or coating deposit (comprising one or more layers) is carried out directly under or directly on another deposit, it is that there can be no interposition of 'no layer between these two deposits.
• all refractive indices are defined at 550 nm.
• the conductive coating has a resistivity less than 5 p 20Q.cm even 10Q.cm Q.cm or 1 and even 10 "Q.cm and greater than the resistivity of the metal grid and is refractive index No. 5 given at least 1, preferably 1 55 6 and more preferably 1: 7.
• ⁇ 1000 ⁇
• e 5 100 nm
• a resistivity of less than 0.1 ⁇ .cm is preferred.
• B of 200 ⁇ m and e 5 100 nm, a resistivity of less than 1 ⁇ .cm is preferred.
• the electroconductive coating according to the invention contributes to a better distribution of the current.
• the electroconductive coating is preferably monolayer rather than multilayered.
• the surface of the coating can reproduce the surface roughness of the grid, in particular obtained by vapor deposition.
• the coating above the central area may be sub-flush with the upper surface.
• the electroconductive coating may thus comprise (or preferably consists of) an inorganic layer having a refractive index n is between 1, 7 and 2.3, preferably which is the last layer of the coating (furthest from the substrate) and even the only one, preferably of thickness less than 150 nm, based on electroconductive transparent oxide, simple or mixed oxide:
• metal oxides in particular based on at least one of the following metal oxides, optionally doped: tin oxide, indium oxide, zinc oxide, molybdenum oxide MoO 3 , tungsten oxide WO 3 , vanadium oxide V 2 0 5,
• ITO preferably, a layer (in particular amorphous), for example based on zinc oxide and tin SnZnO, or based on indium and zinc oxide (called
• ITZO indium, zinc and tin oxide
• a layer based on zinc oxide is doped with aluminum and / or gallium (AZO or GZO).
• a layer of a ZnO oxide is preferably doped Al (AZO) and / or Ga (GZO) with the sum of the weight percentages of Zn + Al or Zn + Ga or Zn + Ga + Al or Zn + other dopant of preferably selected from B, Se, or Sb or even from Y, F, V, Si, Ge, Ti, Zr, Hf and even by In which is at least 90% by total weight of metal better than at least 95 % and even at least 97.
• an AZO layer according to the invention that the percentage by weight of aluminum on the sum of the percentages by weight of aluminum and zinc, in other words AI / (AI + Zn), is less than 10% preferably less than or equal to 5%.
• a ceramic target of aluminum oxide and zinc oxide such that the percentage by weight of aluminum oxide on the sum of the percentages by weight of zinc oxide and of aluminum oxide, typically Al 2 O 3 / (Al 2 O 3 + ZnO), is less than 14%, preferably less than or equal to 7%.
• the percentage by weight of gallium over the sum of the percentages by weight of zinc and gallium in other words Ga / (Ga + Zn), is less than 10% and preferably less than 10%. or equal to 5%.
• a zinc oxide and gallium oxide ceramic target such as the percentage by weight of gallium oxide on the sum of the weight percentages of zinc oxide and gallium oxide, typically Ga 2 O 3 / (Ga 2 O 3 + ZnO) is less than 1 1%, preferably less than or equal to 5%.
• the total weight percentage of Sn metal is preferably from 20 to 90% (and preferably from 80 to 10% for Zn) and 30 to 80% (and preferably 70 to 20% for Zn), in particular the weight ratio Sn / (Sn + Zn) is preferably from 20 to 90% and in particular from 30 to 80%.
• the inorganic layer preferably ITO or zinc oxide-based, preferably has a thickness less than or equal to 60nm, 50nm or 40nm or even 30nm and even 10 nm and resistivity is less than 10 "From Q.cm.
• Is preferably meant indium tin oxide (or tin-doped indium oxide or ITO for the English name: Indium tin oxide) a mixed oxide or a mixture obtained from indium oxides ( III) (In 2 0 3 ) and tin (IV) (SnO 2 ), preferably in the mass proportions of between 70 and 95% for the first oxide and 5 to 20% for the second oxide.
• a typical mass proportion is about 90% by weight of ln 2 0 3 for about 10% by weight of Sn0 2 .
