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
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—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 of an organic material and at least one non-metal coating
• • 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
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
  • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
  • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
• • 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
• • 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
  • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
  • C03C2217/45—Inorganic continuous phases
  • C03C2217/452—Glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/365—Coating different sides of a glass substrate
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
  • H10K2102/301—Details of OLEDs
  • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249967—Inorganic matrix in void-containing component
  • Y10T428/249969—Of silicon-containing material [e.g., glass, 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249967—Inorganic matrix in void-containing component
  • Y10T428/24997—Of metal-containing material

Definitions

• the present invention relates to a support for an organic light-emitting diode device. It relates more particularly to a support for an organic light-emitting diode device comprising a transparent glass substrate coated with a diffusing layer, and such a device.
• OLED Organic Light Emitting Diodes
• OLED comprises a material, or a stack of materials, electroluminescent (s) organic (s), and is framed by two electrodes, one of the electrodes, called lower, generally the anode being constituted by that associated with a glass substrate and the other electrode, said upper, usually the cathode, being arranged on the organic electroluminescent system.
• 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 front and rear emission devices that is to say with both a lower (semi) transparent electrode and an upper (semi) transparent electrode.
• the invention relates to OLED devices emitting from the rear and possibly also from the front.
• An OLED usually finds its application in a display screen or more recently in a lighting device.
• the light extracted from the OLED is a "white” light emitting in some or all wavelengths of the 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 nevertheless 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 FR2937467 discloses in particular an OLED device whose mineral glass substrate comprises, on the main face opposite to that carrying the first electrode, a diffusing layer comprising a mineral binder and diffusing particles dispersed in the binder, as well as particles dispersed in the binder and absorbing ultraviolet (UV) radiation in the wavelength range of 325 to 400 nm.
• a diffusing layer comprising a mineral binder and diffusing particles dispersed in the binder, as well as particles dispersed in the binder and absorbing ultraviolet (UV) radiation in the wavelength range of 325 to 400 nm.
• the binder is obtained from a glass frit, potassium silicate, sodium or lithium.
• the diffusing particles are alumina or else BaSO 4 , ZrO 2, SiO 2 or CaCO 3
• the proportion of the binder is of the order of 30 to 70% of the total weight of the diffusing layer, and the proportion of diffusing particles is of the order of 25 to 60% of the total weight of the layer, and the proportion of particles absorbing UV radiation is between 2 to 15% of the total weight of the layer.
• a preferred example of a diffusing and anti-UV layer with a thickness of 1 ⁇ is as follows:
• the diffusing layer is applied against the substrate by screen printing or any other suitable technique such as by coating, by dip-coating, by spraying.
• the diffusing function of this layer allows a "re-mixing" of the colors forming the white light, which makes it possible to extract a much more homogeneous light.
• the aim of the invention is, in particular, to achieve a robust OLED device without sacrificing the optical performance of the OLED (in particular the light extraction and / or the limitation of the colorimetric variation as a function of the observation angle of the selected emitted light polychromatic, especially white) or improve them, nor cause difficulties of realization.
• Another important goal is to make it possible to manufacture such a device that is compatible with the manufacturing process of the OLED device.
• the present invention proposes for this purpose a support for an organic light-emitting diode device successively comprising a transparent mineral glass substrate provided with first and second main faces. opposed, the substrate being coated (directly) on its second face with a diffusing layer which comprises a binder (essentially) inorganic and scattering elements dispersed in the binder, the vitreous binder comprising between 40% to 60% by weight of oxide of bismuth B12O3 including these values, or even between 45% and 58% by weight of bismuth oxide B12O3 including these values, the proportion of vitreous binder is at least 20% of the total weight of the diffusing layer.
• the appropriate proportion of bismuth oxide in the diffusing layer according to the invention guarantees enhanced chemical resistance.
• the diffusing layer according to the invention is resistant to these different chemical treatments that the substrate undergoes during the production of OLED, unlike conventional frits. .
• the vitreous binder may be what the skilled person calls an enamel or a glass frit.
• the diffusing layer according to the invention makes it possible:
• the diffusing layer preferably has a main outer surface in the open air.
• the substrate according to the invention is considered laid horizontally, with its first face facing downwards and its second face, opposite the first face, facing upwards; the meanings of the expressions “above” and “below” are thus to be considered in relation to this orientation.
• the terms “above” and “below” do not necessarily mean that the two elements are arranged in contact with each other.
• index refers to the optical refractive index, measured at the wavelength of 590 nm.
