Classifications

• • 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
  • H10K50/85—Arrangements for extracting light from the devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/81—Anodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/82—Cathodes
  • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
• • 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
  • H10K50/85—Arrangements for extracting light from the devices
  • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
• • 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
  • H10K50/85—Arrangements for extracting light from the devices
  • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
• • 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.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
  • Y10T428/24471—Crackled, crazed or slit

Definitions

• the present invention relates to an organic light-emitting diode device comprising a particular support and its method of manufacture.
• the invention also relates to a support coated with an electrode particularly suitable for preparing said diode devices.
• the invention relates to the use of the support in an organic light-emitting diode device.
• the OLED (OLED for "Organic Light Emitting Diodes” in English) comprises a material, or a stack of materials, electroluminescent (s) organic (s), and is framed by two electrodes.
• One of the so-called lower electrodes, generally the anode, is associated with a support such as a glass substrate and the other, so-called upper electrode, generally the cathode, is arranged on the opposite organic material or materials. of the anode.
• OLED is a device that emits light by electroluminescence using the recombination energy of holes injected from the anode and electrons injected from the cathode.
• top emission in English
• front emission devices that is to say with an upper (semi) transparent electrode and a lower reflective electrode
• the front and rear emission devices that is to say with both a lower (semi) transparent electrode and an upper (semi) transparent electrode which may be called hereinafter transparent OLED device .
• the invention relates more particularly to OLED devices with rear emission and front and rear transmission.
• an OLED device comprises a support as a front substrate, or glass-function substrate (hereinafter glass substrate) and a possible encapsulation system.
• the support provides mechanical protection, while allowing good radiation transmission.
• Encapsulation systems are conventionally made of a hollow glass cover glued to the support.
• the cavity between the support and the hood is generally filled with an inert gas such as nitrogen and may contain a desiccant compound to minimize moisture near the organic layers.
• the cathode In the case of the use of OLED in an emissive device whose emission is only one side, the cathode is generally not transparent, and the photons emitted cross the transparent anode and the support OLED to provide light outside the device.
• the cathode and the anode are transparent, and the emitted photons pass through the transparent anode and / or cathode to provide the light outside the device.
• OLED devices Organic light-emitting diode devices
• OLED devices are new efficient light sources and low consumption.
• air side solutions which consist in extracting the light reflected at the air / support interface.
• One known strategy for increasing the energy conversion efficiency of an OLED device is to improve the transmission properties of the support forming the front substrate, by limiting the reflection of the incident radiation on this support.
• the OLED device texture at least the outer major surface of the support facing away from the OLED device, by providing it with a plurality of geometric patterns in relief, concave or convex with respect to a general plane of this device. face.
• These patterns may have a micrometric or millimetric scale.
• the patterns may in particular be pyramids or cones, or else patterns having a preferred longitudinal direction, such as grooves or ribs.
• Optical efficiency is the ratio of the light extracted in the air from the light available in the glass.
• the reflection by a glazing is said diffuse when radiation incident on the glazing with a given angle of incidence is reflected by the glazing in a plurality of directions.
• the reflection by a glazing is said specular when radiation incident on the glazing with a given angle of incidence is reflected by the glazing with a reflection angle equal to the angle of incidence.
• the transmission through a glazing is said specular when radiation incident on the glazing with a given angle of incidence is transmitted by the glazing with a transmission angle equal to the angle of incidence.
• the invention more particularly intends to remedy by proposing a support for OLED comprising a particular layered element.
• the proposed solution according to the invention allows in all cases the improvement of the extraction of light available in the air by extraction of the light reflected at the air / support interface.
• the extraction solution also makes it possible to introduce a maximum of light into the support by minimizing the guiding effect of the transparent electrode and the organic layers.
• the subject of the invention is an organic light-emitting diode device 6 comprising at least one organic light-emitting diode 7 and a support 5 comprising a transparent layered element 1 having two smooth external main surfaces (2A, 4A), characterized in that what the layered element comprises:
• two outer layers (2, 4) which each form one of the two outer main surfaces (2A, 4A) of the layered element and which consist of transparent materials, preferably dielectric materials, having substantially the same refractive index ( n2, n4), and
• this central layer 3 interposed between the outer layers, this central layer 3 being formed either by a single layer which is a transparent layer, preferably a dielectric layer, with a refractive index (n3) different from that of the outer layers, or a metal layer or by a stack of layers (3i, 3 2, 3 k) which comprises at least one transparent layer, preferably dielectric, refractive index (n3i, 2 n3, n3 k) different from that of the outer layers or metal layer,
• each contact surface (S 0 , Si, S k ) between two adjacent layers of the layered element which are a transparent refractive index (n2, n3, n4, n3i, n3 2 , ... or n3 k ) and the other metallic, or which are two transparent layers of different refractive indices, is textured and parallel to the other textured contact surfaces between two adjacent layers which are a transparent refractive index (n2 , n3, n4, n3i, n3 2 , ... or n3 k ) the other metallic or which are two transparent layers of different refractive indices.
• the transparent layers on the other hand, preferably dielectric, of refractive index determined, for which the difference in refractive index with respect to that of the outer layers is to be considered.
• the particular support used according to the invention makes it possible to obtain a specular transmission of an incident radiation coming from the diode on the layered element and a diffuse reflection of a radiation regardless of the direction of the source through the support. .
• Specular transmission of radiation from the diode or through the diode through the carrier makes the support of the invention useful as an extraction solution for transparent OLED devices. This same specular transmission property also makes it possible to maintain the mirror appearance in the case of diode devices comprising a reflective cathode provided with the particular support of the invention.
• the support therefore comprises a transparent element in transmission with diffuse reflection.
• the support according to the invention is considered to be laid horizontally, with its first downwardly facing face defining a lower outer main surface and its second facing opposite to the first face, facing upwards defining an upper outermost surface. ; the meanings of the expressions “above” and “below” are thus to be considered in relation to this orientation. In the absence of specific stipulation, the expressions "above” and
• the light-emitting diode (s) are placed above or below the support, that is to say either in contact with the second face of the support when the diodes are placed above or in contact with the first face when the diodes are placed below.
• the organic light-emitting diode comprises:
• a first electrode preferably transparent, in the form of a layer (s)
• a second electrode in the form of a layer (s), deposited on the organic electroluminescent system (s) opposite the first electrode.
• a transparent organic light-emitting diode device a first and a second transparent electrode are used.
• a first transparent electrode and a second reflective electrode are used.
• the invention also relates to a support as defined above coated with an electrode for an organic electroluminescent diode device, characterized in that said support comprises at least one layered element.
• the support comprises a first face and a second face opposite to the first face and comprises above its second face or below its first face the electrode in the form of a layer.
• the invention relates to the use of a support in an organic light-emitting diode device, characterized in that said support comprises a transparent layered element 1.
• the electrodes of the OLED preferably comprise at least one electrically conductive layer.
• the electrode in contact with the support is an anode.
• the electrically conductive layer may consist of one or more materials chosen from ITO, ZnO: Al, SnO2: F, or a thin layer or a stack of thin layers containing a thin conductive metal layer such as Ag, Au, Cu.
• the support may further comprise at least one additional layer positioned above or below the layered element.
• the said additional layer or layers of the support may consist of transparent materials, preferably dielectric materials, all having substantially the same refractive index or having different indices of refraction as the transparent, preferably dielectric, materials of the outer layers of the element. layers.
• the support comprises two upper and lower outer major surfaces.
• the main external surfaces of the support are combined with the surfaces external principal of the layered element if the support does not include an additional layer.
