Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
  • C03C17/23—Oxides
  • C03C17/25—Oxides by deposition from the liquid phase
• • 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
  • C03C17/3668—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
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/81—Anodes
  • H10K50/816—Multilayers, e.g. transparent multilayers
• • 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
  • H10K50/85—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
  • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
  • H10K77/10—Substrates, e.g. flexible substrates
• • 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
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer
  • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
  • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
  • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
  • C03C2217/475—Inorganic materials
  • C03C2217/478—Silica
• • 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
  • Y10T428/19—Sheets or webs edge spliced or joined
  • Y10T428/192—Sheets or webs coplanar
• • 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.]
• • 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.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31656—With metal layer

Definitions

• the invention relates to a method for producing a textured surface structure comprising a surface-textured mineral glass substrate for 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, 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.
• US 2004/0227462 shows for this purpose an OLED whose transparent support substrate of the anode and the organic layer is textured.
• 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 object of the invention is therefore to propose a method for manufacturing a polychromatic (white) OLED support, which allows both a gain in light extraction from the OLED, a sufficiently homogeneous white light and increased reliability.
• the method of manufacturing a textured surface structure comprising a mineral glass substrate having a given texturing, for organic light-emitting diode device, the method comprising: - the supply of a rough substrate, of defined roughness by a roughness parameter Ra ranging from 1 to 5 ⁇ m, preferably ranging from 1 to 3 ⁇ m, over an analysis length of 15 mm, and with a Gaussian filter with a cut-off frequency of 0.8 mm,
• the method incorporates a roughness control step.
• the choice of a rough glass according to the invention provides a random texturing (preserved even after smoothing) to obtain a gain in extraction for a wide band of wavelengths (no visible colorimetric effect), and an angular distribution of the almost lambertian light emitted.
• 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 some wavelengths and will emit for example more in blue or red.
• the roughness of the substrate is characterized by the well-known roughness parameter Ra which is the arithmetic average deviation of the profile, reflecting the average amplitude.
• the well-known roughness parameter RSm which is the mean value of the widths of the elements of the profile.
• the parameter RSm may thus range from 40 ⁇ m to 100 ⁇ m, even more preferably from 45 to 65 ⁇ m, over the analysis length of 15 mm, and with a Gaussian filter with a cut-off frequency of 0.8 mm.
• the analysis length is thus suitably chosen depending on the roughness to be measured.
• the Gaussian cutoff filter serves to eliminate wavelengths in roughness ranges that are irrelevant for defining the roughness suitable for the invention.
• the roughness parameters of the rough surface of the glass can be measured in different ways:
• the height of the roughness peaks is micron, and the surface is uneven.
• the height of the texturing is submicron (nanometric), with a rounded, undulating surface.
• a dual roughness criterion with:
• the well-known roughness parameter Rdq indicating the average slope, and setting a maximum value
• the well-known roughness parameter Rmax indicating the maximum height, and setting a maximum value, possibly cumulated at a minimum value to favor extraction.
• 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 a roughness parameter Rmax less than 250 nm, preferably less than or equal to 200 nm, over an analysis length of 180 ⁇ m, and with a Gaussian filter with a cut-off frequency of 25 ⁇ m.
• the roughness parameters of the textured surface can be measured in different ways, for example by optical interferometry, for example using the NEWVIEW device from ZIGO,
• Another method for defining the softening of the textured surface by the smoothing layer is to say that the angle formed by the tangent to the normal to the substrate is greater than or equal to 30 °, and preferably at least 45 °, for the majority of the given points of this surface.
• RMS parameter for "Root Mean Square” (or Rq) that is to say the mean square deviation of the roughness, thus quantifying on average the height of the peaks and troughs of roughness, compared to the average height.
• an RMS of less than 550 nm or even less than or equal to 500 nm can be chosen over an analysis length of 180 ⁇ m and with a Gaussian filter with a cut-off frequency of 25 ⁇ m.
• at least 50%, even 70% and even 80%, of the rough surface of the substrate which is to be covered by the active layer (s) of the OLED (to form one or several zones of light) has submicron texturing and sufficiently softened (typically rounded, wavy) by the smoothing layer according to the invention above.
• N of active light-emitting area (s) of an OLED preferably at least 70%, or even at least 80%, of the N active area (s).
• N active area (s) comprises (s) a softened textured surface according to the invention.