• the electroconductive coating may be made of the mineral layer having a refractive index n is between 1, 7 and 2.3, then equal to n 5.
• the electroconductive coating may be multilayer and comprises (preferably directly) under the aforementioned mineral layer (in particular the last layer), a first layer directly on the metal grid (monolayer or multilayer grid), in electroconductive transparent oxide, of thickness e '. Less than 200 nm, with an index of between 1.7 and 2.3, especially chosen from:
• a layer based on zinc oxide doped in particular aluminum and / or gallium AZO or GZO
• ITZO and / or a layer in particular amorphous
• zinc oxide and SnZnO tin preferably less than 100 nm thick, or based on indium and zinc oxide (called IZO) , or based on indium oxide, zinc and tin (referred to as ITZO).
• the AZO or GZO layer may, for example, make it possible to reduce the thickness of the mineral layer, in particular of the ITO layer, to less than 50 nm.
• 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 1 m 2 and a lower electrode substantially occupying the surface (the structuring zones).
• the plastic substrate may be substantially transparent, polycarbonate PC or polymethyl methacrylate PMMA or PET, polyvinyl butyral PVB, polyurethane PU, polytetrafluoroethylene PTFE etc ...
• the thickness of the substrate may be at least 0.1 mm, preferably in a range from 0.1 to 6 mm, in particular from 0.3 to 3 mm.
• the support as defined above may further comprise an electrochromic system deposited (preferably directly) on the electroconductive coating and the passivation layer.
• the invention also relates to an electrochromic device incorporating the electroconductive support as defined above, the electrode with the metal grid forming the so-called lower electrode, the closest to the first surface, generally the anode, in particular covered by a electrochromic system, covered by the upper electrode - conventionally a thick layer of ITO-.
• the electroconductive support in the case of the liquid electrolyte, it is alternatively or cumulatively also possible to use the electroconductive support as defined above according to the invention.
• the invention finally relates to a method of manufacturing an electroconductive support as defined above which comprises the following steps in this order:
• the supply of the substrate comprising:
• the metal gate comprising a liquid deposit, preferably autocatalytic, of a first metallic material of the gate in the cavities or through holes, the first material being deposited on the flanks (of the first boundary layer) cavities and entirely on the inner surfaces of the masking layer, thus forming the strand side areas flush with the upper surface and less rough than the central strand areas
• the deposition of the electroconductive coating preferably mineral for example by physical vapor deposition
• the insulating grid passivation layer formed of insulating tracks above the central zones of the strands, passivation layer preferably on the electroconductive coating present on the central zones.
• the etching is performed by a wet etching process. Cavity depth is controlled by solution concentration, solution type, etch time, and / or solution temperature.
• the masking layer, (photo) sensitive, is then resistant to the etching solution.
• Engraving with a wet solution is vertical and lateral in the sense that the etching solution attacks (digs) in all directions.
• the etching profile can be in bowl, semi-spherical type.
• the cavities have flanks flared in the opposite direction of the substrate (widening away from the substrate).
• the section can be in bowl, even (type) semi-spherical.
• the invention therefore also relates to a method of manufacturing an electroconductive support as defined above (with an overlay on the first layer) which comprises the following steps in this order:
• the supply of the substrate comprising:
• an electrically insulating continuous layer in the composition of the first layer, (directly) on the anchoring layer, an electrically insulating continuous layer called an additional layer, made of a material of the overcoat, the formation of the blind or through apertures in the additional layer, thus forming the overlay entirely or partially structured in thickness, forming comprising:
• the formation of the metal gate comprising a liquid deposit, preferably an autocatalytic deposit, of a first metallic material of the gate in the cavities or through holes of the first layer and in the through-holes of the overlay, thereby forming the zones lateral strands flush with the upper surface beneath the inner surfaces being less rough than the central strand regions, the first material settling on the flanks of the through holes of the overlayer, entirely on the other inner surfaces of the overlayer, on the surfaces the masking layer, thus forming the edge zones and the lateral strand zones
• the deposition of the electroconductive coating preferably mineral for example by physical vapor deposition
• the depth of the cavities (and / or holes in the overlay) is controlled by the concentration, solution type, etching time, and / or temperature of the solution.
