Classifications

• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/81—Anodes
  • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/85—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
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to an electroconductive support, the organic electroluminescent device incorporating it and its manufacture.
• OLEDs for "Organic Light Emitting Diodes"
• OLEDs Organic Light Emitting Diodes
• OLEDs Conventionly comprise a material or a stack of organic electroluminescent materials supplied with electricity by two electrodes generally framing it in the form of electroconductive layers.
• the upper electrode is a reflective metal layer, for example aluminum
• the lower electrode is a transparent layer based on indium oxide, generally the indium oxide doped with tin better known under the abbreviation ITO of thickness of the order of 100 to 150nm.
• ITO abbreviation of thickness of the order of 100 to 150nm.
• Patent application WO2009071822 proposes an alternative lower electrode. More specifically, the lower electrode comprises firstly an aperiodic gate conductor, 1 ⁇ thick, formed of irregular strands based on silver, of average width A of the order of 3 ⁇ , and spaced apart from one another by mean distance B of the order of 30 ⁇ , with a B / A ratio of 10.
• This electroconductive grid is manufactured by evaporation of silver on a mask with a network of self-organized openings. The mask is removed afterwards.
• the square resistance of this particularly low gate is about 60.0 / square.
• the light transmission T L of this grid is about 70% and the strands are invisible to the naked eye.
• a high-indexed melt-glass filler layer is added, in the embodiment in connection with FIG. 3.
• the surface formed by the strands of the grid and the glass frit melted is smoothed by mechanical polishing using for example a polishing alumina, or oxide cerium etc.
• glass frit is deposited between the grid strands and beyond to form an overlayer on the strands. After annealing, the surface is then leveled to the level of the strands.
• An electroconductive coating covering the grid and the filler layer preserves the smoothing and distributes the current.
• the electroconductive coating is ⁇ deposited by spraying to obtain a resistivity p1 of the order of 10 4 4 OOhhmm. cm, with a thickness starting from 40 nm or is PEDOT / PSS deposited by liquid way.
• the present invention a conductive support for OLED comprising in this order:
• a glass substrate transparent, optionally translucent, in particular if textured on the surface
• organic or inorganic glass of refractive index n-1 in a range from 1.3 to 1.6, with a first main surface, referred to as the first surface;
• an electrode which comprises a layer arranged in a grid, referred to as a metal grid, made of metal material (pure or alloy, monolayer or multilayer) having a resistance per square less than 20 ⁇ / a, better at 10 ⁇ / a the metal gate having a thickness e2 of at least 100 nm and preferably at most 1500 nm, the gate being formed of strands (in other words tracks),
• the support comprising (on the side of the first surface and) under the metal grid:
• an electrically insulating light extraction layer typically by volume and / or surface diffusion of the light, of given thickness e 0 , preferably comprising (consisting of):
• the first surface of the substrate which is diffusing textured to be diffusing
• an additional diffusing layer (preferably directly) on the first surface of the substrate (plane or textured), of material, preferably (essentially) mineral, with diffusing elements, for example material which has a refractive index n 4 of From 1.7 to 2.3, preferably from 1.80 to 2.10, and in particular from 1.85 to 2.00, and with diffusing elements preferably having a refractive index n e distinct from n 4 , preferably distinct. at least 0.1, preferably at least 0.2 and in particular at least 0.25,
• a layer partially structured in thickness preferably electrically insulating, with a given composition of refractive index n 3 of 1.70 to 2.3, preferably from 1.80 to 2.10 and in particular from 1.85 to 2.00, which is (preferably directly) on the light extraction layer, partially structured layer in particular underlying and in contact with the gate if necessary, the difference in absolute value n 3 - n 4 being preferably less than 0.1 -, a partially structured layer formed:
• a structured region (furthest from the light extraction layer) with cavities, preferably electrically insulating region, including the non-electroconductive domains, the cavities at least partially containing the metal gate,
• low region Another region, the closest to the light extraction layer, called low region (unstructured), preferably directly on the light extraction layer, and preferably electrically insulating.
• the partially structured layer is not entirely under the grid.
• the bottom of the cavities is under the grid.
• the structured region at least partially houses the metal grid.