• the smoothing layer substantially covers the rough surface.
• the substrate can be rough substantially over the entire main face in play.
• the liquid channel is preferred to a physical deposition path, such as by a physical vapor deposition under vacuum, called in English "PVD" for Physical Vapor Deposition), because it ensures a profile that is not precisely consistent with the rugged terrain of the rough substrate, and thus allows to sufficiently soften the roughness appropriately.
• PVD physical vapor deposition under vacuum
• the deposition technique for the formation of the chosen sol-gel layer-type smoothing layer comprising the deposition of at least one sol and obtained by the liquid route can be done in a known manner in different ways, such as by coating, by impregnation in solution or soaking ("dip-coating" in English), by spraying ("spray coating” in English), by spreading with a spin coating ("spin coating” in English), etc.
• the smoothing layer may be chosen as a sol gel layer (over the entire smoothing layer or at least at its surface).
• sol-gel layer has the advantage of being carried out at room temperature.
• the starting point is a homogeneous solution of precursors molecular, which is converted into a solid by chemical reaction of inorganic polymerization at room temperature.
• the solution of more or less polymerized precursors is called sol, and turns into a gel during aging.
• the homogeneous solid obtained is porous, amorphous and densifies at low temperature, which makes it possible, under mild conditions, to produce glasses, ceramics or, in this case, a thin layer.
• an initial composition of materials is prepared, to obtain a final mixture of materials, called "sol", by polymerization of the initial composition, to deposit on the glass substrate this soil, and to dry the soil once deposited to form the smoothing layer.
• a sol-gel chosen smoothing layer and / or the sol gel binder are made from a sol whose initial composition is based on silicon alkoxide, and optionally a solvent, of the isopropanol type.
• This method which is of low cost has the advantage of being able to be achieved over large areas, and is completely reproducible.
• the layer obtained by the sol-gel route does not generate the risk over time of delamination of the texturing.
• the product obtained is resistant to heat treatments, thermal quenching and / or chemical treatments which are often necessary thereafter for the final destination of said product, such as its integration into an OLED.
• a sol gel silica layer is obtained from an initial composition based on a silicon alkoxide, in particular tetraethoxysilane (Si (OC 2 H 5 ) 4 and called "TEOS”), and a solvent, isopropanol.
• a silicon alkoxide in particular tetraethoxysilane (Si (OC 2 H 5 ) 4 and called "TEOS)
• TEOS tetraethoxysilane
• solvent isopropanol
• the formation of the smoothing layer may comprise the deposition of a first layer based on an aqueous dispersion of (nano) silica particles, optionally with a silica binder, especially a silica gel sol, which therefore has the same chemical nature as the (nano) particles.
• the formation of the smoothing layer may comprise the deposition of a dispersion of (nano) silica particles, which is essentially binderless, then the deposition of a layer to form a silica binder (nano) particles, in particular a Soil silica gel therefore of the same chemical nature as the (nano) particles, the binder penetrating into the thickness of (nano) particles and covering the (nano) particles.
• the smoothing layer in particular sol-gel, has a refractive index substantially equal to that of the glass.
• Its deposition is such that its surface is sufficiently corrugated, preferably of RMS parameter greater than 30 nm (greater than 50, or even 150 nm), and / or roughness parameter Rmax greater than or equal to 20 nm over a length of analysis of 180 microns, and with a Gaussian filter of cutoff frequency at 25 microns.
• the random roughness of the substrate is preferably achieved by a treatment of the glass substrate, in particular by etching or even sandblasting.
• the OLED includes a first electrode deposited on the smoothing layer.
• This first electrode in the form of thin layer (s) deposited (s) directly on the smoothing layer, may be substantially conformal to the surface (and preferably thus reproduce the texturing after softening), for example by deposition ( s) in the vapor phase, in particular by magnetron sputtering, by evaporation.
• the first electrode is generally index (average) from 1, 7 or even beyond (1, 8 even 1, 9).
• the organic layer (s) of the OLED are generally index (average) from 1, 8 or even beyond (1, 9 even more).
• the invention also relates to a textured surface structure comprising a rough inorganic glass substrate, with a roughness defined by a roughness parameter Ra ranging from 1 to 5 ⁇ m (preferably from 1 to 3 ⁇ m), over a length of analysis of 15 mm and with a Gaussian filter of cutoff frequency at 0.8 mm, the rough surface being sufficiently softened by a silica smoothing layer (directly) deposited on the rough substrate.