• the support includes:
• the upper outer main surface of the support will be merged with the upper outer main surface of the upper additional layer
• the lower outer major surface of the support will be merged with the lower outer major surface of the lower additional layer.
• index refers to the optical refractive index, measured at the wavelength of 550 nm.
• a thin layer is a layer with a thickness of less than 1 ⁇ .
• Two transparent materials or transparent layers, preferably dielectric have substantially the same refractive index, or have their refractive indices substantially equal, when the two transparent materials, preferably dielectric, have refractive indices whose absolute value of the difference between their refractive indices at 550 nm is less than or equal to 0.15.
• the absolute value of the difference in refractive index at 550 nm between the transparent, preferably dielectric, materials constituting the two outer layers of the layered element is less than 0.05 and preferably less than 0.015.
• Two transparent materials or transparent layers, preferably dielectric, have different refractive indices when the absolute value of the difference between their refractive indices at 550 nm is strictly greater than 0.15.
• the absolute value of the difference in refractive index at 550 nm between, on the one hand, the outer layers and, on the other hand, at least one transparent refractive index layer (n3, n3i , n3 2 , n3 k ) of the central layer is greater than or equal to 0.3, preferably greater than or equal to 0.5, more preferably greater than or equal to 0.8.
• the rays from the diode that were initially in the output cone exit at the support / air interface.
• the relatively large difference in refractive index occurring at at least one textured contact surface internal to the layered element makes it possible to promote the reflection of radiation on this textured contact surface.
• the rays that would have been trapped by total internal reflection at the support / air interface can be reflected and scattered by the textured surface of the central layer and thereby extracted into the air after a second reflection.
• the contact area between two adjacent layers is the interface between the two adjacent layers.
• a transparent element is an element through which there is radiation transmission at least in the wavelength ranges useful for the intended application of the element.
• the element when used as a building or vehicle glazing, it is transparent at least in the wavelength range of the visible.
• the transparent materials or the transparent layers refer in particular to:
• the outer layers (2, 4) made of transparent materials of refractive index (n2, n4),
• n3i, n3 2, ..., or n3 k different from the outer layers.
• the transparent materials or transparent layers are of organic or mineral nature.
• the transparent materials or transparent layers are not metallic.
• the transparent materials or transparent mineral layers may be chosen from oxides, nitrides or halides of one or more transition metals, non-metals or alkaline-earth metals.
• the transition metals, non-metals or alkaline-earth metals are preferably chosen from silicon, titanium, tin, zinc, indium, aluminum, molybdenum, niobium, zirconium and magnesium.
• the organic dielectric materials or layers are chosen from polymers.
• a material or dielectric layer is a non-metallic material or layer. It is considered that a material or dielectric layer is a material or a layer of low electrical conductivity, preferably less than 10 4 S / m and possibly less than 100 S / m. It can also be considered that a material or dielectric layer is a material or a layer having a higher resistivity than that of metals.
• the dielectric materials or layers of the invention have a resistivity greater than 1 ohm centimeter (Q.cm), preferably greater than 10 ⁇ .cm and possibly greater than 10 4 ⁇ .cm.
• the central layer and / or the upper outer layer of the layered element may constitute an electrode of the OLED device, preferably the lower electrode.
• the central layer preferably comprises at least one metal layer.
• the layers located above this layer are transparent layers of refractive index n2, n3i, 2 n3, n3 k, these layers must be conductive to a certain extent.
• Transparent materials or transparent layers can therefore be electrically conductive layers. Indeed, these transparent materials or transparent layers must have a sufficiently "low" resistivity not to render insulating the electrode consisting of this or these layers and the central layer of the layered element.
• These layers or materials preferably have a resistivity of less than 1 ohm. cm, preferably less than 10 -2 ohm cm.
• a textured or rough surface is a surface for which the surface properties vary on a scale larger than the wavelength of radiation incident on the surface. The incident radiation is then transmitted and diffuse reflected by the surface.
• a textured or rough surface according to the invention has a roughness parameter corresponding to the arithmetical average deviation Ra of at least 0.5 ⁇ , in particular between 1 and 5 m (corresponding to the arithmetic mean of all absolute distances of the roughness profile R measured from a median line of the profile over an evaluation length).
• a smooth surface is a surface for which the surface irregularities are such that the radiation is not deflected by these surface irregularities. The incident radiation is then transmitted and reflected specularly by the surface.
• a smooth surface is a surface for which the surface irregularities are smaller than the wavelength of radiation incident on the surface or much larger (large-scale ripples).
• the outer layers or the additional layers may have certain surface irregularities provided that these layers are in contact with one or more additional layers made of dielectric materials having substantially the same refractive index and which have on their opposite side to that in contact with said layer having certain irregularities, a smooth surface as defined above.
• a smooth surface is a surface having either a roughness parameter corresponding to the average arithmetic deviation Ra less than 0.1 ⁇ , preferably less than 0.01 ⁇ , or slopes less than 10 °.
• a glazing corresponds to an organic or mineral transparent substrate.
• the layered element can be rigid or flexible. It may be in particular a glazing, consisting for example of glass or polymer material. It may also be a flexible film based on polymeric material, in particular adapted to be attached to a surface.
• the specular transmission results from the fact that the two outer layers of the layered element have smooth outer major surfaces and consist of materials having substantially the same refractive index, and that each textured contact surface between two adjacent layers of the layered element which are transparent and metallic, or which are two transparent layers of different refractive indices, is parallel to the other textured contact surfaces between two adjacent layers which are one transparent and the other other metal or which are two transparent layers of different refractive indices.
• the smooth outer surfaces of the layered element allow specular transmission of radiation to the air / outer layer interface, i.e. allow the entry of radiation from the diode into the upper outer layer and outputting radiation from the lower outer layer into the air, without changing the direction of the radiation.
• the parallelism of the textured contact surfaces implies that the or each constituent layer of the central layer which is transparent of refractive index different from that of the outer layers, or which is metallic, has a uniform thickness perpendicular to the contact surfaces of the layer. central with the outer layers.
• This uniformity of the thickness can be global over the whole extent of the texture, or local on sections of the texture.
• the thickness between two consecutive textured contact surfaces can change, by section, depending on the slope of the texture, the textured contact surfaces always remaining parallel to each other.
• This case is particularly present for a layer deposited by sputtering, where the thickness of the layer is even lower than the slope of the texture increases.
• the thickness of the layer remains constant, but the thickness of the layer is different between a first texture section having a first slope and a second texture section having a second slope different from the first slope.
• the layer or each layer constituting the central layer is a layer deposited by sputtering.
• cathodic sputtering in particular sputtering assisted by a magnetic field, ensures that the surfaces delimiting the layer are parallel to each other, which is not the case with other deposition techniques such as evaporation or chemical vapor deposition (CVD), or the sol-gel process.
• CVD chemical vapor deposition
• the parallelism of the textured contact surfaces within the layered element is essential to obtain specular transmission through the element.
• Incident radiation on a first outer layer of the layered element passes through this first outer layer without modification of its direction. Due to the difference in nature, dielectric or metallic, or the difference in refractive index between the first outer layer and at least one layer of the core layer, the radiation is then refracted in the core layer.
• the refraction angle of the radiation in the second outer layer from the central layer is equal to the angle of incidence of the radiation on the central layer from the first outer layer, in accordance with the Snell-Descartes law for refraction.
• the radiation thus emerges from the second outer layer of the layered element in a direction that is the same as its direction of incidence on the first outer layer of the element.
• the transmission of radiation by the layered element is thus specular.