• the masking layer, (photo) sensitive, is resistant to the etching solution (the first and second etching solutions).
• the cavities (and / or the holes of the overlayer) are flared in the opposite direction of the substrate (widening away from the substrate).
• Engraving with a wet solution is vertical and lateral in the sense that the etching solution attacks (digs) in all directions.
• the etching profile can be in bowl, semi-spherical type. This attack in all directions is the origin of the areas of the masking layer suspended above the cavities or blind or through holes.
• Wc> W1 is preferred because it is thus easier to create peripheral peripheral areas flush with the upper surface that are smooth.
• the electroconductive coating is inorganic because the latter is more resistant to the aqueous chemical solutions used during the chemical development steps of the layer of photosensitive material and / or removal of a portion of the layer of photosensitive material.
• the manufacturing method comprises the formation of the insulating grid passivation layer formed of insulating tracks on the central zones of the strands and comprises:
• the passivation process includes a photolithography step but without the use of a photolithography mask or an alignment step which would generate additional cost and complexity.
• each (opaque) metal strand forms a UV shield so that the positive photosensitive material above the strand is not exposed and is insoluble in the developing solution.
• the insulating grid is self-aligned on the metal grid. Depending on the development the flanks will be more or less oblique generally such that the width of the insulating strands decreases with the thickness.
• the width of the insulating tracks can be controlled, via the conditions of UV illumination and development of the layer of the positive photosensitive material, so as to be greater than that of the central regions of strands, in order to make the suppression of the leakage currents more efficient, freeing edge effects.
• the height of the insulating tracks can be controlled via the concentration of the photosensitive passivation material solution, as well as the UV illumination conditions and the development conditions (time and concentration).
• the formation of the passivation layer is particularly simple and fast because there is no need for deposition step of another sacrificial material to be eliminated thereafter fully.
• the formation of the insulating gate passivation layer formed of insulating tracks on the central zones of the strands comprises:
• the removal of the masking layer (before the electroconductive coating is deposited) creates metal protuberances with a height of at least 10 nm along the inner edges of the lateral zones of the metal grid, and the after removal of the masking layer and before the deposition of the electroconductive coating, the process comprises a wet etching step to remove the protuberances.
• the liquid deposition of the first metallic material is preferably a silver and preferably the grid is a monolayer.
• the liquid deposit (preferably the only deposit for the metal gate) may be a silvering and preferably the gate is a monolayer and even the first material (which is based on silver) is deposited directly in the bottom of cavities or blind holes.
• the solution for the silvering step may contain a silver salt, a silver ion reducer and even a chelating agent.
• the silvering step may be carried out according to standard procedures commonly used in the field of the manufacture of mirrors and described for example in Chapter 17 of the book "Electroless Plating - Fundamentals and Applications", published by Mallory, Glenn O .; Hajdu, Juan B. (1990) William Andrew Publishing / Noyes.
• the silvering step comprises (by dipping into a bath or by spraying a solution) contacting the substrate having the underneath, the first layer, the possible overlayer and the through-hole masking layer with a mixture of two aqueous solutions, one containing the metal salt, for example silver nitrate, and the other containing the ion-reducing agent Metals (Ag + ions), for example sodium, potassium, aldehydes, alcohols, sugars.
• the metal salt for example silver nitrate
• Metals Al + ions
• the most commonly used reductants are Rochelle salt (KNaC 4 H 4 O 6 , 4H 2 0 sodium and potassium double tartrate), glucose, sodium gluconate and formaldehyde.
• the silvering step comprises a sensitization step (of the surface of the cavities and / or holes of the overlay) preferably comprising a treatment with tin salt and / or a step activation (of the surface of the cavities and / or holes of the overcoat) preferably comprising a treatment with a palladium salt.
• a sensitization step of the surface of the cavities and / or holes of the overlay
• a step activation of the surface of the cavities and / or holes of the overcoat
• a treatment with a palladium salt preferably comprising a treatment with a palladium salt.