• the chemical resistance of the diffusing layer of vitreous material according to the invention may be accentuated by the fact that the binder has a composition of water-soluble oxides which is weak.
• the water-soluble oxides in particular the alkaline oxides of sodium and potassium type, preferably have a content of less than 15% by weight and even more preferably less than 5%.
• the vitreous binder of the diffusing layer (monolayer or multilayer) according to the invention comprises, by weight:
• the binder according to the invention may preferably comprise between 5 and 30% by weight of ZnO including these values and preferably between 10 and 25% by weight of ZnO including these values.
• the chemical resistance is further enhanced by the combined action of these two oxides in their specific ranges.
• Said diffusing layer according to the invention (single layer or multilayer) preferably has a thickness (total) between 1 ⁇ and 50 ⁇ by including these values, or even between 5 ⁇ and 30 ⁇ including these values.
• the diffusing elements preferably have a characteristic dimension comparable to or greater than the wavelength of the light in the vitreous medium, which corresponds to dimensions of between a few hundred nanometers and a few microns.
• the diffusing elements according to the invention may comprise porosities in volume (therefore in the layer) or even on the surface.
• the diffusing elements may comprise diffusing particles, in particular of material of index different from the index of the substrate, preferably in a proportion of less than 60% of the total weight of the layer, and possibly volume or even surface porosities.
• the porosities are naturally present in the diffusing layer while ad hoc scattering particles are added. Closed porosities promote volume diffusion. Open porosities promote surface diffusion.
• the porosities arise for example from the cooking (elimination) of the organic medium.
• the porosities are large, larger than 500 nm.
• diffusing element As another diffusing element according to the invention, mention may be made of crystals, such as, for example, zircon or baddeleyite crystals naturally present in the diffusing layer.
• the diffusing elements according to the invention may comprise mineral diffusing particles, in particular chosen from one or more of the following particles: particles of alumina, zirconia ZrO 2, silica S102 , titanium oxide TiO 2 or CaCO 3 , of BaSO 4 .
• a diffusing layer according to the invention with a binder (essentially) mineral and preferably by diffusing (essentially) mineral elements (in particular with at least 80% of mineral diffusing elements including mineral particles, crystals, porosities) present a very good temperature resistance, particularly at about 400 ° C, so as not to be degraded during the manufacturing process of the entire OLED.
• the proportion of vitreous binder according to the invention is between 40 and 80% of the total weight of the diffusing layer including these values, in particular between 50 and 75% by including these values, and the proportion of the diffusing particles chosen.
• in alumina is between 20% and 60% including these values, especially between 25 and 50% of the total weight of the layer including these values.
• the diffusing layer according to the invention may have a rough external surface, which is rough, with a roughness parameter defined by a roughness parameter Ra greater than 500 nm, or even at 900 nm over a length of analysis of 200 ⁇ .
• 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.
• a mechanical profilometer such as the DEKTAK device from VEECO is chosen.
• the substrate coated with this diffusing layer according to the invention can have a light transmission (TL) of at least 50% and a blur (that is to say the ratio TL / TD where TD is the diffuse transmission) of at least 80% or even 90%.
• TL light transmission
• blur that is to say the ratio TL / TD where TD is the diffuse transmission
• the glass substrate may have a conventional index between 1, 4 and 1, 6 or be high index so index greater than or equal to 1.7.
• the glass substrate is for example of thickness between 0.7 and 6 mm depending on the applications, preferably between 0.7 and 3 mm including these values. It can be a clear, extraclear glass.
• the bare substrate has a TL of at least 80% or even 90%.
• the support according to the invention may comprise several diffusing layers in particular based on said vitreous bismuth oxide binder each having a diffusion or even different chemical resistance:
• At least the last diffusing layer must be chemically resistant. Below one can optionally choose a "classic" diffusing layer, especially based on zinc borate frit.
• a first diffusing layer comprises between 40% and 60% by weight of bismuth oxide B12O3 including these values
• a second diffusing layer of vitreous material comprises between 45% and 58% by weight of Bi 2 O 3 bismuth oxide including these values.
• the diffusing layer (monolayer or multilayer with a binder, whether distinct or not, and diffuse or distinct scattering elements) is preferably directly on the second face of the substrate.
• the first transparent electrode in the form of a layer (s), is deposited on the first face of the substrate;
• an organic electroluminescent system in particular an organic coating, preferably a polychromatic visible radiation emitting system, and a second electrode, in the form of a layer (s), and deposited on the organic system. (s) opposite the first electrode; a second electrode, in the form of a layer (s), is deposited on the organic system (s) opposite the first electrode.