• a clear vision is obtained through the layered element, that is to say without the layered element being translucent, thanks to the specular transmission properties of the layered element.
• the device of the invention makes it possible to obtain a light transmission measured according to the ISO 9050: 2003 standard of at least 50%, preferably at least 60% and better still at least 75% and a blur in transmission measured according to ASTM D 1003 less than 20%, preferably less than 10% and better still less than 5%. These values being measured on the support side.
• At least one of the two outer layers of the layered element made of transparent materials, preferably dielectric materials, is chosen from:
• transparent substrates one of the main surfaces of which is textured and the other of which is smooth, preferably chosen from polymers, glasses and ceramics, a layer of transparent material chosen from oxides, nitrides or halides of one or more transition metals, non-metals or alkaline-earth metals,
• a layer based on curable materials initially in a viscous, liquid or pasty state suitable for shaping operations comprising:
• thermoformable or pressure-sensitive plastic inserts or leaflets which may preferably be based on polymers chosen from polyvinylbutyral (PVB), polyvinyl chloride (PVC), polyurethane (PU), polyethylene terephthalate or ethylenes vinyl acetate (EVA).
• PVB polyvinylbutyral
• PVC polyvinyl chloride
• PU polyurethane
• EVA ethylenes vinyl acetate
• the transparent substrates of which one of the main surfaces is textured and the other smooth, are preferably used as the lower outer layer.
• the texturing of one of the main surfaces of the transparent substrates may be obtained by any known method of texturing, for example by embossing the surface of the previously heated substrate to a temperature at which it is possible to deform it, in particular by rolling with means of a roller having on its surface a texturing complementary to the texturing to be formed on the substrate; by abrasion by means of abrasive particles or surfaces, in particular by sanding; by chemical treatment, especially acid treatment in the case of a glass substrate; by molding, especially injection molding in the case of a thermoplastic polymer substrate; by engraving.
• the transparent substrate is made of polymer, it can be rigid or flexible.
• suitable polymers according to the invention include, in particular:
• polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN);
• polyacrylates such as polymethyl methacrylate (PMMA);
• fluorinated polymers such as fluoroesters: ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP); photocurable and / or photopolymerizable resins, such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate and
• These polymers generally have a range of refractive index ranging from 1.3 to 1.7. However, it is interesting to note that some of these polymers, and in particular the polymers comprising sulfur, such as polythiourethanes, may have high refractive indices of up to 1.74.
• glass substrates directly usable as the outer layer of the layered element include:
• the glass substrates sold by Saint-Gobain Glass in the ALBARINO® S, P or G range or in the MASTERGLASS® range which have, on one of their main surfaces, a texture obtained by rolling,
• each of the two outer layers of the layered element is formed by a transparent substrate
• the two transparent substrates have complementary textures with respect to each other.
• the textured outer layer of the layered element may simply consist of a layer of dielectric material selected from oxides, nitrides or halides of one or more transition metals, nonmetals or alkaline earth metals.
• the transition metals, non-metals or alkaline earth metals are preferably selected from silicon, titanium, tin, zinc, aluminum, molybdenum, niobium, zirconium, magnesium.
• This thin layer of dielectric material may consist of materials chosen from high refractive index materials such as Si 3 N 4 , AlN, NbN, SnO 2 , ZnO, SnZnO, ⁇ 2 O 3 , MoO 3 , NbO, TiO 2 , Zr0 2 , InO and materials with low refractive indices such as Si0 2 , MgF 2 , AIF 3 .
• This layer is preferably used as the upper outer layer of the layered element and can be deposited by a cathodic sputtering technique in particular assisted by a magnetic field, by evaporation, by chemical vapor deposition (CVD), on a support already coated with a lower outer layer and a core layer.
• dielectric layers thus comprise a textured surface conforming to the surface roughness of the central layer and an external main surface opposite this surface which is flat.
• the outer layers of the layered element may also be based on curable materials initially in a viscous, liquid or pasty state suitable for shaping operations. Preferably, these layers are used as the outermost layers of the layered element.
• the initially deposited layer in a viscous, liquid or pasty state may be a layer of photocrosslinkable and / or photopolymerizable material.
• this photocrosslinkable and / or photopolymerizable material is in liquid form at room temperature and gives, when it has been irradiated and photocrosslinked and / or photopolymerized, a transparent solid free of bubbles or any other irregularity.
• It may be in particular a resin such as those usually used as adhesives, adhesives or surface coatings. These resins are generally based on monomers / comonomers / pre-polymers of the epoxy type, epoxysilane, acrylate, methacrylate, acrylic acid, methacrylic acid.
• a resin instead of a resin, it may be a photocurable aqueous gel, such as a polyacrylamide gel.
• photocurable and / or photopolymerizable resins usable in the present invention include the products sold by Norland Optics under the trade name NOA® Norland Optical Adhesives, such as NOA®65 and NOA®75, for example.
• the outer layer initially deposited in a viscous, liquid or pasty state may be a layer deposited by a sol-gel process, for example a sol-gel deposited silica glass.
• the precursors for the sol-gel deposition of a silica glass are Si (OR) 4 silicon alkoxides, which give rise in the presence of water to hydrolysis-condensation type polymerization reactions. These polymerization reactions lead to the formation of more and more condensed species, which lead to colloidal silica particles forming soils and then gels. Drying and densification of these silica gels, at a temperature of the order of a few hundred degrees, leads to a glass whose characteristics are similar to those of a conventional glass.
• the colloidal solution or the gel can be deposited easily on the textured main surface of the central layer opposite the first outer layer, conforming to the texture of this surface.
• This deposit can in particular be made by soaking-withdrawal ("dip-coating"), spin coating ("spin-coating") or blade coating ("blading").
• the layers deposited by sol-gel process provide a planarization of the surface of the layered element.
• the outer major surface of this so-called planarization layer may have certain surface irregularities.
• an additional layer having substantially the same refractive index as said outer layer such as an interlayer or a sheet plastic material described below.
• an outer layer may be obtained by depositing an enamel based on a glass frit on a glass substrate, for example soda-lime.
• the enamel is not diffusing in itself and does not include compounds or structures such as the presence of air bubbles, likely to confer such properties.
• the enamel layer corresponds to a layer based on curable materials initially in a liquid, viscous or pasty state suitable for shaping operations.
• the enamel layer when used as a lower outer layer, can then be roughened or textured by etching in extreme pH solutions, i.e., either strongly acidic (pH ⁇ 2) or strongly basic (pH> 12).
• extreme pH solutions i.e., either strongly acidic (pH ⁇ 2) or strongly basic (pH> 12).
• the glass substrate is an additional layer of the support and the enamel layer constitutes the outer layer of the layered element.
• the enamel layer can also be used as an upper outer layer.
• the textured upper outer layer of the layered element may simply consist of an enamel composition based on glass frit deposited by a liquid deposition technique (such as screen printing or slot coating ) on a support already coated with a lower outer layer and a core layer.
• the enamel layer will "fill" the roughness of the central layer.
• This layer comprises a surface conforming to the surface roughness of the central layer which is thus textured and an outer major surface opposite that surface which is flat.
• the materials used for the support that is to say the materials of the outer layer coated with the central layer, are likely not to deform following this cooking step.
• the enamel composition comprising the glass frit intended to form the upper outer layer has a temperature of vitreous transition Tg less than the glass transition temperature of the frit composition used to form the enamel of the lower outer layer.
