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
  • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
• • 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
  • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
• • 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
• • 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
  • C03C17/3602—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 the metal being present as a layer
  • C03C17/3607—Coatings of the type glass/inorganic compound/metal
• • 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
  • C03C17/3602—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 the metal being present as a layer
  • C03C17/3642—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 the metal being present as a layer the multilayer coating containing a metal layer
• • 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
  • C03C17/3602—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 the metal being present as a layer
  • C03C17/3668—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 the metal being present as a layer the multilayer coating having electrical properties
  • C03C17/3671—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 the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/77—Coatings having a rough surface
• • 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.]
  • Y10T428/24446—Wrinkled, creased, crinkled or creped

Definitions

• the invention relates to a method for producing a textured surface structure provided with a transparent inorganic glass substrate supporting an organic light-emitting diode device and such a structure.
• An OLED for "Organic Light Emitting Diodes” in English comprises a material or a stack of organic electroluminescent materials, and is framed by two electrodes, one of the electrodes, generally the anode, being constituted by that associated with the glass substrate and the Another electrode, the cathode, being arranged on the organic materials opposite 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.
• the emitted photons pass through the transparent anode and the glass substrate supporting the OLED to provide light outside the device.
• An OLED usually finds its application in a display screen or more recently in a lighting device, but with different constraints.
• the light extracted from the OLED is a "white” light emitting in some or all wavelengths of the visible spectrum. It must be so in a homogeneous way.
• Lambertian emission that is to say obeying Lambert's law, being characterized by a photometric luminance equal in all directions.
• an OLED has a low light extraction efficiency: the ratio between the light that actually leaves the glass substrate and that emitted by the electroluminescent materials is relatively low, of the order of 0.25.
• Document US 2004/0227462 shows a diffractive optical solution for which the transparent substrate of the OLED, support of the anode and of the organic layer, is texture.
• the surface of the substrate thus has an alternation of excrescences and recesses whose profile is followed by the anode and the organic layer deposited on it.
• the profile of the substrate is obtained by applying a photoresist mask on the surface of the substrate whose pattern corresponds to the desired one of the growths, then etching the surface through the mask.
• a photoresist mask on the surface of the substrate whose pattern corresponds to the desired one of the growths
• the invention therefore proposes a method of manufacturing a substrate, in particular for polychromatic (white) OLED, providing both an extraction gain, a sufficiently homogeneous white light and increased reliability.
• the invention therefore relates to a method for obtaining a textured surface structure constituting the support of an organic light-emitting diode device, the structure being provided with a transparent mineral glass substrate coated with a possible layer of light-emitting diode. mineral glass interface, the texturing profile being formed of protuberances and troughs, the method comprising, to form the textured surface,
• a coating layer preferably an essentially inorganic layer, on one of the main faces of the substrate, preferably substantially all over the surface, or respectively on said optional interface layer, the coating layer being thickness less than or equal to 300 nm, preferably less than or equal to 100 nm, even less than or equal to 50 nm, and at least 10 times thinner, preferably at least 100 times, than the substrate or said interface layer respectively,
• ⁇ l - ⁇ 2 ( ⁇ l - ⁇ 2) (ri-7g) in which ⁇ 1 is the average linear thermal expansion coefficient of the glass above Tg and ⁇ 2 is the average linear thermal expansion coefficient of the coating layer above Tg, is at least 0.1%, preferably greater than 0.3% or even greater than or equal to 0.55%.
• the network of the prior art optimizes the extraction gain around a certain wavelength but on the other hand does not promote a white light emission, on the contrary, it tends to select certain lengths of light. wave and will emit for example more in blue or red.
• the texturing profile obtained by the method of the invention provides protrusions whose characteristic dimensions in terms of period and depth are in particular adapted to the light extraction of an OLED.
• too sharp excrescences at too sharp angles could generate an electrical contact between the anode and the cathode, thus deteriorating the OLED,
• the well-known roughness parameter Rdq indicating the average slope, and setting a maximum value, and possibly the well-known roughness parameter Rmax indicating the maximum height, and setting a possibly accumulated maximum value to a minimum value to favor extraction
• the contraction is such that the textured surface of the structure is defined by a roughness parameter Rdq of less than 1, 5 °, preferably less than 1 °, or even less than or equal to 0, 7 °, and preferably a roughness parameter Rmax greater than or equal to 20 nm, and possibly less than 100 nm, on an analysis surface of 5 ⁇ m by 5 ⁇ m, for example with 512 measurement points.