• the present invention also relates to the use of a support with a diffusing layer defined as above, as a support in an organic light-emitting diode device for lighting (especially general).
• the diffusing layer according to the invention constitutes a particularly chemically resistant layer while providing a significant gain of extraction of the light emerging from the diffusing OLED device according to the invention.
• Another advantage provided by the diffusing layer according to the invention is to further reduce the colorimetric variations perceived by an observer facing the diffusing OLED device according to the invention.
• the OLED may preferably output a spectrum of polychromatic light, in particular white.
• white light several methods are possible: compound mixing (red, green, blue emission) in a single layer, stacking of three organic structures (red, green, blue emission) or two organic structures (yellow and yellow). blue), a series of three adjacent organic structures (red, green, blue emission).
• the colorimetric variation V c is evaluated, for example with a spectrophotometer, as a function of the angle of observation. That is, the length of the path (of various shapes, such as a straight line or an arc of a circle), in the CIE XYZ 1931 color diagram, between the spectrum emitted at 0 ° and the spectrum emitted at 75 °, this every 5 °.
• the colorimetric coordinates for each angle spectrum ⁇ are expressed as the pair of coordinates (x (0,); y (0i)) in the CIE XYZ 1931 colorimetric diagram.
• the length of the path V c i for the device according to the invention between the spectrum emitted at 0 ° and the spectrum emitted at 75 °, and passing through the intermediate angles with a pitch of 5 °, can therefore be calculated using the formula following known:
• the length of the path must be as short as possible.
• a second path length Vc2 of identically, Vc1A / c2 is obtained which is less than or equal to 0.25 or even 0.2 and even 0.1, and preferably Vc2 is less than or equal to 10 -1 ;
• a third path length Vc3 is defined identically and Vc1A / c3 is obtained less than or equal to 0.9 or even 0.7, and even 0.5 and preferably Vc3 less than or equal to 10 -1
• the diffusing layer is deposited on the second face before a deposit of the first electrode on the first face;
• said diffusing layer is deposited from a glass frit, preferably with an organic medium, by screen printing and the glass frit is melted to form the vitreous binder and preferably in the presence of diffusing elements comprising diffusing particles.
• the chemical resistance is obtained by the action of the bismuth oxide in its specific range.
• this chemical resistance makes it possible to use the substrate coated with the diffusing layer in methods of manufacturing the OLED device as already seen: during various cleanings, in particular cleaning the substrate before depositing the first electrode;
• the substrates must primarily support manual or automated cleaning procedures in baths. These cleaning procedures must rid the substrates of all traces of organic or inorganic matter as well as any trace of particles before the deposition of the organic electroluminescent system. Each substrate therefore passes successively in contact with basic and acidic detergent solutions with intermediate rinsing between each step. The cleaning power is also often accentuated by the presence of detergents and / or ultrasound and / or by the use of a temperature close to about 40 ° C.
• An example of a bath chain can thus consist of:
• Each bath is regulated at a temperature of at least 30 to 40 ° C and the detergent baths previously named one and two, can be equipped with ultrasonic source which facilitates the renewal of the active solution and increases cleaning efficiency.
• the fifth bath may have a higher frequency ultrasonic source for the purpose of removing solid particles or fibers.
• FIG. 1 shows a schematic sectional view of an OLED according to the invention
• FIG. 2a shows a SEM and tilt view at a magnification of 1000 of a diffusing layer according to the invention with a vitreous bismuth oxide binder with 30% alumina and large porosities;
• FIG. 2b shows a SEM view in section and tilt at a magnification of 5000 of a diffusing layer according to the invention with a vitreous bismuth oxide binder with 30% alumina and large porosities;
• FIG. 3 shows a top SEM view at a magnification of 1000 of a diffusing layer according to the invention with a vitreous bismuth oxide binder with 30% alumina and large porosities;
• FIG. 4 shows a SEM view in section and tilt at a magnification of 1000 of a diffusing layer according to the invention with a vitreous bismuth oxide binder with porosities and without adding scattering particles.
• OLED illustrated schematically and not to scale in FIG. 1, comprises successively: a transparent substrate 10 with a diffusing layer 2 according to the invention,
• a second electroconductive coating 13 which forms a second electrode facing the organic layer and preferably forming a reflective or semi-reflecting surface intended to return the light emitted by the organic layer to the opposite direction, that of the transparent substrate 10.
• the transparent substrate 10 is of thickness adapted to the desired final application (lighting device).
• the glass is of standard composition or may be a so-called glass known as "extra-clear" because conferring a minimized light absorption.