• This method of preparation using glass enamel compositions makes it possible to obtain external layers for the layered element having low or high refractive indices. For example, by depositing a high-index enamel composition, a substrate coated with a high-index textured outer layer is obtained. To obtain high refractive index enamel layers, it suffices to use an enamel composition comprising a glass frit rich in heavy elements such as a Bismuth-rich enamel having, for example, a Bismuth content greater than 40. %.
• the outer layer may comprise a layer of thermoformable or pressure-sensitive plastic interlayer or sheet positioned against the textured main surface of the central layer opposite to the first outer layer and shaped against this textured surface by compression and / or heating.
• This layer based on a polymeric material may be, in particular, a layer based on polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET), polyvinyl chloride (PVC). These layers can be shaped by compression and / or heating.
• the thickness of the outer layer is preferably between 1 ⁇ and 6 mm and varies according to the choice of transparent material, preferably dielectric.
• the flat or textured glass substrates preferably have a thickness of between 0.4 and 6 mm, preferably 0.7 and 2 mm.
• the flat or textured polymer substrates preferably have a thickness of between 0.020 and 2 mm, preferably 0.025 and 0.25 mm.
• the outer layers consist of a layer of transparent materials, preferably dielectric preferably have a thickness between 0.2 and 20 ⁇ , preferably 0.5 and 2 ⁇ .
• the layers based on curable materials initially in a viscous, liquid or pasty state suitable for shaping operations preferably have a thickness of between 0.5 and 40 ⁇ , preferably between 0.5 and 7 ⁇ .
• the layers based on photocurable and / or photopolymerizable materials preferably have a thickness of between 0.5 and 20 ⁇ , preferably 0.7 and 10 ⁇ .
• the layers deposited by a sol-gel process preferably have a thickness of between 1 and 40 ⁇ , preferably between 10 and 15 ⁇ .
• the glass frit enamel layers preferably have a thickness of between 3 and 30 ⁇ , preferably 5 and 20 ⁇ .
• the layers based on a spacer or plastic sheet preferably have a thickness of between 10 ⁇ and 1 mm, preferably between 0.3 and 1 mm.
• Transparent materials or transparent layers, preferably dielectric layers may have:
• the materials used to form the upper and lower layers of the layered element are high refractive index materials.
• the resulting extraction solution allows both to introduce into the support a maximum of light by minimizing the guiding effect of the transparent electrode and the organic layers and to extract the light reflected at the air / support interface .
• the term "high refractive index material” is understood to mean a material comprising an index comprised between 1.7 and 2.4, preferably between 1.75 and 2.1 or even between 1.8 and 2.0.
• These high refractive index materials may especially be chosen from glasses, polymers such as sulfur polymers, layers of dielectric materials and enamel layers.
• the layer or stack of layers of the central layer of the layered element may comprise a layer chosen from:
• At least one adhesive layer made of transparent polymer made of transparent polymer
• At least one thin layer consisting of a transparent material, preferably a dielectric material, chosen from oxides, nitrides or halides of one or more transition metals, non-metals or alkaline-earth metals,
• At least one thin metallic layer in particular a thin layer of silver, gold, copper, titanium, niobium, silicon, aluminum, nickel-chromium alloy (NiCr), stainless steel , or their alloys.
• the thin layer consisting of a transparent material, preferably a dielectric material, may be chosen from:
• At least one thin layer made of a transparent material, preferably a dielectric material, with a high refractive index, different from the refractive index of the outer layers, such as Si 3 N 4 , AlN, NbN, SnO 2 , ZnO, SnZnO, Al 2 0 3, Mo0 3, NbO, Ti0 2, Zr0 2, InO,
• a transparent material preferably a dielectric material
• At least one thin layer made of a transparent material, preferably dielectric, with a low refractive index, different from the refractive index of the outer layers, such as Si0 2 , MgF 2 , AIF 3 .
• the core layer comprises an oxide
• it can be doped.
• the core layer may be, for example, tin doped indium oxide, aluminum doped zinc oxide or fluorine doped tin oxide layer.
• the outer layers are assembled together by means of this central layer formed by a layer of dielectric material of refractive index different from that of the outer layers.
• the choice of the thickness of the central layer depends on a number of parameters. In general, it is considered that the total thickness of the central layer is between 5 and 200 nm and the thickness of a layer of the central layer is between 1 and 200 nm.
• the thickness of a layer is preferably between 5 to 40 nm, better still between 6 and 30 nm and more preferably 6 to 20 nm.
• the central layer is a transparent layer, preferably a dielectric layer, for example of TiO 2 , it preferably has a thickness of between 20 and 100 nm and better still of 55 and 65 nm and / or a refractive index of between 2.2. and 2.4.
• the OLED device is transparent, that is to say it comprises an anode and a transparent cathode, it is possible to adjust the light level emitted by each side of the diode for example by choosing the thickness and the nature of the central layer, including its reflection coefficient. Indeed, it is easily understood that in a transparent diode device, the more the central layer is reflective, the more we promote the emission side opposite to that of the support.
• the use of the particular support of the invention makes it possible not only to favor the extraction but also to adapt the light level on each side of the device.
• Another possibility to change the light level emitted by each side of the diode may be to choose a central layer having a reflection coefficient different according to the side where one is located. For example, a central layer having a high reflection coefficient on the air-support interface side and low diode-support side will favor the air-support side lighting.
• the composition of the central layer of the layered element can be adjusted to confer additional properties to the layered element, for example thermal properties, solar control type and / or low emissivity.
• the central layer of the layered element is a transparent stack of thin layers comprising an alternation of "n" metal functional layers, especially functional layers based on silver or metal alloy containing silver, and "(n + 1)" antireflection coatings, with n> 1, where each metal functional layer is disposed between two antireflection coatings.
• such a metal functional layer stack has reflection properties in the field of solar radiation and / or in the field of long-wave infrared radiation.
• the metal functional layers essentially determine the thermal performance, while the antireflection coatings that surround them act on the optical appearance interferentially. Indeed, if the metallic functional layers make it possible to obtain desired thermal performance even at a small geometrical thickness, of the order of 10 nm for each metal functional layer, they strongly oppose the passage of radiation in the field of wavelengths of the visible. Therefore, antireflection coatings on both sides of each metal functional layer are necessary to ensure good light transmission in the visible range.
• the device of the invention can be used in a glazing in which the support is placed on the outside and the diode on the interior side of the habitat.
• the support of the invention makes it possible, in addition to constituting an extraction solution for OLED, to protect the OLED against harmful radiation such as UV.
• the system can realize the solar control function, when the central layer is sufficiently conductive.
• the texture of each contact surface between two adjacent layers of the layered element which are one transparent (preferably non-metallic) and the other metallic, or which are two transparent layers of different refractive indices is formed by a plurality of recessed or protruding patterns with respect to a general plane of the contact surface.
• the average height of the patterns of each contact surface between two adjacent layers of the layered element, which are one transparent and the other metallic, or which are two transparent layers of different refractive indices is included between 1 micrometer and 1 millimeter.
• the average height of the patterns of the contact surface is defined as the arithmetical mean of the distances y, in absolute value, taken between the vertex and the general plane of the contact surface for each pattern of the
• the patterns of the texture of each contact surface between two adjacent layers of the layered element, which are transparent and metallic, or which are two transparent layers of different refractive indices can be distributed random on the contact surface.
• the texture patterns of each contact surface between two adjacent layers of the layered element which are transparent and metallic, or which are two transparent layers of different refractive indices may be distributed periodically on the contact surface.
• These patterns may be, in particular, cones, pyramids, grooves, ribs, wavelets.