• a roughness parameter Rdq of less than 1, 5 °, preferably less than 1 °, or even less than or equal to 0, 7 °
• Rmax greater than or equal to 20 nm, and possibly less than 100 nm, on an analysis surface of 5 ⁇ m by 5 ⁇ m, for example with 512 measurement points.
• the analysis surface is suitably selected according to the roughness to be measured.
• the roughness parameters of the surface are preferably measured by atomic force microscopy (AFM).
• the method can also ensure that the structure is such that at any point of its textured surface, the angle formed by the tangent at any point of the profile relative to the normal to the substrate is greater than 30 °, preferably 45 ° .
• a texturing typically a pleating of a glass-base structure is provided in a simple way, and potentially over large areas.
• the temperature rise results from the heating of the substrate for the deposition of the coating layer.
• the temperature rise is subsequent to the deposition of the coating layer, and carried out by heating at said heating temperature T1, and the method then comprises removing the coating layer.
• the temperature rise up to the heating temperature T1 is at least 100 ° C., preferably at least 300 ° C., greater than the glass transition temperature Tg.
• the glass frit interface layer with a glass transition temperature Tg 'lower than that of the substrate Tg is preferably deposited by screen printing; this interface layer is in particular a glass frit with a glass transition temperature Tg 'less than or equal to 500 ° C.
• the coating layer is deposited at the heating temperature by CVD on the laminated glass line substrate, after the rolling operation, or on a float process line, or by taking up the glass.
• the coating layer is magnetically deposited on the substrate.
• the cooling is carried out at ambient temperature, in a re-cooking arch or under the conditions of a thermal quenching.
• the coating layer in particular metal, is removed by differential etching between the layer and the substrate or the optional interface layer.
• the process thus provides a contraction that forms an isotropic texturing.
• it forms an anisotropic texturing, by applying unidirectional traction simultaneously with cooling.
• the subject of the invention is also a textured surface structure constituting the support of an organic light-emitting diode device, the structure being provided with a transparent inorganic glass substrate on which an inorganic glass interface layer is optionally deposited.
• the texturing profile of the surface being formed of excrescences and depressions and obtainable by the method defined above.
• the growths of such a profile are predominantly (or at least 70% and even 80% or more) in the form of folds (preferably with substantially rounded tops), which are
• a pitch or pseudo period (that is to say with at least three repetitions of folds of substantially the same height and the same width in a given direction) ranging from 200 nm to 4 ⁇ m, preferably from 300 nm to 2 ⁇ m and even more preferably ranging from 400 nm to 700 nm, preferably a maximum number of folds in the same given direction less than 100 times the largest pseudo period, preferably less than 50 times, even more preferably less than 20. times,
• the texturing (which may be referred to herein as pleating) of the invention may furthermore be defined by its Fourier transform.
• the invention thus relates to a textured surface structure constituting the support of an organic light-emitting diode device, structure provided with a transparent mineral glass substrate on which is optionally deposited a mineral glass interface layer, the profile texturing of the surface being formed of excrescences and recesses and obtainable by the method defined above.
• a random texture does not show a peak in the TF, but the TF has a decreasing pitch with k.
• the signature of the texturations according to the invention is therefore the following: the presence of a (pseudo) period, the TF remains rather flat when k increases to decrease abruptly for even higher k's , and preferably the TF passes through a maximum to decrease abruptly for even higher k's.
• This texturing is suitable for the OLED because it presents a minimum of useless frequencies. Usually in a random texture, the TF decreases slowly.
• the invention also also relates to a textured surface structure constituting the support of an organic light-emitting diode device, structure provided with a transparent mineral glass substrate on which is optionally deposited a mineral glass interface layer , the texturing profile of the surface being formed of excrescences and depressions and obtainable by the method defined above.