• the support comprises on the side of the first surface:
• an electrically insulating light extraction layer typically by volume and / or surface diffusion of the light, of given thickness e 0 , under the metal grid, preferably comprising (consisting of):
• the first surface of the substrate which is diffusing textured to be diffusing
• an additional diffusing layer (preferably directly) on the first surface of the substrate (plane or textured), of material, preferably (essentially) mineral, with diffusing elements, for example material which has a refractive index n 4 of From 1.7 to 2.3, preferably from 1.80 to 2.10, and in particular from 1.85 to 2.00, and with diffusing elements preferably having a refractive index n e distinct from n 4 , preferably distinct. at least 0.1, preferably at least 0.2 and in particular at least 0.25,
• low region Another region, the closest to the light extraction layer, called low region (unstructured), under the metal gate, preferably directly on the light extraction layer.
• the gap H between the so-called high surface (farthest from the substrate) of the non-electroconductive domains and the surface of the metal gate (said upper surface, furthest from the substrate) is, in absolute value, less than or equal to 100 nm, preferably less than or equal to 50 nm, still more preferably less than or equal to 20 nm. It is further preferred to measure H between the top surface and the grid surface at the center of the cavity.
• the total thickness E between the first surface of the substrate and the (lower face of the) metal gate is preferably at least 1 ⁇ better between 5 and 30 ⁇ .
• the surface of the grid assembly and high surface is sufficiently leveled by the small gap H. This limits the risk of short circuits.
• the grid can indifferently emerge from the high surface or be recessed in the cavities.
• the grid is preferable for the grid to be flush with the high surface, particularly for simplicity of embodiment.
• the thickness e 2 of the metal gate is (preferably) lower, greater than or equal to the height e c of the cavities between the non-electroconductive domains preferably e c of at least 80 nm or even 100 nm. It is easy to make deep cavities so e c can easily be higher than the grid even thicker.
• the strands are interconnected in the active area of the OLED or connected (only) via their ends to electrical contacts.
• the grid not be in contact with the surface of the light extraction layer but anchored in the partially structured layer preferably planar locally at least to the relevant scale for short circuits or in a range of lengths. less than 50 ⁇ and for example greater than 10 ⁇ .
• the partially textured layer is preferably directly on the light extraction layer, in particular preferably able to cover or fill the roughness profile of the first diffusing surface of the glass or of an additional diffusing layer.
• the upper surface of the partially structured layer therefore does not reproduce (nor amplify) the roughness of the first diffusing surface of the glass or of the additional diffusing layer.
• the partially structured layer has little or no scattering particles, and even does not have a (significant) scattering function.
• the structured region in particular made of vitreous material and preferably enamel, is preferably free of scattering particles throughout its thickness.
• the structured region preferably electrically insulating, preferably vitreous material and better still enamel, contains no or few surface pores and even in thickness.
• the lower region in particular vitreous material and preferably enamel, is preferably free of scattering particles throughout its thickness.
• the lower region optionally contains (only) pores (air or gas bubble), diffusing or not, especially a volume concentration of less than 0.5%, preferably less than 0.2% and in particular less than 0.1 %.
• the lower region especially in vitreous material and preferably in enamel, may contain pores but in such a small quantity and / or so small (non-diffusing) that they do not render the partially structured layer diffusing , in particular, does not increase the blur value of the substrate / light extraction layer / partially structured layer assembly with respect to substrate blurring / light extraction layer alone.
• the partially structured layer may contain pores but in such a small amount and / or so small (non-diffusing) that they do not make this layer (significantly) diffusing and preferably do not disturb not the high surface.
• the upper surface of the partially structured layer, especially of vitreous material and preferably enamel may preferably have a roughness Ra (well known parameter Ra which is the arithmetic average deviation of the profile) less than 5 nm, better 3 nm and even 1 nm.
• Ra can be defined according to the IS04287 standard and measured by atomic force microscopy in 256points on 10 ⁇ by 10 ⁇ .
• the number of macroscopic defects (greater than 5 ⁇ m in size) of the upper surface is less than 1 per cm 2 . This number can be evaluated by optical microscopy.
• the surface of the layer intended to form the partially structured layer may have large-scale corrugations, for example an amplitude of 1 ⁇ over 100 to 200 ⁇ of lateral period W.