• the silvering can be carried out by immersing the substrate having the optional sublayer, the first layer, the optional overlayer and the through-hole masking layer, in (photo) resin, in trays, each with a of the following three solutions in this order:
• a third which is a mixture of the silver salt solution preferably of silver nitrate and the solution of the silver reducing agent, preferably of sodium gluconate, preferably with stirring (preferably for less than 15min and even 5min, for example 0.5 to 3min), then rinsing with water (distilled).
• the coated and thus silvery substrate is then removed from the last bath and rinsed with water (distilled).
• Another embodiment consists in spraying the three preceding solutions in the same order as before rather than in plunging the substrate having the optional underlayer, the first layer, the possible overlayer and the through-hole masking layer in (photo )resin.
• the removal of the masking layer (before the electroconductive coating is deposited) is preferably carried out by a liquid route, in particular by ultrasound in a solvent (acetone, etc.).
• the deposition of the electroconductive coating, directly on the grid and (directly) on the first layer or the possible overlayer, monolayer or multilayer and / or mono or multi-material coating may be by physical vapor deposition, in particular by sputtering, with a possible first deposition of SnZnO or AZO and a second or last or preferably single deposit of ITO or based on ZnO (doped), or even Mo0 3 , WO 3 , or v 2 o 5 .
• the process may comprise, prior to deposition of the electroconductive coating, a heating step, preferably of between 150 ° C. and 550 ° C., for a duration of preferably between 5 minutes and 120 minutes, in particular between 15 and 90 minutes and / or a heating step after the deposition of the inorganic electroconductive coating, before or after the deposition of the passivation layer, at a temperature of preferably between 150 ° C. and 550 ° C., for a duration of preferably between 5 minutes and 120 minutes especially between 15 and 90 minutes.
• a heating step preferably of between 150 ° C. and 550 ° C., for a duration of preferably between 5 minutes and 120 minutes especially between 15 and 90 minutes.
• FIG. 1 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a first embodiment of the invention in which the strand central zone is flush with the upper surface;
• FIG. 1a illustrates a detail view of FIG. 1 without the passivation layer
• FIG. 1b illustrates a schematic detail view of a section of a cavity of the first layer partially structured with the strand of a grid deposited by PVD in a comparative example produced by the Applicant
• FIG. 2 is a schematic sectional view of an electroconductive support for an electrochromic device according to a second embodiment of the invention in which the first layer is entirely structured
• FIG. 3 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a third embodiment of the invention in which the passivation is between the central zone and the electroconductive coating;
• FIG. 4 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a fourth embodiment of the invention in which the grid is flush with the high surface;
• FIG. 5 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a fifth embodiment of the invention in which the grid is flush with the surface of the electroconductive coating absent from the central zone;
• FIG. 6 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a sixth embodiment in which the gate is anchored in a structured first layer and overcoat,
• FIG. 6 is a detailed view of FIG. 6,
• FIGS. 7a to 7i are schematic views of the steps of the method of manufacturing the electroconductive support in relation to the first embodiment.
• Figure 1 shows in side section an electroconductive support 100 for electrochromic device.
• This support 100 comprises a glass substrate having a refractive index n s of 1.45 to 1.8-smooth with a first main face January 1, said first surface, carrying in this order away from the substrate:
• a possible moisture barrier layer 4 such as silicon nitride 41 or a stack of thin layers
• low region 30 a region (continuous) called low region 30, which is here directly on the under layer, of given thickness e ' 3 (preferably micron), covering the surface of the under layer,
• an electrode 2 comprising a layer arranged in grid 2, called a metal grid, made of metallic material (s) obtained by autocatalytic deposition, preferably monolayer of silver (obtained by silvering), the gate being here a monolayer formed strands - in other words, tracks - 20 anchored in the cavities, the strands having a width A less than 50 ⁇ m at the level of the upper surface 34, better than or equal to 30 ⁇ m (and at least 1 ⁇ m) and being spaced at the same time.
• the metal grid having a resistance by square less than 10Q / D, and even less than 5 ⁇ / D, OR 1 ⁇ / ⁇ ,
• the cavities have flanks flared due to the method of wet etching a layer continues when forming the first partially detailed structured layer later.