• the The thickness of this layer is small relative to the average height of the patterns of each of its contact surfaces with the adjacent layers. Such a small thickness makes it possible to increase the probability that the input interface of a radiation in this layer and the output interface of the radiation out of this layer are parallel, and therefore to increase the percentage of specular transmission of radiation through the layered element.
• the thickness of each layer of the central layer which is interposed between two layers of nature, transparent (preferably non-metallic) or metallic, different from his own or refractive indices different from his, where this thickness is taken perpendicular to its contact surfaces with the adjacent layers, is less than 1/4 of the average height of the patterns of each of its contact surfaces with the adjacent layers.
• the core layer is formed either by a single layer conformably deposited on the textured main surface of the first outer layer, or by a stack of layers successively deposited conformably on the textured main surface of the first outer layer.
• the central layer is conformably deposited on the main textured surface of the first outer layer, if following deposition, the upper surface of the central layer is textured and parallel to the textured contact surface of the first outer layer.
• Deposition of the central layer conformably, or layers of the central layer successively in accordance with the textured main surface of the first outer layer is preferably carried out by cathodic sputtering, in particular assisted by a magnetic field.
• the additional layers are preferably chosen from:
• transparent substrates chosen from polymers, glasses or ceramics as defined above but comprising two smooth main surfaces,
• curable materials initially in a viscous, liquid or pasty state suitable for shaping operations as described above,
• thermoformable or pressure sensitive plastic material inserts or sheets of thermoformable or pressure sensitive plastic material as described above.
• the smooth outer surfaces of the layered element and / or the smooth outer surfaces of the support are flat or curved, preferably these smooth outer main surfaces are parallel to each other. This helps to limit the light scatter for radiation passing through the layered element, and thus to improve the clarity of vision through the layered element.
• the support may be a rigid glazing or a flexible film.
• a flexible film is advantageously provided, on one of its external main surfaces, with an adhesive layer covered with a protective strip intended to be removed for bonding the film.
• the support comprising the layered element in the form of a flexible film is then adapted to be reported by gluing on an existing surface, for example, on an OLED and thus forming the device of the invention.
• a first outer layer of the two outer layers of the layered element is a transparent substrate.
• the core layer is formed either by a single layer conformably deposited on the textured main surface of the first outer layer, or by a stack of layers successively deposited conformably on the textured main surface of the first outer layer.
• the central layer is deposited by cathodic sputtering, in particular assisted by a magnetic field.
• the second outer layer or upper outer layer preferably comprises a curable material layer initially in a viscous, liquid or pasty state or a spacer of thermoformable or pressure-sensitive material, deposited on the main textured surface of the central layer opposite to the first outer layer.
• an additional layer may be used as a counter-substrate.
• the layer initially deposited in a viscous, liquid or pasty state then ensures a bonding between the lower outer layer provided with the central layer and the counter-substrate.
• the upper outer layer comprises a layer based on a spacer or sheet of thermoformable or pressure-sensitive plastic material
• an additional layer for example, a transparent refractive index substrate. substantially equal to those of the outer layers can be used.
• the layer based on a spacer or plastic sheet then corresponds to a lamination interlayer ensuring the connection between the lower outer layer of the layered element coated with the core layer and the additional layer.
• the support of the organic light-emitting diode device of the invention preferably comprises the following stack:
• At least one lower additional layer chosen from transparent substrates whose two main surfaces are smooth, such as polymers and glasses and inserts made of thermoformable or pressure-sensitive plastics material, a lower outer layer chosen from transparent substrates such as polymers and glasses and curable materials initially in a viscous, liquid or pasty state suitable for shaping operations such as enamel layers,
• a central layer comprising a thin layer made of a transparent material of refractive index (n3), preferably dielectric, or a thin metallic layer,
• an upper outer layer chosen from transparent substrates chosen from polymers and glasses, curable materials initially in a viscous, liquid or pasty state suitable for shaping operations and inserts made of thermoformable or pressure-sensitive plastics material;
• thermoformable plastic material or pressure sensitive optionally at least one additional upper layer selected from transparent substrates whose two main surfaces are smooth selected from polymers and glasses and inserts of thermoformable plastic material or pressure sensitive.
• the support of the organic light-emitting diode device comprises:
• a lower outer layer chosen from transparent substrates made of rough glass
• a central layer preferably comprising a thin TiO 2 layer
• an upper outer layer chosen from photocurable and / or photopolymerizable resins
• an upper additional layer chosen from transparent substrates made of flat glass.
• the support of the organic light-emitting diode device of the invention preferably comprises the following stack:
• a central layer preferably comprising a thin TiO 2 layer
• an upper outer layer chosen from inserts made of thermoformable or pressure-sensitive plastics material, preferably a layer based on polybutyral vinyl,
• the support of the organic light-emitting diode device of the invention comprises the following stack:
• a lower outer layer chosen from transparent substrates made of rough glass
• a central layer preferably comprising a thin TiO 2 layer
• an upper outer layer chosen from a layer obtained by a sol-gel process
• an additional upper layer selected from the spacers of thermoformable material or pressure sensitive which is preferably superimposed another additional top layer selected from the transparent glass substrates.
• the upper and lower outer layers of the layered element consist of transparent materials, preferably dielectric materials, comprising a high refractive index between 1 , 7 and 2.4, preferably between 1.75 and 2.1, and more preferably between 1.8 and 2.
• the support preferably comprises the following stack:
• a lower outer layer chosen from transparent substrates made of glass and high-index polymer or
• an additional lower layer selected from transparent glass substrates coated with an outer layer consisting of a high refractive index enamel layer, for example an enamel layer obtained from an enamel composition comprising a bismuth mass content greater than 40%, and
• a central layer comprising a thin layer made of a transparent material, preferably a dielectric material, preferably SiO 2 or TiO 2, or a thin metallic layer, preferably a layer consisting of Ag, NiCr, Ti, Cu , from Au,
• an upper outer layer chosen from a high-index transparent polymer or glass substrate, a high-index enamel layer, a high-index, transparent, preferably dielectric material layer.
• the central layer of the layer element and / or the outer upper layer of the layered element may constitute the lower electrode (or first electrode) of the organic light-emitting diode.
• the central layer is preferably metal or optionally comprises a metal layer for imparting the electrode function to the core layer.
• the upper outer layer of the layered element is preferably made of transparent materials, preferably non-metallic having a resistivity of less than 1 ohm. cm, preferably less than 10 -1 ohm cm and better still less than 10 -2 ohm. cm.
• this embodiment preferably comprises upper and lower outer layers of the layered element made of transparent materials comprising a high refractive index.
• the support of the organic light-emitting diode device of the invention preferably comprises the following stack:
• a lower outer layer chosen from glass substrates and substrates made of polymer or
• a lower additional layer selected from transparent glass substrates coated with an outer layer consisting of a high refractive index enamel composition
• a central layer preferably a metal layer such as a thin layer consisting of Ag, and
• an upper outer layer comprising a layer of transparent material.
• the lower outer layer preferably comprises a glass or high refractive index polymer substrate.
• the upper outer layer preferably comprises a layer of transparent material selected from Si 3 N 4, AlN, NbN, Sn0 2, ZnO, SnZnO, Al 2 0 3, Mo0 3, NbO, Ti0 2, Zr0 2, and more particularly SnZnO , Si 3 N 4 or ZnO, having a resistivity of less than 1 ohm. cm and preferably having a thickness between 0.5 and 20 ⁇ .
• the materials used to form the upper and lower layers of the layered element are low refractive index materials.