• the upper surface of the partially structured layer may have the same corrugations for B of at least 300 ⁇ . They are not a source of short circuit.
• the partially structured layer may be of thickness e3 greater than 3 ⁇ , preferably less than 30 ⁇ .
• the light extraction layer is an additional diffusing layer in a high index matrix and with scattering particles dispersed in the matrix
• the preferred range is 5 to 15 ⁇ m.
• e 3 is greater than 5 ⁇ and even ⁇ and even better 9 ⁇ , and preferably e 3 is less than 30 ⁇ and better than or equal to 25 ⁇ .
• the preferred range is 9 to 20 ⁇ .
• the partially structured layer preferably electrically insulating, is mineral, preferably based on oxide (s) or substantially oxide (s), and even more preferably a vitreous material, in particular an enamel, based on molten glass frit.
• the partially structured layer may for example consist of the vitreous material of the additional diffusing layer, or of another vitreous material.
• the interface between the additional diffusing layer and the partially structured layer is not necessarily "marked” / observable even if deposited one after the other.
• the partially enameled layer may contain pores but in such small amounts and / or so small that they do not render the (significantly) diffusing layer and / or preferably do not disturb the upper surface.
• the additional diffusing layer may be a monolayer or a multilayer, may have a gradient of diffusing elements (preferably a decrease of diffusing elements including particles and / or bubbles in the direction of the grid) in particular be a bilayer with a gradient of diffusing elements and / or distinct diffusing elements (nature and / or concentration).
• the additional diffusing layer in particular enamel, may have a thickness e 4 of between 1 ⁇ and ⁇ , in particular from 2 to 30 ⁇ and even from 3 to 20 ⁇ .
• the diffusing elements in particular the diffusing particles, can be distributed homogeneously in the vitreous material. They may alternatively be distributed in a heterogeneous manner, for example by providing gradients.
• the additional diffusing layer may also consist of several elementary layers differentiating from each other by a different nature, size or proportion of diffusing elements.
• the diffusing elements are chosen from particles and pores.
• the additional diffusing layer can contain both particles and pores.
• the particles are preferably chosen from particles of alumina, zirconia, silica, titanium dioxide, calcium carbonate and barium sulfate.
• the diffusing layer may comprise a single type of particles, or several different types of particles.
• the diffusing elements preferably have a characteristic dimension allowing diffusion of the visible light.
• the diffusing elements (particles in particular) preferably have a mean diameter, determined by DLS ("dynamic light scattering" in English), between 0.05 and 5 ⁇ , in particular between 0, 1 and 3 ⁇ .
• the mass concentration of diffusing particles of the additional diffusing layer is preferably in a range from 0.2 to 10%, especially from 0.5 to 8%, and even from 0.8 to 5%.
• the chemical nature of the scattering particles is not particularly limited, they are preferably selected from TiO 2 and SiO 2 particles.
• a diffusing layer in the form of a polymeric material comprising diffusing particles for example described in EP1406474 is possible.
• the optional additional diffusing layer is preferably inorganic, preferably based on oxide (s), more preferably on oxide (s), and the partially structured layer is preferably mineral, preferably based on oxide (s). , in particular identical to the additional diffusing layer and preferably the glass is mineral.
• the additional diffusing layer is a mineral layer, directly on the substrate, of high-index mineral material based on oxide (s), preferably a vitreous material, in particular an enamel, and the diffusing elements preferably are of mineral type (pores, precipitated crystals, hollow or solid particles, for example oxides or non-oxide ceramics, etc.).
• oxide preferably a vitreous material, in particular an enamel
• the diffusing elements preferably are of mineral type (pores, precipitated crystals, hollow or solid particles, for example oxides or non-oxide ceramics, etc.).
• the substrate is preferably made of mineral glass
• the light extraction layer comprises (or consists of) an additional diffusing layer with diffusing elements and a material which comprises (in particular consists of) a vitreous material, preferably a enamel
• the composition of the partially structured layer comprises (in particular consists of) a vitreous material, preferably an enamel, composition preferably identical to the material of the additional diffusing layer
• the composition of the partially structured layer comprises (in particular consists of) a material vitreous, preferably an enamel.