• the strands 20 have along their length a central zone 21 between lateral zones 22, 22 'which are flush with the upper surface 34 and the surface roughness of the central zone 21 is greater than the surface roughness of the lateral zones 22, 22'.
• A, B, e 2 is represented , as is the width of the central zone A m and for the cavities the width A c at the bottom of the cavity and e c is the height from the center of the bottom of the cavity.
• the flanks are flared (widening away from the substrate 1), a horizontal distance L is defined between X and Y such that X is the highest point of the flank and Y is the point at the end of the bottom of the flange. the cavity. L is greater than e c , L ⁇ 2e c and even L ⁇ 1, 4e c .
• the middle of the strand surface and the upper surface are spaced apart from a vertical distance H taken normal to the first surface and which is less than or equal to 500 nm.
• the central zone 21 is flush with the upper surface 34.
• the strands have a rougher central zone 21 than the lateral zones due to autocatalytic deposition such as silvering and smooth lateral zones 22, 22 'of width L1.
• the width of the central zone A m is not necessarily greater than L1 that depends on the values of A, H and e c .
• Examples of roughness parameters of the central zones and of the plane lateral zones are recorded in the following table according to the thickness e 2 .
• the ITO coating 5 is deposited preferably by magnetron sputtering, its surface is then in conformity with the underlying surface: surface of the first partially structured layer 3, flat and smooth lateral zones 22, 22 ', central zones 21 rougher than the side areas.
• the passivation layer 6 forms a grid of insulating tracks located above the central zones 21 and above the lateral zones 22, 22 'of the strands, covering the central zones and partially or completely covering the lateral zones and not projecting laterally. outer edges of the strands or protruding laterally from the outer edges of the strands of at most 1 ⁇ .
• the flanks 6f of each insulating strip are oblique with an angle a with the upper surface 34 of the order of 45 °.
• the section of each insulating track is dome-shaped, with no sharp angles.
• the upper surface 6s of each insulating strip and the flanks 6f of each insulating strip being smooth the passivation layer 6 planarise the central zone 21 and maintains the smooth character of the lateral zones 22, 22 '.
• an electrochromic device is added an electrochromic system, an upper electrode which may be identical in the case of a liquid electrolyte.
• the metal grid is preferably of random pattern.
• the glass substrate 1 is flat, smooth with a refractive index of 1.5, for example 2 mm thick and T L of at least 90%.
• the barrier layer is a stack of thin layers of metal oxides or nitrides or silicon.
• the first layer is a TiO x sol-gel layer with a thickness of 400 nm. This layer may alternatively be deposited by sputtering.
• the thickness e c is 350 nm.
• the cavities of the first layer 3 are obtained by etching as detailed later.
• the first partially structured layer 3 is locally flat.
• the roughness of the high surface 34 is defined by a Rq of less than 4 nm.
• the grid 2 is a monolayer of silver deposited directly in the cavities by silvering as detailed later.
• the silver partially fills the cavities here, with e 2 equal to about 300 nm.
• H is equal to 50nm.
• the grid pattern which is a mesh, is hexagonal.
• the width A equal to 12 ⁇ and the maximum distance B of 560 ⁇ .
• the coverage rate T is 4.5%.
• the electroconductive coating 5 consists of an indium oxide layer and tin ITO 50nm 2 refractive index of about, resistivity p 5 less than 10 "Q.cm.
• the ratio of the assembly (after annealing at 150 ° C. for 30 min), measured by the conventional 4-point method, is approximately 2.5 ohm / square.
• the passivation layer forming the insulated gate located in turn is a layer of positive photosensitive polyimide with e6 of the order of the order of 300 nm.
• FIGS. 7a to 7i are schematic (not to scale) views of the manufacture of the electroconductive support according to the first embodiment, particularly in relation to Example No. 1, with the manufacture of the first layer partially structured by etching chemical, and making the silver grid by silvering.
• the first step illustrated in FIG. 7a consists, from the glass substrate 1 coated with the underlayer: to form on the under layer, an anchoring layer 3a, which comprises the material of the first layer,
• the deposited photosensitive material is then fired at 100 ° C. for 20 minutes in a convective oven.