• the structure obtained by the method of the invention provides a pleating extending in a multitude of directions parallel to the surface of the substrate. This multidirectional arrangement defines the isotropic nature of the structure. The structure then has a percentage of isotropy.
• the profile of the texturing of the invention is preferably similar to a "quasi-periodic" curve. This profile is adapted by the thickness of the coating layer, and its nature and by the method of manufacturing the texturing proposed by the invention.
• the pitch separating two protuberances is quasi-periodic of the order of the wavelength of light, between 200 nm and 2 ⁇ m, preferably between 300 nm and 1 ⁇ m, and in particular between 400 nm. and 700 nm for visible light.
• a certain width of wavelength is obtained around this periodicity to thus have a wider band behavior. This is what is meant by "quasi-periodic" profile. This profile will be detailed further by its characterization according to the Fourier transform.
• the texturing of the structure, the way in which this profile is obtained, the nature of the coating layer are characteristics which, combined, further optimize the light extraction and the homogenization of this light.
• the textured surface of the structure is defined by a majority of points whose tangent to the normal to the opposite face of the textured face is at an angle greater than or equal to 45 °, and / or defined by a roughness parameter Rdq less than 1, 5 °, preferably less than 1 °, or even less than or equal to 0.7 °, and preferably a roughness parameter Rmax greater than or equal to 20 nm, and possibly less than 100; nm, on an analysis surface of 5 ⁇ m by 5 ⁇ m, for example with 512 measurement points.
• the coating layer may preferably be:
• Essentially mineral especially for good thermal behavior, and / or dielectric (in the non-metallic sense), preferably electrically insulating (in general, having a bulk electrical resistivity, as known in the literature, greater than 10 9 ⁇ .cm), or semiconductor (in general of bulk electrical resistivity, as known in the literature, greater than 10 -3 ⁇ .cm and less than 10 9 ⁇ .cm), and and / or does not significantly alter the transparency of the substrate, for example the substrate coated with this layer may have a light transmission T L greater than or equal to 70%, or even 80%.
• the coating layer is dielectric, in particular a refractory ceramic, particularly Si ⁇ lSU, SiC> 2, TiC> 2, ZnO, SnO 2 or SnZnO.
• the dielectric layer has an index greater than or equal to 1.8, and preferably less than or equal to 2.
• a refractory and / or noble metal coating layer such as Zr, Ti, Mo, Nb, W, Si, Al, Au , Pt and their alloys, is also interesting, especially in the case where it is desired to remove the coating layer, because such a layer is generally easier to remove from the surface of the glasses, a ceramic layer.
• the interface layer is a layer obtained from molten glass frit, preferably having a glass transition temperature Tg 'less than or equal to 600 ° C., or even lower than or equal to 500 ° C.
• the invention finally relates to an organic electroluminescent diode device incorporating the structure defined above or obtained by the method of the invention.
• the device also comprises a first transparent electro-conductive coating, forming a first (lower) electrode and deposited on the textured face of the structure, an OLED system based on layer (s) of organic material (s) deposited ( s) on the first electrode, and a second electroconductive coating which forms a second (upper) electrode and is deposited on the OLED system.
• the first electroconductive coating has a surface substantially conforming to the surface of the structure and has an optical index greater than or equal to that of the coating layer.
• the OLED can form a lighting panel, or backlight (substantially white and / or uniform) including surface (full) electrode greater than or equal to 1x1 cm 2 , or even up to 5x5 cm 2 even 10x10 cm 2 and beyond.
• the OLED can be designed to form a single illuminating pad (with a single electrode surface) in polychromatic light (substantially white) or a multitude of illuminating patches (with multiple electrode surfaces) in polychromatic light (substantially white ), each illuminating pad having a (full) electrode surface greater than or equal to 1x1 cm 2 , or even 5x5 cm 2 , 10x10 cm 2 and beyond.
• an OLED especially for lighting, one can choose a non-pixelated electrode. It is distinguished from a display screen electrode (“LCD” ”) formed of three juxtaposed pixels, generally of very small dimensions, and each emitting a given quasi-monochromatic radiation (typically red, green or blue).
• LCD display screen electrode
• the OLED system may be designed to emit a polychromatic radiation defined at 0 ° by coordinates (x1, y1) in the CIE XYZ 1931 colorimetric diagram, thus given coordinates for radiation to normal.