• the substrate 10 comprises, according to its largest dimensions, a first face 10a and a second opposite face 10b, the first face comprising the first electrode 11, while the opposite second face 10b is provided with the diffusing layer 2.
• the diffusing layer 2 is attached to the substrate 10 by screen printing or any other suitable technique such as by coating, by dip-coating, by spraying.
• the diffusing layer 2 comprises a vitreous binder 20 and diffusing elements 21.
• the diffusing layer 2 preferably contains a proportion of 30% by total weight of the layer of the diffusing particles of alumina 21 of size of the order of 600 nm.
• the proportion of glassy binder is about 70% by total weight of layer 2.
• the vitreous binder comprises between 40% and 60% by weight of B12O3 bismuth oxide including these values, or even between 45% and 58% by weight of B12O3 bismuth oxide including these values.
• compositions of the glassy binder diffusing layer are given in Table 1 (in% by weight of the glassy binder)
• Example 1 is an example according to the invention, the comparative example is a layer with a vitreous binder with a high content of B12O3 and ZnO and without B12O3, this comparative diffusing layer containing, like the layer of Example 1, a proportion 30% by total weight of the layer of alumina diffusing particles.
• Each of these two examples has undergone a whole set of tests (treatments) with acids (used for example for the etching of electrode), with the bases (serving for example for the withdrawal of a mask of resin or for the 1 1
• the commercial detergents of the cleaning baths are employed at the volume dilutions listed in Table 2.
• the Franklab Neutrax detergent consists of a mixture of organic acids such as acetic acid and sequestering agents, the 1% dilution of which gives the medium a moderate acidic pH of approximately 4.
• Franklab detergent TFD66 is a low foaming alkaline detergent that contains sequestering agents and gives a pH of about 1 1 by 4% dilution.
• RBS 2% is a basic alkaline solution which is a mixture of ionic and nonionic detergents + phosphates and polyphosphates with a volume concentration of 2%, ie having a ph of the order of 1 1.
• test is carried out by immersing in the bath specified in the column on the left a test tube 4 cm wide and 7 cm high and 2 mm thick, each test tube being immersed at 80% of its height in the bath. specimen consisting solely of the substrate coated with the scattering layer of approximately 15 ⁇ .
• Level N3 significant degradation with color change such as iridescence, bleaching, or matting
• TL light transmission
• TD diffuse transmission
• Example 1 By the matrix with bismuth oxide (example 1) the levels of the light transmission TL and the diffuse transmission (TD) remain in the desired range for extraction on the air side. As shown in Table 2, the layers of Example 1 comprising bismuth oxide accept 10 min immersion at 25 ° C or 40 ° C in the following baths:
• acid ph 4 hydrochloric acid, sulfuric acid, phosphoric acid;
• Example 1 have a reinforced strength compared to the layers of the comparative example during immersion 10 minutes in the following baths:
• an example 1a it is a diffusing layer with a binder of composition identical to Example 1 and without addition of scattering particles.
• the porosities (and the crystals) form diffusing elements.
• FIG. 2a shows a SEM view in section and tilt at a magnification of 1000 (20 ⁇ scale in the view) of the scattering layer of example 1.
• FIG. 2b shows a SEM view in section and tilt at a magnification of 5000 (5 ⁇ scale in the view) of the scattering layer 2 of example 1.
• a porosity of micron size is shown and the particles of alumina 21 are also observed.
• FIG. 3 shows a SEM view from above at a magnification of 5000 (20 ⁇ scale in the view) of the diffusing layer 2 of example 1.
• the surface roughness is easily observable.
• FIG. 4 shows an SEM view in section and tilt at a magnification of 1000 of a diffusing layer 2 according to the invention with a vitreous binder 20 with bismuth oxide with porosities 22 and without the addition of diffusing particles, corresponding in example 1a.
• the porosities are smaller and the surface smoother.
• the manufacture of the diffusion layer with enhanced chemical resistance can be carried out according to various industrial processes and preferably by screen printing. Dough
• the screen printing paste will be constituted in mass proportions between 10 and 50% of a silkscreen medium which will serve as a vehicle for the particles to pass through the application screen.
• This medium can be organic, consisting of alcohols, glycols, esters, terpineol which, combined with fine mineral particles such as fumed silica or cellulose ethers, gives threshold fluid properties to the dough.
• the combustion of the organic medium generates the porosities.
• the paste used is prepared, for example, by dispersing a glass frit in a conventional screen-printing medium composed of a mixture of glycols such as the medium 80840 sold by the company Ferro.
• the rheological characteristics for the use of the dough by screen printing are optimized by the use of fumed silica or cellulose ethers.