• An enamel layer according to the invention (partially structured layer and / or additional diffusing layer) is preferably obtained by a process in which a glass frit (of the same chemical composition as the material) is mixed with a typically organic medium to form a paste, optionally containing diffusing particles, which is preferably deposited by screen printing on the first surface, in mineral glass, before baking it.
• the pores are preferably formed during cooking by removal of organic compounds, for example medium. They are preferably closed and not connected.
• Enamel diffusing layers and high index enamel layers on diffusing layers are known in the art and are described for example in EP2178343 and WO201 1/089343. High index compositions are also described in WO2010084922 and WO2010084925.
• the partially structured enamel layer of index n 3 can comprise a high level of bismuth oxide, for example at least 40% by weight and better still at least 55%, and preferably at least 55% by weight. 'not more than 85%.
• the Tg is measured by Differential Scanning Calorimetry (DLC).
• the firing temperature to form the enamel is greater than the Tg but must not soften the glass substrate.
• the cooking temperature is below 600 ° C., even below 570 ° C., especially when the Tg is less than or equal to 500 ° C.
• the additional diffusing layer can (also) be enamel (diffusing).
• An enamel with a glass transition temperature Tg of less than 600 ° C. and better still less than or equal to 550 ° C. or even lower than or equal to 500 ° C. is preferably chosen.
• the diffusing enamel may have a high index, of at least 1.7, comprising a high level of bismuth oxide, for example at least 40% by weight and better still at less than 55% by weight, and preferably not more than 85%.
• the Tg is measured by Differential Scanning Calorimetry (DLC).
• the firing temperature to form the enamel is greater than the Tg but must not soften the glass substrate, preferably the firing temperature is lower. at 600 ° C., even below 570 ° C., especially when the Tg is less than or equal to 500 ° C.
• the first surface may be rough enough to be diffusing.
• Rough interfaces for extracting the light emitted by the OLED organic layers are known and described, for example, in WO2010 / 1 12786, WO02 / 37568 and WO201 1/089343.
• the roughness of the first surface of the substrate may be obtained by any appropriate means known, for example by acid etching (hydrofluoric acid), sanding or abrasion.
• the texturing of the first surface of the (diffused) substrate is preferably non-periodic, especially random, for the white light application.
• 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.
• Ra can to be defined according to IS04287 and measured by atomic force microscopy.
• Ra is micronic, preferably less than 5 ⁇ or even 3 ⁇ .
• the blur of the glass substrate assembly and the light extraction layer and possibly the partially structured layer
• the blur is at least 60%, better 70, and even 80% or 90%.
• the blur sometimes called “veil” is measured by a haze-meter, like that of the BYK company, taking the protocol defined in ASTM D1003.
• the substrate is not diffusing (by a first diffusing surface, rough), it is preferred that it has a blur of less than 5%, better still 2% and even less than 1%.
• the substrate and light extraction layer have a light transmission T L of at least 40% or even 50% and preferably an absorption of at most 5% or even 3%,
• the substrate - light extraction layer preferably glassy material, enamel
• the substrate - light extraction layer preferably glassy material, enamel
• the substrate - light extraction layer partially structured layer (preferably vitreous material, better enamel and directly on the light extraction layer) has a T L of at least 40% or even 50%, and preferably an absorption of at most 5% or even 3%.
• the partially structured layer (and preferably the electrode) preferably electrically insulating covers at least 80%, especially 90% and even 95% of the surface of the substrate.
• the partially structured layer according to the invention may be over a large area, for example an area greater than or equal to 0.02 m 2 or even greater than or equal to 0.5 m 2 or 1 m 2 .
• the grid according to the invention may be over a large area, for example an area greater than or equal to 0.02 m 2 or even greater than or equal to 0.5 m 2 or 1 m 2 .
• This layer for example deposited by physical vapor deposition PVD is generally surface-conforming to the surface of the substrate, to the underlying surface and therefore does not play (or little) the role of planarization.
• the alkali barrier or etch protection layer may be based on silicon nitride, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, or silica, alumina, titanium oxide, silicon dioxide, silicon tin oxide, aluminum nitride, titanium nitride, Ti (Zr) O for example of thickness less than or equal to 30 nm and preferably greater than or equal to 3 nm or even 5 nm. It can be a multilayer.