• the OLED can be emission from the bottom and possibly also from the top depending on whether the upper electrode is reflective or semi-reflective, or even transparent (in particular TL comparable to the anode, typically from 60% and preferably greater than or equal to 80%).
• the OLED system can be adapted to emit (substantially) white light, as close as possible to the coordinates (0.33, 0.33) or coordinates (0.45, 0.41), especially at 0 °.
• mixture of compounds green red emission, blue
• stack on the face of the electrodes of three organic structures green red emission, blue
• two organic structures yellow and blue
• the OLED can be adapted to output (substantially) white light, as close as possible to coordinates (0.33, 0.33), or coordinates (0.45, 0.41), especially at 0 ° .
• the device can be part of a multiple glazing, including a vacuum glazing or with air knife or other gas.
• the device can also be monolithic, include a monolithic glazing to gain compactness and / or lightness.
• the OLED may be glued or preferably laminated with another flat substrate said cover, preferably transparent such as a glass, using a lamination interlayer, especially extra-clear.
• the invention also relates to the various applications that can be found in these OLEDs, forming one or more transparent and / or reflecting luminous surfaces (mirror function) arranged both outside and inside.
• the device can form (alternative or cumulative choice) an illuminating, decorative, architectural system, etc.), a signaling display panel - for example of the type drawing, logo, alphanumeric signaling, including an emergency exit sign.
• OLED can be arranged to produce a uniform polychromatic light, especially for homogeneous illumination, or to produce different light areas of the same intensity or distinct intensity.
• an illuminating window can in particular be produced. Improved lighting of the room is not achieved at the expense of light transmission. By also limiting the light reflection, especially on the outside of the illuminating window, this also makes it possible to control the level of reflection, for example to comply with the anti-glare standards in force for the facades of buildings.
• the device in particular transparent part (s) or entirely, may be: intended for the building, such as an external light glazing, an internal light partition or a (part of) light glass door including sliding, for a transport vehicle, such as a bright roof, a (part of) side window light, an internal light partition of a land vehicle, aquatic or aerial (car, truck train, plane, boat, etc.), for furniture urban or professional such as a bus shelter panel, a wall of a display, a jewelery or showcase display, a wall of a greenhouse, an illuminating slab, intended for interior furnishing, a shelf or furniture element, a cabinet facade, an illuminating slab, a ceiling lamp, a refrigerator lighting shelf, an aquarium wall, for the backlighting of electronic equipment, in particular visualization or display, possibly double screen, like a TV or computer screen, a touch screen.
• OLEDs are generally dissociated into two major families depending on the organic material used.
• SM-OLED Small Molecule Organic Light Emitting Diodes
• HIL hole injection layers
• HTL hole transport layer
• ETL electron transport layer
• Electron Transporting Layer in English.
• Examples of organic electroluminescent stacks are for example described in the document entitled “oven wavelength white organic light emitting diodes using 4, 4'-bis [carbazoyl- (9)] - stilbene as a deep blue emissive layer” of CH. Jeong et al., Published in Organics Electronics 8 (2007) pages 683-689.
• organic electroluminescent layers are polymers, it is called PLED ("Polymer Light Emitting Diodes" in English).
• Figure 1 is a schematic sectional view of a textured structure according to the invention.
• Figure 2 is a variant of Figure 1;
• Figure 3a shows an optical microscope view of the textured surface of the structure in a first embodiment of the invention
• Figure 3b shows the Fourier transform of the view of Figure 3a
• Figure 3c illustrates the profile of the Fourier transform of the view of Figure 3b
• Figure 4a shows an optical microscope view of the textured surface of the structure in a second embodiment of the invention
• FIG. 4b represents the Fourier transform of the view of FIG. 4a;
• Figure 4c illustrates the profile of the Fourier transform of the view of Figure 4b
• Figure 5a is an anisotropically and quasi-periodically texturing scanning electron microscope view of the structure in a third embodiment of the invention
• FIG. 5b represents the Fourier transform of the view of FIG. 5a;
• FIG. 6 is an optical microscope view of an example of texturing with an interface layer that does not fall within the scope of the invention nor is it part of the state of the art;
• FIG. 7 is a schematic sectional view of an OLED according to the invention.