• the thickness of the photosensitive material is 800 nm.
• the second step illustrated in FIG. 7b consists of the generation of the photoresist pattern.
• a photolithography mask 70 with discontinuities 71 is applied to the resin 60 and the UV resin 60 is irradiated on the side of the first main face 11 with a Hg lamp at 20 mW / cm 2 (at 365 nm). for 10seconds through the discontinuities 71, according to an irregular arrangement better random.
• the third step illustrated in FIG. 7c consists of the creation of the through-openings in the photosensitive material 60.
• the irradiated zones are removed by dissolution in a specific development solution based on tetramethylammonium hydroxide (TMAH) and rinsed with the deionized water, thereby forming through apertures through the photoresist.
• TMAH tetramethylammonium hydroxide
• the sides 61 of the photosensitive material delimiting the through openings are flared away from the substrate.
• the width of each through opening is greater than the width W 0 at the upper surface 34.
• the fourth step illustrated in FIG. 7d consists of creating the cavities in the dielectric preferably continuous dielectric anchoring layer 3a such as the TiOx layer. It is preferred to form the first partially structured layer by wet rather than dry etching at room temperature.
• the selected resin 60 is therefore resistant to the etching solution which is here a solution based on NH 3 and H 2 O 2.
• the etching forms cavities of depth e c , flanks 32, and the cavities are flared away from the glass 1.
• _e c is equal to 350 nm.
• the etching solution attacks in all directions: vertically and laterally.
• the engraving profile is in bowl.
• the wet etching of the anchoring layer 3a creates zones of the masking layer in suspension above the cavities and thus defining portions of surfaces called inner surfaces 62, 62 'of the masking layer 60 facing the cavities 32
• Each cavity has a width Wc (at the level of the upper surface) greater than the width W0.
• the bottom 33 of the cavities is flat.
• the fifth step illustrated in FIG. 7e consists of the deposition of the gate material 2, by liquid and more precisely autocatalytic way, and preferably by silvering. The deposit is made through the openings of the photosensitive material 60 (resistant to etching, in the cavities to fill them preferably partially as illustrated here.
• the silver is deposited, in the bottom of the cavities, on the flanks of the cavities, on the internal surfaces 62, 62 'of the photosensitive material, on the sides of the photosensitive material (and is absent from the upper surface of the layer 3) and on the discontinuous upper surface 63.
• each cavity partially fills each cavity and is deposited in the bottom, on the flanks and entirely on the internal surfaces 62, 62 'of the masking layer, thus forming the strand lateral zones 22, 22' flush with the surface high and less rough than the strand central zone 21 opposite the through opening.
• the width L1 of each lateral zone 22, 22 ' is approximately equal to L0 + e2.
• the silver layer is deposited in the first partially structured layer 3 according to the following procedure for a thickness e 2 of about 300 nm (with H equal to 50 nm and the central zone under flush):
• the sixth step illustrated in FIG. 7f consists in the removal of the photosensitive material by a liquid route with an acetone solvent and the use of ultrasound.
• the electroconductive support is then preferably immersed in a solution of H 2 O: H 2 O 2: NH 3 (500: 20: 1) for 3 to 5 min at room temperature in order to remove silver protuberances.
• This chemical treatment is particularly recommended in the case of a grid under flush with H less than 100nm, or when the grid is overflowing.
• the seventh step illustrated in FIG. 7g consists in the sputtering deposition of the electroconductive coating 5.
• No. 1 it is a layer of indium and tin oxide ITO.
• the ITO is deposited by magnetron sputtering as a mixture of argon and oxygen 0 2 / (Ar + 0 2) to 1% at a pressure of 2 10 3 mbar with a ceramic target made of indium oxide (90 % by weight) and tin oxide (10% by weight).
• AZO, GZO or AGZO are chosen.
• a first annealing is then carried out at 250 ° C. for 30 minutes.
• the eighth step consists of:
• a layer 6a of positive photosensitive material which is, for example No. 1, a photosensitive polyimide (Polyimide PIMELTM series I-700), by spincoating, covering the electroconductive coating 5, followed by an annealing step in a convection oven (100 ° C, 20min)
• an ultraviolet source which is for example no. 1 a Hg lamp at 20 mW / cm 2 (at 365 nm) on the side of the second main face 12.