• a moisture barrier layer can be added to the selected plastic substrate (diffuse rendered surface or flat surface).
• the barrier layer may be based on silicon nitride, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, or silica, alumina, titanium oxide, tin oxide, aluminum nitride, titanium nitride, for example with a thickness of less than or equal to 10 nm and preferably greater than or equal to 3 nm or even 5 nm. It can be a multilayer.
• all refractive indices are defined at 550 nm.
• the electroconductive support according to the invention can be used for a rear-emission organic electroluminescent device ("bottom emission” in English) or for an organic electroluminescent device emitting from the rear and the front.
• any dielectric layer can be doped. Doping is understood in a usual way as exposing a presence of the element in an amount of less than 10% by weight of metal element in the layer.
• a metal oxide or nitride may be doped in particular between 0.5 and 5%.
• Any metal oxide layer according to the invention may be a single oxide or a mixed oxide doped or not.
• a layer or coating deposit (comprising one or more layers) is carried out directly under or directly on another deposit, it is that there can be no interposition of 'no layer between these two deposits.
• the cavities are at least partially filled by the metal grid.
• Cavities (U-type) are delimited by a bottom and straight flanks (normal, perpendicular to the substrate) or flared away from the substrate.
• L between the high surface and the low surface
• L ⁇ 1, 4e c better ⁇ 1, 2e c in order to preserve the transparency. It is thus preferred to limit the spreading (lateral) cavities to reduce the width of the strands at best.
• a large thickness is preferred to a large size of the strands to gain transparency.
• the cavities may form one-dimensional grooves, regularly spaced or not (of a distance B c ), in particular disjoint (at least in the light-emitting zone) of any shape, for example linear or sinuous.
• the cavities may form a mesh, that is to say a network of interconnected openings (two-dimensional), periodic or aperiodic, of regular or irregular mesh, of any shape: geometric in particular (square, rectangle, honeycomb).
• the mesh can be defined by a maximum width (between two stitches) B c .
• the cavities separating the non-electroconductive domains may be of height e c of at least 50 nm or even 80 nm, or 100 nm and preferably less than 1500 nm or 1200 nm and of width A c less than or equal to 50 ⁇ m, better at 30 ⁇ m and preferably from minus 1 ⁇ , or 1, 5 ⁇ .
• e c is preferably taken in the center of the cavity.
• a gate strand emerges from the cavity, it is preferred that the strand does not extend over the edges of the high surface at the periphery of the cavity, or over a reduced distance of less than 500 nm, better still less than 200 nm and even less than 50 nm or 10 nm.
• the grid may be in the form of linear strands parallel to each other and connected
• the grid may have a zone with lines (strands or strips) and a zone with closed patterns (strands or meshed tracks).
• the structuring of the partially structured layer is adapted for this purpose.
• the thickness e2 is not necessarily constant in a cavity. It can preferably be defined in the center (so-called central thickness).
• the width A is not necessarily constant in a cavity. It can be defined at the top surface of the grid and / or preferably as the maximum width.
• B the maximum distance between the strands in particular corresponding to a maximum distance between two points of a mesh or the maximum distance between two disjoint neighboring strands type grooves (rights or not).
• a and B may vary from one strand to another. As the grid may be irregular and / or the edges of the strands may be inclined, the dimensions A and B are therefore preferably average dimensions on the strands as e 2 .
• the thickness e 2 may be less than 1500 nm, more preferably 1000 nm, especially 100 nm to 1000 nm, or 800 nm and in particular 200 nm to 800 nm or 650 nm.
• the width (average, preferably maximum) A is less than 30 ⁇ , preferably 1 to 20 ⁇ , even more preferably 1, 5 ⁇ to 20 ⁇ or 15 ⁇ .
• B can be at least 50 ⁇ and even at least 200 ⁇ and B is less than 5000 ⁇ , better than 2000 ⁇ or even ⁇ ⁇ .
• Another possible characterization of the metal grid according to the invention is a coverage ratio T which is preferably less than 25% and more preferably 10%, and even 6% or 2%.