• FIG. 1 illustrates a textured structure 1 according to the invention, preferably isotropic and quasi-periodic. It has on one of its principal faces 1 a texturing which is intended, when photons strike this textured face and are led to cross said structure, to generate less light reflection to optimize ultimately gain in extraction, and to obtain a white light by minimizing its extraction over too narrow wavelength ranges, as well as the most homogeneous light possible, in particular in space.
• the structure 1 comprises once made by the method of the invention, a transparent mineral glass substrate 10, optionally a transparent coating layer 11, which is a layer of suitable properties (described later in support of the examples), and potentially in a variant, a transparent mineral glass interface layer 2 disposed between the coating layer and the substrate (FIG. 2).
• the substrate 10 is made of mineral glass with a thickness of between 0.7 mm and 3 mm. It has a first main face 12 and a second opposite main face 13 which is coated on its entire surface, the coating layer 11 when it has not been removed after obtaining pleating, or the layer of interface 2 in the variant embodiment.
• Structure 1 is textured on its face 1a so that it comprises a multitude of excrescences 14 forming an alternation of recesses 15.
• the structure 1 comprises only the coating layer 11, the texturing being reproduced in the thickness of the coating layer as well as on a certain depth of the glass substrate.
• the second face 13 of the glass substrate is not flat and has a profile which is identical to that of the coating layer 1 1, one and the other marrying.
• the thickness of the coating layer 11 is uniform over the entire surface and is at least 5 nm. To obtain the desired structure, the thickness depends on the nature of the layer and also on the rate of contraction imposed on the hot glass or on the viscous interface layer 2 between the glass and the coating layer 11.
• the textured surface is defined by a roughness parameter Rdq of less than 1.5 ° and preferably a roughness parameter Rmax less than or equal to 100 nm on an analysis surface of 5 ⁇ m by 5 ⁇ m. preferably by AFM.
• the tangent may also form in a majority of points of the textured surface with the normal to the opposite planar face, an angle greater than or equal to 30 °, and preferably at least 45 °.
• the heating temperature for the contraction according to the process of the invention is at least 100 ° C. to 300 ° C. higher than the glass transition temperature of the glass, a temperature corresponding to a sufficiently low viscosity for the substrate or for the interface layer of mineral glass.
• Preferred examples of material for the coating layer 11 are Si 3 N 4 or SiO 2 .
• the face 13 of the glass substrate and the coating layer 1 1 which are intimately secured to one another, thus constitute a unitary assembly with identical profile.
• the face 13 of the glass substrate remains flat, the texturing obtained thanks to the coating layer 11, as will be seen later by the description of the manufacturing process, is carried out on the coating layer.
• the profile obtained by contraction of the interface layer 2 is thus formed along the entire thickness of the coating layer 11 and the entire thickness of said interface layer.
• the face 13 of the substrate thus has a textured surface.
• the texturing profile is adapted by the thickness of the coating layer 11, its nature and the method of manufacturing the texturing proposed by the invention.
• Figure 3a shows an optical microscope image of a textured surface in a first embodiment of the invention.
• a silicosodocalcic glass substrate with a thickness of the order of one millimeter, a glass transition temperature equal to T 9 at 550 ° C., and an average linear thermal expansion coefficient in the region of 10 -6 6 K were chosen for higher temperatures. at 550 ° C (Tg).
• the heating temperature T1 for contraction of the substrate by cooling is chosen to be equal to 750 ° C.
• the coating layer is vacuum magnetron deposited on the unheated glass substrate.
• This layer consists of ZnO, with a thickness equal to 50 nm and an average linear thermal expansion coefficient of around 60 10 -7 / K for temperatures above 550 ° C. (Tg)
• Figure 3b corresponds to the Fourier transform (TF) of the image shown in Figure 3a.
• the Fourier transform indicates that pleating is practically isotropic.
• the TF does not have a perfect rotation symmetry, which means that the texturing is slightly oriented.
• Figure 3c illustrates the profile of the Fourier transform of the view of Figure 3b.