• the solid fraction (forming the vitreous binder) is a glass frit with a high proportion of bismuth oxide as already indicated which confers the chemical resistance of the layer.
• the mashing of the constituents takes place at high speed in planetary mixers, disk dispersers.
• Low speed systems can also be used in addition, either before or after the high speed operation. These low-speed systems consist of agitator-type kneader, drummer or bottles with beads that are placed for several hours on agitators with rolls driven at low speeds of a few revolutions per minute. The quality of the dough is appreciated by the absence of grains or aggregates using an Egman gauge.
• the depositing machines can be of reduced format of electronic type (EKRA, DEK) or of industrial size (THIEME) as for the flat glass.
• the screens will be made of textile mesh (example: polyester) or metallic.
• the masks may be made of photoresist or metal foils.
• Topping tools and squeegee will be polymer, carbon or metal.
• the deposited thicknesses are between 10 and 100 m on a glass substrate. The control of the thickness is first ensured by the choice of the mesh of the screen and its tension.
• Control of the thickness is also ensured by the adjustments of the distance between the screen and the substrate as well as the pressures and the speeds of displacement applied to the doctor blade.
• the thicknesses will be controlled using a Rodenstock laser optical bench between a coated zone or not.
• the deposits are dried at a temperature of the order of 100 to 150 ° C in an infrared or UV radiation tunnel depending on the nature of the medium used.
• the deposition of the diffusing layer may also be carried out by means other than screen printing: for example by roll coating, dip coating, knife coating ), spray deposition, spin coating ("spin coating") or deposition by vertical topping ("flow coating”).
• the changes in the powder-to-liquid ratios and the use of additive is used to adapt the rheology of the composition to the chosen deposition mode. Two different deposition modes can be used successively to make a stack of similar layers or different compositions or gradient of one or more components.
• the furnaces employed can be dynamic with transport on rollers as for automotive rear window baking or preferably static with positioning on metal plates or glass-ceramic for maintaining the flatness of the substrate.
• the cooking temperature is above 580 ° C.
• the electronics sector commonly uses clean room substrates with or without layers that must primarily support manual cleaning procedures or automated baths. These cleaning procedures must rid the substrates of all traces of organic or mineral matter as well as particles. The substrates thus successively pass steps in contact with basic and acidic detergent solutions with intermediate rinses. The cleaning power is accentuated by the presence of detergents, ultrasounds and a temperature often close to 40 ° C.
• composition rich in bismuth oxide of the diffusing vitreous layer according to the invention gives it a high resistance in these aggressive media such as the abovementioned baths.
• a vitreous layer of the comparative example developed according to the same production process is completely destroyed under the same cleaning conditions.
• Example 1 by adding the diffusing layer of Example 1 (Examples A1 and A1 bis and A1 ter).
• a first organic light-emitting diode is used for lighting called Orbeos® sold by OSRAM and providing a white light.
• a second organic light-emitting diode is therefore used for lighting called Lumiotec® sold by LUMIOTEC and providing a white light.
• a third organic light-emitting diode is used for the lighting is called Lumiblade® sold by the company PHILIPS and providing a white light.
• the extraction gain is defined as the relative increase in the amount of light extracted, i.e., the ratio between the difference in the amount of light emitted by the device with and without the solution of the invention (addition of the scattering layer), and the amount of light emitted by the device without solution. To measure it, it is therefore a question of comparing the total luminous flux coming out of an OLED without solution and that coming out of an OLED with solution. To ensure that the entire flow is collected in both cases, the two OLEDs are one by one, in a known manner, placed inside an integrating sphere.
• the gain is approximately 40% for the examples with comparative diffusing layers (REF 2 and REF 2ter) or scattering layers according to Example 1 (A1 and A1 ter), 40% by compared to diodes without diffusing plastic film (REF 1 and REF 1 ter).
• the gain is approximately 25% for the examples with diffusing layers according to the invention without diffusing particles, made according to Example 1 bis 25% with respect to the diodes without diffusing plastic film (REF 1 and REF 1 ter).
• Table 4 lists the lengths of the optical paths Vc1 to Vc3 for the aforementioned examples REF1 to A1 ter.
• the angular colorimetric variation is therefore much lower with a diffusing layer and in particular with the diffusing layer according to the invention, thus ensuring a much more homogeneous white light.
• the diffusing layer according to the invention on the substrate makes it possible at the same time to increase the extraction gain of the OLED, to reduce the colorimetric variations of the emitted light so as to provide a more homogeneous light and to be chemically and thermally resistant.

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