• An industrial glass is preferably chosen, in particular silicates, preferably at low cost. It is preferably a silicosocalocalic glass.
• the rough surface of the substrate preferably comprises substantially pyramidal excrescences distributed randomly.
• the texturing of the structure (in other words, the surface of the smoothing layer) is also random.
• the textured surface of the structure can be 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 a roughness parameter Rmax of less than 250 nm, preferably less than or equal to 200 nm, over an analysis length of 180 ⁇ m, and with a Gaussian filter with a cut-off frequency of 25 nm. .mu.m.
• the silica smoothing layer in particular sol-gel at least for its surface part: - is essentially mineral, in particular for a good thermal resistance,
• dielectric in the non-metallic sense, for example based on optionally metallic oxides
• electrically insulating in general of electrical resistivity in the solid state, as known in the literature, greater than 10 9 ⁇ .cm
• semi-conductor generally solid state electrical resistivity, as known in the literature, greater than 10 "3 ⁇ .cm and less than 10 9 ⁇ .cm
• the substrate coated with the smoothing layer may have a light transmission T L greater than or equal to 70%, or even 80%.
• the silica smoothing layer in particular sol-gel, has a refractive index substantially equal to that of glass, in particular a conventional glass of index 1, about 5.
• the smoothing layer is deposited so that the surface of the layer is sufficiently corrugated, preferably with an RMS parameter greater than 30 nm, preferably greater than 50 nm, or even 150 nm, over an analysis length of 180 ⁇ m, and with a Gaussian filter with a cutoff frequency of 25 ⁇ m. It is thus necessary to soften sufficiently to avoid electrical damage while maintaining a certain level texturing of the surface to ensure extraction. Indeed; undulation disrupts the modal distribution of energy.
• the smoothing layer has a thickness (at the hollows) ranging from 500 nm to 10 ⁇ m depending on the desired degree of softening, and preferably ranging from 1 ⁇ m to 10 ⁇ m.
• the smallest thickness is present on the summits or growths of the relief, the strongest in the hollows.
• This thickness is related to the dry extract of the initial composition based on molecular precursors.
• the solids content is defined as the ratio between the mass of materials generated in the soil that will be present in the layer after drying, and the mass of the materials of the initial composition.
• the dry extract is advantageously from 15 to 30%.
• the smoothing layer may be based on silica nanoparticles covered by a silica gel sol.
• the nanoparticles have an average diameter of preferably ranging from 10 to 50 nm to better limit and control the roughness of the deposit.
• the (nano) particles can be deposited from a dispersion in a solvent (alcohol, ketone, water, glycol, etc.).
• a solvent alcohol, ketone, water, glycol, etc.
• the silica binder can be prepared by sol-gel (mineral, or inorganic organic hybrid ).
• the silica binder may be based on organometallic precursors, therefore of the same chemical nature as the (nano) particles.
• Another alternative is to coat the layer (nano) silica particles without binder with a silica binder.
• the binder penetrates between the nanoparticles (at least on the outermost part of the layer) thus acting as a cement between the particles, for example at less than half the thickness.
• the binder remains on the surface, smoothing the surface and can protect the layer from mechanical aggression.
• the binder may be a silica gel sol based on organometallic precursors, therefore of the same chemical nature as the (nano) silica particles.
• the subject of the invention is an organic light-emitting diode device incorporating the textured outer surface structure defined above, the textured surface of the structure being arranged on the organic electroluminescent layer (s) side (OLED system), that is to say inside the device, the opposite side to the emitting light side outside the device.
• the textured outer surface structure is therefore under a first electrode underlying the (x) electroluminescent layer (s) organic (s).
• the OLED can form a lighting panel, or a backlighting panel (substantially white and / or uniform) in particular with a (full) electrode surface greater than or equal to 1 ⁇ 1 cm 2 , or even up to 5 ⁇ 5 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.
• a non-pixelated electrode it differs from the display screen electrodes ("LCD" ...) formed of three juxtaposed pixels, generally of very small dimensions, and each emitting a given almost monochromatic radiation (typically red, green or blue).
• 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 respectively 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 may further include an upper electrode above said OLED system.
• 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.
• the OLED can be arranged to produce a uniform polychromatic light, especially for uniform 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.