• the ratio: TF module (k ') / TF module (k' / 2) 1
• the ratio: TF module (k ') / TF module (1, 5k') 4
• the percentage isotropy is of the order of 80%. The percentage of isotropy is evaluated as described above in the preamble of the description.
• Figure 4a shows an optical microscope image of a textured surface in a second embodiment of the invention.
• An aluminosilicate glass substrate having a thickness of about 1 mm, a glass transition temperature Tg equal to 690 ° C., and an average linear thermal expansion coefficient in the region of 10 -6 / 6 K were chosen for temperatures greater than 690 0 C (Tg).
• the heating temperature T1 for contraction of the substrate by cooling is chosen equal to 900 ° C.
• the coating layer is vacuum magnetron deposited on the substrate which is unheated. It consists of SiO 2 with a thickness equal to 50 nm and a coefficient of linear thermal expansion neighbor medium May 10 "7 / K, for temperatures above 690 0 C (Tg).
• the difference between the free thermal contraction ⁇ l of the glass and the free thermal contraction of the coating layer ⁇ 2, from the heating temperature T1 to the glass transition temperature Tg is therefore 0.62%.
• the submicron excrescences are mainly in the form of folds which are:
• Figure 4b corresponds to the Fourier transform of the image shown in Figure 4a.
• the Fourier transform indicates that the pleating is practically isotropic.
• the TF has a ring around the center, a signature that a specific step is present in the texturing.
• the maximum of the TF is for values of the order of 4.2 ⁇ m -1 .
• the TF does not have a perfect symmetry of rotation, which means that the texturing of Figure 4a is slightly oriented.
• the decay of the TF is quite steep for higher values of the vector k.
• the value is almost zero at 9 ⁇ m "1 .
• the inventors have demonstrated that not only should there be sufficient isotropy of the profile but also preferably a quasi-periodicity of the profile.
• modulus of the TF (k ') / modulus of the TF (k' / 2) is 3.5.
• the ratio: TF module (k ') / TF module (1.5k') is 3.5.
• the curve of FIG. 4c also has a peak with a substantially Gaussian appearance.
• the deviation of this peak from the origin 0 of the graph corresponds to the average period, that is to say, the average step between two adjacent excrescences 14.
• is, according to the invention, between 100 nm and 2 ⁇ m.
• Texturing with such a profile thus covers the visible spectrum, ensuring that white light is extracted, and not light reduced to a restricted range of wavelength corresponding, for example, to a given color of the spectrum.
• the percentage of isotropy is of the order of 75%.
• Figure 5a is a scanning electron microscope view of anisotropic pleating, oriented substantially in the same direction in a third embodiment of the invention. It was obtained by adding anisotropic deformation to the glass substrate during the manufacturing process by a vertical pull of the still hot structure.
• a silicosodocalcic glass substrate having a thickness of the order of one millimeter, a glass transition temperature Tg equal to 550 ° C., and an average linear thermal expansion coefficient of approximately 30 ⁇ 10 -6 / K were chosen for temperatures greater than 550 0 C (Tg).
• the coating layer is formed of SnO 2 and deposited by CVD on an already hot substrate at a temperature of 800 ° C. (heating temperature T1 for contraction of the substrate by cooling). Its thickness is 15 nm and its coefficient of linear thermal expansion is close to 4.5 10 "6 / K for temperatures above 550 ° C (Tg) The difference between the free thermal contraction ⁇ l of the glass and the free thermal contraction of the coating layer ⁇ 2, from the heating temperature T1 to the glass transition temperature Tg is therefore approximately 0.635%.
• the submicron excrescences are mainly in the form of folds which are:
• Figure 5b corresponds to the Fourier transform of the image shown in Figure 5a. Anisotropy is clearly visible.
• the decay of the TF is quite steep for higher values of the vector k.
• the value is almost zero at 10 ⁇ m "1 .
• modulus of the TF (k ') / modulus of the TF (k' / 2) is 4.
• modulus of TF (k ') / modulus of TF (1.5k') is 10;
• Figure 6 is an optical microscope view of anisotropic pleating obtained on a substrate coated with an interface layer.