• the ninth step illustrated in FIG. 7i consists of the result of the development of the positive photosensitive material in a solution based on tetramethylammonium hydroxide (TMAH) and a rinsing step with deionized water until the layer of polyimide 6, leaving the unexposed polyimide (due to screening by the silver strand) in the areas of the electroconductive coating 5 located above the silver strands 20.
• TMAH tetramethylammonium hydroxide
• the polyimide passivation layer forming the insulated insulated gate 6 has a thickness of the order of 300 nm.
• a second annealing is then carried out at 300 ° C. for 60 min, eliminating or not the first annealing. After this second annealing, the thickness of the polyimide passivation layer decreases from 380 to 300 nm.
• the electroconductive support according to the invention thus makes it possible to manufacture electrochromic devices of large size (by obtaining a low square resistance) with a better switching time, and this without degradation of the leakage currents, due to passivation. of the metal grid.
• FIG. 1b illustrates a schematic detail view of a section of a cavity of the first layer partially structured with the strand of a PVD-deposited grid in a comparative example produced by the Applicant, showing the high surface 34 and the strand anchored in a first structured layer (as in Example 1).
• the lateral zones 22 "a and 22" b create morphological breaks generating leakage currents.
• Figure 2 is a schematic sectional view of an electroconductive support for electrochromic device according to a second embodiment of the invention wherein the first layer 3 is fully structured and the sub-layer removed.
• the manufacturing conditions of Example 1 are modified by the etching time of the first anchoring layer so that ec decreases from 350 nm to 400 nm.
• FIG. 3 is a schematic sectional view of an electroconductive support for an electrochromic device according to a third embodiment of the invention in which the passivation 6 is between the central zone 21 and the electroconductive coating 5.
• FIG. 4 is a diagrammatic cross-sectional view of an electroconductive support for an electrochromic device according to a fourth embodiment of the invention which differs from the first embodiment in that the central zone of the wire overlaps the high surface 34.
• the conditions are modified of manufacture of Example 1 by the etching time of the first anchor layer so ec decreases from 350nm to 250nm.
• FIG. 5 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a fifth embodiment of the invention in which the grid is flush with the surface of the discontinuous electroconductive coating while being absent from the central zone 21.
• the coating has was deposited before the formation of the metal gate and the passivation layer, the discontinuity can be achieved by wet etching.
• FIG. 6 is a diagrammatic sectional view of an electroconductive support for an electrochromic device according to a sixth embodiment of the invention which differs from the first embodiment in that the gate 2, still deposited by autocatalytic deposition such as the silvering, is anchored in the first partially structured layer and also in a structured overlay 3 'on the first layer 3.
• H is then defined between the surface of the central zone of the strand 21 and the surface of the overlay 34'.
• the overlay 3 ' made of electrically insulating material, preferably mineral, is structured discontinuous defining through holes, of thickness e z from 20 to 100 nm.
• the through holes are of width W1 with Wc> W1.
• Zones of strands called edge zones 22a, 22'a, are contiguous to the lateral zones 22, 22 'are more peripheral than the lateral zones and are in the cavities under the overlay, thus flush with the surface 34 of the first layer 3.
• edge zones 22a, 22'a are of width L2 defined as the distance between points X 'and Y,
• L3 is the distance between X "and Y", Y "being the orthogonal projection of Y in the plane of the surface of the lateral zones 22, 22 '.
• L3 is greater than the total height e c + e ' c and L3 ⁇ 2 (e c + e' c ) where e c is the height of the cavities and e ' c is the height of the holes of the overlay 3.
• the first layer is a titanium oxide layer of 400 nm and the overlayer is a silica oxide layer of thickness e z equal to 30 nm for example deposited by PVD or sol gel or alternatively a layer of silica the finest possible. This can be a multilayer. Generally, e c is greater than e ' c (e z ).

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  • 2014-09-11 FR FR1458559A patent/FR3025944B1/fr not_active Expired - Fee Related
• 2015
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