• a B between 2000 and 5000 ⁇ when e 2 is between 800 and 1500nm and A is between 10 and 50 ⁇ . This corresponds to a coverage rate of between 0.4 and 6.0%.
• a B may be desired between 200 and ⁇ ⁇ when e 2 is less than 500 nm and A is between 3 and 20 ⁇ m or even 3 to 10 ⁇ m. This corresponds to a coverage rate of between 0.5 and 22% or even 0.5 to 1 1%.
• the metal grid is obtained by silvering and even better directly in the cavities.
• PVD physical vapor deposition
• a mask such as a (photo) resin
• the lateral zones of the strands are in a bowl , forming a rupture of morphology that sometimes generate short circuits, even if the surface roughness of the grid is quite low.
• silvering is simple, less complex (no vacuum installations etc.) than "PVD", and is suitable for any grid size.
• silvering conventionally used in a full layer is well suited for depositing in cavities.
• the electrical conductivity of the silver-deposited silver is satisfactory.
• the strands are elongated- disjoint or interconnected (at least in the light emitting region), in particular in mesh, the strands having along their length a central zone between peripheral lateral zones, lateral peripheral zones (flat and) flush with the upper surface, and surface roughness of the central zone, preferably flush with the upper surface, is greater than the surface roughness in the peripheral zones.
• each peripheral (planar) lateral zone is at most 5 nm and even at most 3 nm and even at most 2 nm or 1 nm. And preferably Rmax (maximum height) in each peripheral (planar) peripheral zone is at most 20 nm and even at most 10 nm.
• each peripheral lateral zone is of width L1 greater than or equal to the height e c of the cavity with L1 ⁇ 1, 4e c and even L1 ⁇ 1, 2e c .
• L1 is generally substantially equal to the horizontal distance L.
• the roughness parameter (well known) Rq (or rms) in the central zone (the roughest) is at least 10 nm and even at least 20 nm (and preferably at most 60 nm). And preferably Rmax (maximum height) in the central zone (rough) is at least 100 nm and even at least 150 nm (and preferably at most 500 nm).
• the roughness of the central zone will depend on the thickness of the metal grid, will increase with thickness.
• Rmax and Rq of the grid can be defined according to the standard IS04287 and measured by atomic force microscopy.
• a lateral zone flush with the upper surface may be strictly on the same plane as the upper surface or deviate from it by at most 10 nm and better not more than 5 nm.
• the metal gate according to the invention may have a square resistance of less than or equal to 10 ohm / square, preferably less than or equal to 50 MHz / square, and even 10 oh / square.
• the grid may be based on a pure metallic material selected from silver, aluminum or even platinum, gold, copper, palladium, chromium or based on said alloy material or doped with at least one other material: Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn.
• the material or materials of the metal grid are chosen particularly in the group consisting of silver, copper, aluminum, gold, and alloys based on these metals and is preferably based on silver. Silver is preferred (optionally oxidized on the surface).
• the metal grid may be monolayer (silver) or multilayer (preferably with at least 80% even 90% silver).
• the metal grid may be multilayer, in particular multilayer silver, and include (or be incorporated) -in this order-:
• a first metallic layer in particular a bonding layer (directly on the bottom of the cavities or metal layer closest to the bottom of the cavities), preferably in a first metallic material, which is preferably based on silver, or even consisting of silver, forming less than 15% and even 10% of the total thickness e 2 of the gate and / or at least 3 nm, 5 nm or even at least 10 nm, and preferably less than 100 nm or even 50 nm,
• a second metal layer (on the first layer, away from the substrate), in particular with a discernable interface with the first layer, based on a second metal material which is preferably chosen from silver, aluminum or copper , forming at least 70%, 80% and even 90% of the total thickness e 2 of the second layer grid which is preferably based on silver or even made of silver, especially as the first layer.
• first silver-based metal layer according to a first deposition method, for example deposited by silver-plating, preferably with a thickness of at least 20 nm and even 30 nm, or by vacuum deposition (sputtering) and a second layer.
• silver-based metal with a thickness of at least 3 nm or even 5 nm, according to a second method of deposition preferably which is electroplating.
• the advantage of electroplating is a higher silver utilization rate than silvering and a less expensive method of spraying.