• the support of the organic light-emitting diode device of the invention may comprise a layered element comprising the following stack:
• a lower outer layer made of materials chosen from low-index glass substrates, low-index glass-frit enamel layers and low-index polymer substrates,
• a central layer preferably a dielectric layer consisting of Si0 2 or TiO 2 or a metal layer such as a layer consisting of Ag, NiCr, Ti, Cu, Au optionally surrounded by thin layers of other materials, an upper outer layer made of materials chosen from a low-index polymer substrate, a low-index glass substrate, a low-index glass-frit enamel layer and a layer of transparent, preferably dielectric material; , low index.
• Another object of the invention is a method of manufacturing a device as described above, comprising the following steps:
• a central layer is deposited on the textured main surface of the lower outer layer, ie, when the central layer is formed by a single layer, which is a transparent layer, preferably a dielectric layer, with a refractive index different from that of the lower outer layer or a metal layer, by depositing the central layer conformably on said textured main surface, ie, when the central layer is formed by a stack of layers comprising at least one transparent layer, preferably dielectric, of refraction different from that of the lower outer layer or a metal layer, by depositing the layers of the core layer successively in accordance with said textured main surface;
• the second outer layer or upper outer layer is formed on the main textured surface of the central layer opposite to the lower outer layer, where the outer lower and upper layers consist of transparent materials, preferably dielectric materials, having substantially the same index of refraction,
• At least one upper and / or lower additional layer is formed on the smooth outer main surface (s) of the layered element
• Another subject of the invention is a method of manufacturing a support coated with an electrode as described above, comprising the following steps:
• a central layer is deposited on the textured main surface of the lower outer layer, ie, when the central layer is formed by a single layer, which is a transparent layer, preferably a dielectric layer, with a refractive index different from that of the lower outer layer or a metal layer, by depositing the central layer conformably on said textured main surface, ie, when the central layer is formed by a stack of layers comprising at least one transparent layer, preferably dielectric, of refraction different from that of the lower outer layer or a metal layer, by depositing the layers of the core layer successively in accordance with said textured main surface;
• the second outer layer or upper outer layer is formed on the main textured surface of the central layer opposite to the lower outer layer, where the outer lower and upper layers consist of transparent materials, preferably dielectric materials, having substantially the same index of refraction,
• At least one upper and / or lower additional layer is formed on the smooth outer main surface (s) of the layered element
• the second outer layer is formed by depositing, on the main textured surface of the central layer opposite to the first outer layer, a layer of a material which has substantially the same refractive index as the first outer layer and which is initially in a viscous, liquid or pasty state suitable for shaping operations.
• the second outer layer may thus be formed, for example, by a process comprising the deposition of a layer of photocrosslinkable and / or photopolymerizable material initially in fluid form and then the irradiation of this layer, or by deposition of a layer by a sol-gel process.
• the second outer layer is formed by positioning, against the main textured surface of the central layer opposite to the first outer layer, a layer based on a polymeric material having substantially the same refractive index as the first outer layer, and then conforming this layer based on polymeric material against the main textured surface of the core layer by compression and / or heating at least at the glass transition temperature of the polymeric material.
• the layer based on polymeric material is in this case a spacer of thermoformable or pressure sensitive plastic material.
• the second outer layer is formed by injection into a mold of a polymer in the molten state capable of giving after curing a transparent polymer substrate.
• the transparent substrate obtained after curing is preferably chosen from transparent substrates made of polyacrylic polymer and in particular of the PMMA type.
• FIG. 1 is a schematic cross section of a diode device according to the invention.
• FIG. 2 is a view on a larger scale of the detail I of FIG. 1 for a first variant of the layered element
• FIG. 3 is an enlarged view of detail I of FIG. 1 for a second variant of the layered element
• FIG. 6 is a graph showing the colorimetric variations for the various OLED devices tested.
• the relative thicknesses of the different layers in the figures have not been rigorously respected.
• the possible thickness variation of the or each constituent layer of the central layer as a function of the slope of the texture has not been shown in the figures, it being understood that this possible variation in thickness does not affect the parallelism of the textured contact surfaces. Indeed, for each given slope of the texture, the textured contact surfaces are parallel to each other.
• the organic light-emitting diode device 6 illustrated in FIG. 1 comprises a support 5 and an organic light-emitting diode 7.
• the support comprises a layered element 1 comprising two outer layers 2 and 4, which consist of transparent materials having substantially the same index of refraction n2, n4.
• Each outer layer 2 or 4 has a smooth main surface, respectively 2A or 4A, facing outwardly of the layered member, and a surface main textured, respectively 2B or 4B, directed towards the interior of the layered element.
• the smooth outer surfaces 2A and 4A of the layered element 1 allow specular radiation transmission to each surface 2A and 4A, i.e. the entry of radiation into an outer layer or the exit of radiation from an outer layer without changing the direction of the radiation.
• the textures of the internal surfaces 2B and 4B are complementary to each other. As clearly visible in FIG. 1, the textured surfaces 2B and 4B are positioned facing one another, in a configuration in which their textures are strictly parallel to each other.
• the layered element 1 also comprises a central layer 3 interposed in contact between the textured surfaces 2B and 4B.
• the device also comprises an organic light-emitting diode 7 comprising two electrodes 9 and 11 and a layer or a stack of layers of organic material (s) some of which are electroluminescent 10.
• the support also comprises additional upper and lower layers 12.
• the central layer 3 is monolayer and consists of a transparent material which is either metallic or transparent and has a refractive index n3 different from that of the outer layers 2 and 4.
• the central layer 3 is formed by a transparent stack of several layers 3i, 3 2 , ..., 3k , where at least one of the layers 3i to 3k is either a metal layer or a layer transparent refractive index different from that of the outer layers 2 and 4.
• at least each of the two layers 3i and 3k located at the ends of the stack is a metal layer or a transparent layer of refractive index n3i or n3 k different from that of the outer layers 2 and 4.
• S 0 denotes the contact surface between the outer layer 2 and the central layer 3
• Si the contact surface between the central layer 3 and the outer layer 4.
• S 2 to S k are successively denoted by the internal contact surfaces of the central layer 3, starting from the nearest contact surface of the surface S 0 .
• the contact surface S 0 between the outer layer 2 and the core layer 3 is textured and parallel to the contact surface Si between the central layer 3 and the outer layer 4.
• the central layer 3 is a textured layer having over all its extent a uniform thickness e3, taken perpendicularly to the contact surfaces S 0 and Si.
• each contact surface S 2 , ..., S k between two adjacent layers of the constituent stack of the core layer 3 is textured and strictly parallel to the contact surfaces S 0 and Si between the outer layers 2, 4 and the central layer 3.
• all the contact surfaces S 0, S ⁇ , ..., S k between adjacent layers of the elementl that are either of different natures, transparent (preferably non-metallic) or metallic, either transparent of different refractive indices, are textured and parallel to each other.
• each layer 3i, 3 2 ,..., 3 k of the stack constituting the central layer 3 has a thickness e3i, e3 2 ,..., E3 k that is uniform, taken perpendicularly to the contact surfaces S 0 , Si, ..., S k .
• each contact surface S 0 , Si or S 0 , S 1 ,..., S k of the layered element 1 is formed by a plurality of recessed or protruding patterns with respect to a general plane. ⁇ of the contact surface.
• the average height of the patterns of each textured contact surface S 0 , Si or S 0 , S- 1 , ..., S k is between 1 micrometer and 1 millimeter.
• the thickness e3 or e3i, e3 2 ,..., E3 k of the or each constituent layer of the central layer 3 is less than the average height of the patterns of each textured contact surface S 0 , Si or S 0 , S- 1 , ..., S k of the layered element 1.