• 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, - intended for a transport vehicle, such as a bright roof, a (part of) side light window, an internal light partition of a land, water or air vehicle (car, truck train, airplane, boat, etc.), intended for street or professional furniture such as a bus shelter panel, a display wall, a jewelery display or a showcase, a wall of a greenhouse, an illuminated slab, intended for interior furnishing, an element of a shelf or furniture, a front of a piece of furniture, an illuminating slab, a ceiling lamp, a refrigerator lighting tablet, an aquarium wall, intended for the backlighting of electronic equipment, in particular of a screen visualization or display , possibly double screen, like a television 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 Transporting Layer
• 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).
• PLED Polymer Light Emitting Diodes
• FIG. 1 represents a schematic sectional view of an OLED whose glass substrate is rough and sufficiently softened according to the invention
• - Figure 2 is an optical photo of the rough surface of the glass before the deposition of the smoothing layer
• Figure 3a is a sectional view by scanning electron microscopy of the rough glass coated with a layer of smoothing sol gel
• FIG. 3b is a photograph by optical microscopy of the surface of the rough glass coated with a layer of smoothing gel sol.
• FIG. 1 which is not to scale for a better understanding, shows schematically an organic light-emitting diode device 1 which comprises successively,
• a first transparent electroconductive coating 1 1 which forms a first electrode
• a second electroconductive coating 13 which forms a second electrode, and preferably has, facing the organic layer 12, a (semi) reflecting surface intended to return the light emitted by the organic layer towards the opposite direction, that of the transparent substrate 10 from which the light emerges.
• the first electrode 11, or lower electrode comprises, for example, a transparent electroconductive coating such as based on tin-doped indium oxide (ITO) or a silver stack.
• a transparent electroconductive coating such as based on tin-doped indium oxide (ITO) or a silver stack.
• the silver electrode stack comprises, for example: a possible bottom layer (and / or) wet etch stop layer, a possible mixed oxide sub-layer based on zinc and possibly tin doped or a mixed indium tin oxide (ITO) layer or a mixed indium zinc oxide layer (IZO), a metal oxide contact layer selected from ZnO x doped or non-doped, Sn y Zn z O x , ITO or IZO, a metallic functional layer, for example silver, with intrinsic property of electrical conductivity, a possible thin layer of overblocking directly on the functional layer, the thin layer of overblocking comprising a metal layer of thickness less than or equal to 5 nm and / or a layer with a thickness of less than or equal to 10 nm which is based on sub stoichiometric metal oxide, stoichiometric metal oxynitride or metal nitride under stoichiometric (and possibly a protective layer selected from ZnO x
• N 4 / ZnO Al / Ag / Ti or NiCr / ZnO: Al / ITO, respective thicknesses 25nm for Si 3 N 4 , 5 at 20 nm for ZnO: Al, 5 to 15 nm for silver 0.5 to 2 nm for Ti or NiCr, 5 to 20 nm for ZnO: Al, 5 to 20 nm for NTO.
• silver the contact layer, optionally the thin layer of under blocking, - the functional layer, the thin layer of overblocking, optionally the protective layer with water and / or oxygen,
• the final layer remains the overlay.
• the organic layer stack of the OLED comprises a central electroluminescent layer interposed between an electron transport layer and a hole transport layer, themselves interposed between an electron injection layer and a layer of electrons. injection of holes.
• the second electrode of the OLED, or upper electrode is of electrically conductive material and preferably (semi) reflective material, in particular a metallic material of the silver or aluminum type.
• the second face 10b of the substrate facing the first electrode 11 is rough with alternating growths 10c and troughs.
• the roughness 10c is obtained by a frosting of a glass substrate, for example with hydrofluoric acid.
• a rough substrate is the glass called DecorFlou® produced by the company Omnidecor (satin aspect).
• glasses attacked with acid for example: the glass called SatenGlass® produced by Sevasa, - the glass called Satinovo® Mate produced by the company La Veneciana de Saint Gobain,
• Dekormat® produced by the company Dekormat Glass.
• the roughness can also be achieved by sanding.
• An optical profilometer is used for the roughness measurements, according to the principle of the extended field chromatic microscopy, for example using the STI M2 base station Ml M2.
• An analysis length of 15 mm is chosen, and with a Gaussian filter with a cut-off frequency of 0.8 mm. This measurement can be repeated 30 times with profile intervals of 1 mm. A Ra parameter of 2 ⁇ m and a Rsm parameter of 60 ⁇ m are obtained.