• the process which led to the appearance of the plies is as follows: hot CVD deposition of a 100 nm layer of SnO 2 on a soda-lime glass coated with a 10 ⁇ m thick glass frit layer, that is to say, too thick to lead to the texturations according to the invention.
• the glass frit has a glass transition temperature Tg 'of 400 ° C. and the deposition is carried out at 600 ° C.
• a texture is visualized which has a typical very high pitch of the order of 20 ⁇ m relative to the desired pitch for the application.
• the texture is also oriented.
• the textured structure of the invention is more particularly adapted to its incorporation in an OLED, as schematically represented in FIG. 7.
• OLED 3 comprises the textured structure 1, a first transparent electroconductive coating 30 which forms an electrode and which is arranged on the textured face 1a of the structure provided with the coating layer 11, a layer 31 of material (x ) organic (s), and a second electroconductive coating 32 which forms a second electrode and preferably has a (semi) reflecting surface facing the organic layer 31 for returning the light emitted by the organic layer to the opposite direction , that of the transparent substrate.
• the texturing provides indeed for the OLED a significant gain in light extraction and an increase in the diffraction of photons which ensures in the thickness of the substrate 10 a recombination of the different wavelength colors to provide a homogeneous white light and isotropic.
• the textured structure with preferably the isotropic and quasi-periodic profile of the invention is obtained by the manufacturing method of the invention which consists in: depositing on a flat mineral glass substrate a suitable coating layer 1 1, heat-treating the substrate covered with the layer so as to obtain a pleating of the surface structure after cooling, optionally after obtaining pleating, removing the coating layer 1 1.
• the materials Si 3 N 4 SiO 2 , TiO 2 , SnO 2 , or ZnO are particularly suitable for forming the coating layer. If 3 N 4 will be preferred for a light emitting device of the OLED type, because it may advantageously directly form the first layer of the multi-layer electrode 30 of the OLED.
• the deposition of the layer 11 is carried out on a glass substrate 10 which is (unheated), and the heat treatment consists in heating the coated substrate and then cooling it.
• the deposition of the layer on cold substrate is preferably magnetron.
• the heating of the coated substrate is carried out at a temperature T1 of at least 100 ° C. (preferably 300 ° C.) higher than the glass transition temperature Tg of the glass.
• T1 a temperature of at least 100 ° C. (preferably 300 ° C.) higher than the glass transition temperature Tg of the glass.
• the deposition of the layer 11 is performed on a glass substrate 10 which is hot, and the heat treatment consists in cooling the coated substrate.
• the glass substrate Before depositing the layer, the glass substrate is heated to a temperature of at least 100 ° C. (preferably 300 ° C.) higher than the glass transition temperature.
• the substrate is already hot, at a certain temperature T1 of at least 100 ° C (preferably 300 ° C) higher than the glass transition temperature Tg of the glass, because the deposition of the layer 11 is made directly on a rolled glass line, after the rolling operation or on a float process line, in the float enclosure or on uncoated glass reheated after its manufacture.
• the deposition of the layer on a hot substrate is preferably by CVD vapor deposition (Chemical Vapor Deposition).
• the cooling of the coated substrate is a natural cooling at ambient temperature, or that of quenching or thermal curing.
• the first embodiment of deposition of the cold layer it is possible to first deposit a layer of interface glass 2 whose glass transition temperature Tg 'is at a lower temperature than that of the substrate. glass for example of at least 100 ° C.
• glass frit whose glass transition temperature Tg 'is at 400 ° C., for example with a high alkali content and / or boron or even bismuth, is deposited by screen printing.
• the coating layer 11 is then deposited by magnetron, and the entire substrate and layers is heated to a temperature above 550 ° C.
• the cooling of the assembly is advantageously made by thermal quenching.
• the second embodiment in order to avoid having to deposit the layer at a very high temperature and sometimes difficult to reach industrially, it is advantageous as already expressed to coat the surface of a glass with such interface layer 2 having a glass transition less than that of the glass substrate, for example glass frit and heating the layer during the deposition of the coating layer. Indeed, it is generally easier to have a glass frit with a low glass transition than a glass (float) with a low glass transition temperature.
• This contraction process which gives the structure a texture profile with growths suitable slopes for an OLED is thus easy to implement and can be applied to large glass surfaces.

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