• This condition is important for increasing the probability that the input interface of a radiation in a layer of the layer 3 and the radiation output interface out of this layer are parallel, and thus increase the percentage of specular transmission of radiation through the layered element 1. For the sake of visibility of the different layers, this condition has not not strictly respected in the figures.
• the thickness e3 or e3i, e3 2 ,..., E3 k of the or each layer constituting the central layer 3 is less than 1/4 of the average height of the patterns of each textured contact surface of the layered element.
• the thickness e3 or e3i, e3 2 ,..., E3 k of each layer of the central layer 3 is of the order of or less than 1/10 of the average height of the patterns of each textured contact surface of the layered element.
• the radii R td transmitted by the layered element are transmitted with a transmission angle ⁇ equal to their angle of incidence ⁇ on the layered element.
• the transmission of radiation by the layered element 1 is therefore specular.
• FIG. 1 also illustrates an incident radiation R id coming from the diode on the support which is trapped by total internal reflection at the air / substrate interface.
• the reflected ray R r can then be scattered by the rough surface of the central layer of the layered element. This scattered ray R d then has an additional probability of being extracted in the air.
• the central layer 3 is conformably deposited on a textured surface 2B of a transparent, rigid substrate. or flexible, forming the outer layer 2 of the layered element 1.
• the main surface 2A of this substrate opposite the textured surface 2B is smooth.
• This substrate 2 may be, in particular, a textured glass substrate of SATINOVO®, ALBARINO® or MASTERGLASS® type.
• the substrate 2 may be a substrate based on polymeric material, rigid or flexible, for example of polymethyl methacrylate or polycarbonate type.
• the conformal deposition of the central layer 3, whether monolayer or formed by a stack of several layers, is preferably carried out, preferably under vacuum, by magnetic field assisted sputtering (so-called “cathodic magnetron sputtering").
• This technique makes it possible to deposit, on the textured surface 2B of the substrate 2, either the single layer conformably, or the different layers of the stack successively in a compliant manner.
• It may be in particular transparent thin films, preferably dielectric layers, in particular layers of Si 3 N 4 , SnO 2 , ZnO, ZrO 2 , SnZnO x , AlN, NbO, NbN, TiO 2 , SiO 2 , Al 2 0 3 , MgF 2 , AIF 3 , or thin metal layers, especially layers of silver, gold, titanium, niobium, silicon, aluminum, nickel-chromium alloy (NiCr), or alloys of these metals.
• dielectric layers in particular layers of Si 3 N 4 , SnO 2 , ZnO, ZrO 2 , SnZnO x , AlN, NbO, NbN, TiO 2 , SiO 2 , Al 2 0 3 , MgF 2 , AIF 3 , or thin metal layers, especially layers of silver, gold, titanium, niobium, silicon, aluminum, nickel-chromium alloy (NiCr), or alloys of these metal
• the second outer layer 4 of the layered element 1 can be formed by covering the central layer 3 with a layer transparent refractive index substantially equal to that of the substrate 2, a material that is initially in a viscous state, liquid or pasty suitable for shaping operations and is curable.
• This layer comes, in the viscous, liquid or pasty state, to marry the texture of the surface 3B of the central layer 3 opposite the substrate 2.
• the surface of contact If between the central layer 3 and the outer layer 4 is well textured and parallel to the contact surface S 0 between the central layer 3 and the outer layer 2.
• the transparent refractive index layer substantially equal to that of the substrate 2 may also be in the form of an enamel composition based on glass frit applied in the pasty state hardened by a firing step.
• the transparent refractive index layer substantially equal to that of the substrate 2 may also be in the form of a layer of transparent material, preferably dielectric, for example deposited by magnetron deposition, having undergone a step of polishing its surface external superior.
• the transparent refractive index layer substantially equal to that of the substrate 2 may also be in the form of a plastic interlayer.
• This layer undergoes a step of compression and / or heating at a temperature of at least the glass transition temperature of the polymer interlayer, for example in a press or an oven.
• the interlayer forming the upper layer of the textured layer element conforms to the texture and ensures that the contact surface Si between the central layer 3 and the outer layer 4 is well textured and parallel to the contact surface S 0 between the central layer 3 and the outer layer 2.
• the second outer layer 4 of the layered element 1 of FIG. 4 can thus notably be:
• a sol-gel layer in particular, a silica glass deposited by a sol-gel process on the textured surface of the central layer 3,
• the additional layer or layers are preferably a flat glass substrate, a plastic interlayer or an overlap of a spacer and a flat glass substrate.
• the outer layer of the layered element When the outer layer of the layered element has been obtained from a material initially in a viscous, liquid or pasty state, for example a sol-gel layer, it may exist on the smooth main outer surface of this layer some irregularities. In order to compensate for these irregularities, it may be advantageous to form on this sol-gel layer, an additional layer 12 by positioning a laminate interlayer PVB or EVA, against the smooth main outer surface of the layered element. In this case, the additional layer 12 has substantially the same refractive index as the outer layer of the layered element obtained from a material initially in a viscous, liquid or pasty state.
• the additional layer may also be a transparent substrate, for example a flat glass.
• the additional layer is used as a counter-substrate. The layer initially deposited in a viscous, liquid or pasty state then ensures a bonding between the lower outer layer provided with the central layer and the counter-substrate.
• a transparent substrate as an upper additional layer is particularly useful when the outer layer or the additional layer directly below said upper additional layer is formed by a polymeric lamination interlayer.
• the upper outer layer 4 may be formed by a lamination interlayer, for example made of PVB or EVA, positioned against the textured surface of the layer. central 3 opposite to the glass substrate.
• An additional layer 12 consisting of a flat glass substrate can overcome the spacer 4.
• the second outer layer 4 may also be formed by a layer initially deposited in a viscous, liquid or pasty state.
• a first additional layer 12 formed by a PVB or EVA lamination interlayer may be positioned against the outer top surface of the layered member and a second additional layer 12 of a flat glass substrate may overlie the liner.
• the outer layer and the additional layer or layers are associated with the glass substrate, previously coated with the central layer 3, by a conventional method of laminating.
• the polymeric lamination interlayer 3 or the upper outermost surface of the layered element is successively positioned from the textured main surface of the polymeric lamination interlayer and the substrate, and then applied to the structure. laminated thus formed a compression and / or heating, at least at the glass transition temperature of the polymeric lamination interlayer, for example in a press or an oven.
• the interlayer forms the top layer of the textured layer element, it conforms to the texture and ensures that the Si contact surface between the core layer 3 and the outer layer 4 is well textured and parallel to the contact surface S 0 between the central layer 3 and the outer layer 2.
• the insert forms the additional upper layer directly above the layered element whose upper layer is a sol-gel layer, it complies with both the upper surface of the sol-gel layer and the lower surface of the flat glass substrate.
• the support comprising the layered element 1 is a flexible film with a total thickness of the order of 200-300 ⁇ .
• the support is formed by the superposition:
• a second PET film having a thickness of 100 ⁇ so as to form the second outer layer 4 of the layered element 1.
• the flexible film forming the lower additional layer may be a film of polyethylene terephthalate (PET) having a thickness of 100 ⁇
• the outer layer 2 may be a layer of UV curable resin of the KZ6661 type marketed by the company JSR Corporation having a thickness of about 10 ⁇ .
• the flexible film and the layer 2 both have substantially the same refractive index, on the order of 1.65 to 550 nm. In the cured state, the resin layer has good adhesion with the PET.
• the resin layer 2 is applied to the flexible film with a viscosity allowing the introduction of a texturing on its surface 2B opposite to the film 12.