• FIG. 2 shows, by optical microscope, the rough surface of this glass with growths 10c, at a magnification of 20, over a measuring zone whose dimples are substantially pyramidal, distributed randomly, diffusing the light isotropically.
• the inventors have demonstrated that it is essential that the outer surface of the structure to receive the electrode is free of sharp points.
• a smoothing layer with a textured surface defined by a roughness parameter Rdq of less than 1.5 °, and a roughness parameter Rmax of less than 250 nm over an analysis length of 180 ⁇ m. and with a Gaussian cutoff filter of 25 ⁇ m.
• the tangent may also form at a majority of points of the textured surface with the normal to the opposite planar face 10a, an angle greater than or equal to 30 °, and preferably at least 45 °.
• the smoothing layer 2 is a silica gel sol layer, manufactured by a liquid route.
• An initial composition of materials is prepared, to obtain a final mixture of materials, called "sol", by polymerization of the initial composition, to deposit on the glass substrate this soil, and to dry the soil once deposited to form the coating layer. smoothing.
• the initial composition is made from precursor molecules, in particular of the alkoxide type, optionally of complexing agent (s) to adapt the degree of polymerization, and of solvent (s) for diluting the precursor molecules.
• the deposition of the soil is preferably carried out by a liquid method, for example by a spreading technique, using a spin-coating device.
• the thickness is directly related to the dry extract of the layer.
• the solids content is defined as the ratio between the mass of materials generated in the soil that will be present in the layer after drying, and the mass of the materials of the initial composition.
• the smoothing layer is a silica layer having a refractive index substantially equal to the glass.
• the initial composition is based on two silicon alkoxides, tetraethoxysilane (Si (OC 2 Hs) 4 and called “TEOS”) and metyltriethoxysilane (CH 3 Si (OC 2 H 5 ) 3, called "MTEOS”), which are used in water acidified with hydrochloric acid to obtain a pH of 2.5.
• TEOS tetraethoxysilane
• MTEOS metyltriethoxysilane
• the molar percentage of MTEOS relative to the sum TEOS + MTEOS is 70%.
• the preparation of the composition consists in: mixing 4.8 g of acidified deionized water with HCl (the pH of the water being equal to 2.5), 6.7 g of TEOS and 13.5 g of MTEOS; stir the mixture for two hours at room temperature; The sol obtained has a solids content of 28%. The sol obtained is then deposited by spin-coating at 500 rpm on the DecorFlou® rough glass substrate already described, and then dried for half an hour at 120 ° C.
• the resulting layer of silica (SiO 2 ) has a refractive index equal to 1.42.
• FIG. 3a is a SEM 5000 magnification photograph in section of the rough glass coated with this layer of smoothing gel sol.
• FIG. 3b is a view from above of the surface of this magnification optical microscopy smoothing layer of dimensions 690 ⁇ m by 500 ⁇ m.
• the SEM analysis shows that the smoothing layer has a thickness of about 8 ⁇ m in the hollows, and a smaller thickness on the "peaks" or growths.
• Optical interferometry is used for the roughness measurements, for example the NEWVIEW apparatus of the company ZYGO.
• the analysis length being 180 ⁇ m with a Gaussian filter of cutoff frequency at 25 ⁇ m, we obtain:
• the surface of the smoothing layer meets the particular criteria of the glass-electrode interface in an OLED.
• the smoothing layer is in fact formed in two stages. Starting from an initial composition based on SiO 2 nanoparticles, it is easy to form a sufficiently thick first layer for a first level of smoothing of the glass. This first layer of nanoparticles is then coated with a topcoat to erase the roughness generated by the nanoparticles themselves for a second level of smoothing while retaining sufficient texturing.
• the topcoat is based on silicon alkoxide, and a solvent, isopropanol.
• the initial composition of the first layer is a dispersion, for example an aqueous dispersion, of SiO 2 nanoparticles.
• the size of the nanoparticles is, for example, 20 nm.
• the solids content of the dispersion is 20%.
• the smoothing consists of: spin-coating at 500 rpm on an intrinsically textured glass substrate of the SATI NOVO® type the aqueous dispersion of SiO 2 nanoparticles, preferably drying this first layer for 1 h at 120 ° C. depositing by spin-coating at 500 rpm the composition of the silica precursor topcoat, dry the whole 30 min at 120 ° C.

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