• the texturing of the surface 2B can be carried out at the same time. using a roller 13 having on its surface a texturing complementary to that to be formed on the layer 2.
• the flexible film and the resin layer 2 follows are irradiated with UV radiation, as shown by the arrow in Figure 5, which allows the solidification of the resin layer 2 with its texturing and the assembly between the flexible film and the resin layer 2.
• the central layer 3 of refractive index different from that of the outer layer 2 is then conformably deposited on the textured surface 2B by magnetron sputtering.
• This central layer may be monolayer or formed by a stack of layers, as described above. It may be for example a TiO 2 layer having a thickness of between 55 and 65 nm, or of the order of 60 nm and a refractive index of 2.45 at 550 nm.
• a second PET film having a thickness of 100 ⁇ is then deposited on the central layer 3 so as to form the second outer layer 4 of the layered element 1.
• This second outer layer 4 is shaped to the textured surface 3B of the central layer 3 opposite to the outer layer 2 by compression and / or heating at the glass transition temperature of the PET.
• the element layer 1 is thus in the form of a flexible film ready to be reported by gluing on a surface, such as a surface of an electrode or an organic electroluminescent diode.
• the various steps of the method can be carried out continuously on the same production line.
• an electrode may be placed on the smooth surfaces 2A or 4A of the outer layers or possibly on an additional upper or lower layer before or after the assembly of the layered element, depending on the nature of said layers.
• the thickness of each outer layer formed based on a polymer film may be greater than 10 ⁇ , in particular of the order of 10 ⁇ to 1 mm.
• the texturing of the first outer layer 2 in the example of FIG. 5 can be obtained without resorting to a layer of curable resin deposited on the polymer film, but directly by hot embossing a polymer film, in particular by rolling with a textured roll or pressing with a punch.
• a polymeric lamination interlayer may be interposed between the central layer 3 and the second polymer film. This spacer then forms the upper outer layer of the layered element and the second polymer film forms an additional upper layer.
• the lamination interlayer has substantially the same refractive index as the polymer films flanking it.
• it is a conventional method of lamination, in which is applied to the laminated structure compression and / or heating at least at the glass transition temperature of the polymeric lamination interlayer.
• An organic light emitting diode device generally finds its application in a display screen or in a lighting device.
• the rough transparent glass substrate SATINOVO® from the company Saint-Gobain used has a thickness of 0.7 mm and has on one of its main surfaces a texture obtained by etching.
• the average height of the patterns of the texturing of the lower outer layer, which corresponds to the roughness Ra of the textured surface of the Satinovo® glass, is between 1 and 3 ⁇ .
• Its refractive index is 1, 52 and its PV ("peak to valley") corresponding to the maximum gap between the hollows and the peaks is between 12 and 17 ⁇ .
• the additional layers comprise a Planilux® flat glass sold by Saint-Gobain and have a thickness of 0.7 mm.
• the glass SF66 referenced by the company Schott has a refractive index of 1.92. When used as a lower outer layer, it is textured by sanding.
• the NOA75® resin layer from NorlandOptics has a refractive index of 1. 52 and a thickness of 100 ⁇ . This resin is deposited in the liquid state on the textured surface of the central layer opposite the lower outer layer so that it conforms to the texture of the surface and is cured by UV radiation.
• the other core layers were sputtered magnetron sputtering onto the textured surface of the lower outer layer.
• the TiO 2 layer was deposited on a thickness of 60 nm with the following deposition conditions: TiO 2 target, deposition pressure of 2 * 10 -3 mbar, gas consisting of a mixture of argon and oxygen
• the silver layer was deposited to a thickness of 20 nm.
• the upper outer layer consisting of a SnZnO layer is deposited by magnetron.
• the magnetron deposition being in conformity, it is followed by a polishing step in order to obtain a sufficiently smooth outer surface.
• the enamel layer has a high refractive index of 1, 9 and is obtained by depositing on a soda-lime glass substrate a high index glass enamel comprising the following composition, where the values represent percentages by weight:
• the photopolymerizable material is applied to the Satinovo® glass covered with a layer of Ti0 2 . Then, a flat glass is superimposed. The assembly is irradiated with UV so as to polymerize the photopolymerizable material which then allows the joining of all the elements constituting the support.
• the upper outer layer is a transparent layer or a magnetron-deposited SnZnO overcoating layer having an index close to the lower outer layer. This layer could also have been a layer having a suitable refractive index selected from Si 3 N 4 , ZnO or MoO 3 .
• This layer is then polished so as to have a smooth outer main surface.
• the central layer comprises a silver metal layer. This layer could also have been made of gold or copper. This metal layer can then be one of the electrodes of the OLED device.
• the assembly consisting of the central layer and the upper outer layer is preferably the lower electrode of the OLED.
• the light-emitting diodes used are OLEDs providing Lumiblade® white light marketed by Philips in 2012.
• diodes are fixed on the supports 1 to 3 by bonding with dimethyl phthalate marketed by Mercket thus forms the diode devices according to the invention 1 to 3.
• optical properties of the OLED device of the invention comprising the support I hereinafter device (A) were compared to:
• device (B) a device comprising an OLED diode fixed on the smooth side to a 0.7 mm Satinovo®-type glass corresponding to a rough substrate, hereinafter device (B),
• device (C) a device comprising an OLED diode fixed on a 0.7 mm flat glass provided with a scattering layer which is a bismuth frit with 30% alumina particles, hereinafter device (C).
• the table also gives the values of the colorimetric variation Vc as a function of the observation angle, ie the length of the path (of various shapes, such as a line or an arc of a circle), in the colorimetric diagram.
• CIE XYZ 1931 between the spectrum emitted at 0 ° and the spectrum emitted at 75 °, this every 5 °.
• the colorimetric coordinates for each angle spectrum ⁇ are expressed by the pair of coordinates (x (9i); y (9i)) in the CIE XYZ 1931 colorimetric diagram.
• the length of the path Vc1 for the device according to the invention can therefore be calculated using the following known formula:
• the length of the path should be as short as possible to minimize the angle dependence of the color of the OLED.
• the colorimetric variation Vc makes it possible to assess the angular dependence of the color once the OLED has been achieved.
• the device of the invention makes it possible to obtain the best compromise between a good light transmission, a minimum blur, a gain in extraction and a decrease in colorimetric variations in angle.
• the colorimetric variations obtained are shown in FIG. 6.
• the device of the invention makes it possible to obtain at the same time a gain in extraction, a decrease of the colorimetric variations in angle while maintaining a strong transparency (haze lower than 4%).

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• Chemical & Material Sciences (AREA)
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• Electroluminescent Light Sources (AREA)
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• 2012
  • 2012-05-25 FR FR1254868A patent/FR2991101B1/fr not_active Expired - Fee Related
• 2013
  • 2013-05-23 US US14/403,406 patent/US20150171370A1/en not_active Abandoned
  • 2013-05-23 CN CN201380026968.5A patent/CN104303329A/zh active Pending
  • 2013-05-23 EP EP13729401.3A patent/EP2856533A1/de not_active Withdrawn
  • 2013-05-23 WO PCT/FR2013/051123 patent/WO2013175130A1/fr active Application Filing
  • 2013-05-23 JP JP2015513248A patent/JP2015517726A/ja active Pending
  • 2013-05-23 RU RU2014152718A patent/RU2014152718A/ru not_active Application Discontinuation
  • 2013-05-23 KR KR20147032544A patent/KR20150024816A/ko not_active Application Discontinuation
• 2015
  • 2015-03-16 HK HK15102615.4A patent/HK1202186A1/xx unknown

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