• the metal grid may be multilayered with layers of different materials, for example with a final layer of protection against corrosion (water and / or air), for example metallic, in a material distinct from the underlying metallic layer, in particular distinct silver, less than 10nm thick better than 5nm or even 3nm. This layer is useful in particular for a silver-based grid.
• a final layer of protection against corrosion water and / or air
• metallic in a material distinct from the underlying metallic layer, in particular distinct silver, less than 10nm thick better than 5nm or even 3nm. This layer is useful in particular for a silver-based grid.
• the metal grid can be further multilayered with two layers of different materials, for example bilayer, and composed of:
• a (single) metal layer made of the abovementioned materials, preferably based on, or even in silver, with a thickness of at least 100 nm preferably, for example deposited by silver plating or vacuum deposition (spraying),
• an overcoat of protection against corrosion for example metallic, made of a material distinct from the metallic layer, in particular distinct from silver, with a thickness of less than 10 nm, better than 5 nm or even 3nm.
• the protective overcoat can be deposited using the same technique as the deposition of the underlying metal layer, for example by vacuum deposition (evaporation, spraying), in the same deposition frame preferably or by liquid, for example by silvering.
• the metal grid may be multilayer with layers of different materials, for example three-layer and composed:
• the above-mentioned metal multilayer preferably at least one second metallic layer of silver and even preferably a multilayer of silver, and an overcoat of protection against corrosion (water and / or air), for example of metallic material distinct from silver, of thickness less than 10 nm, better than 5 nm or even 3 nm, the overcoat is deposited under vacuum (by evaporation or spraying), and preferably by electrodeposition.
• the protective overlay can be deposited using the same technique as the deposition of the (last) layer of grid, for example by electrodeposition.
• the protective overcoat preferably comprises a metal layer based on at least one of the following metals: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr , Mo, Ta, W, or based on an alloy of at least one of said materials, preferably based on Ni, or Ti, based on a Ni alloy, based on a NiCr alloy.
• it may consist of a layer based on niobium, tantalum, titanium, chromium or nickel or an alloy from at least two of said metals, such as a nickel-chromium alloy.
• a thin layer based on a metal chosen from niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel Ni or an alloy from at least two of these metals is preferred. especially an alloy of niobium and tantalum (Nb / Ta), niobium and chromium (Nb / Cr) or tantalum and chromium (Ta / Cr) or nickel and chromium (Ni / Cr).
• a thin metal blocking layer can be easily manufactured without altering the silver conduction metal layer.
• This metal layer may preferably be deposited in an inert atmosphere (that is to say without voluntary introduction of oxygen or nitrogen) consisting of noble gas (He, Ne, Xe, Ar, Kr). It is not excluded or annoying that on the surface this metal layer is oxidized during the subsequent deposition of a metal oxide layer.
• the thin blocking layer may be partially oxidized of the MO x type, where M is the material and x is a number less than the stoichiometry of the material oxide or of the MNO x type for an oxide of two M and N materials (or more).
• M is the material
• x is a number less than the stoichiometry of the material oxide or of the MNO x type for an oxide of two M and N materials (or more).
• X is preferably between 0.75 and 0.99 times the normal stoichiometry of the oxide.
• x For a monoxide, it is possible in particular to choose x between 0.5 and 0.98 and for a x-dioxide between 1.5 and 1.98.
• the thin blocking layer is based on TiO x and x can be in particular such that 1, 5 x x 1 1, 98 or 1, 5 x x 1 1, 7 or even 1, 7 x ⁇ 1, 95.
• the thin blocking layer may be partially nitrided. It is therefore not deposited in stoichiometric form, but in sub-stoichiometric form, of the type MN y , where M represents the material and is a number less than the stoichiometry of the the nitride of the material is preferably between 0.75 and 0.99 times the normal stoichiometry of the nitride.
• the thin blocking layer can also be partially oxynitrided.
• the thin blocking layer is preferably obtained by spraying or evaporation, in particular on a (last) gate material deposited in the same frame under vacuum, by spraying or evaporation (without venting).
• the grid can be deposited directly on the partially structured layer or on a dielectric underlayer, said hooked (function of hooked to facilitate the deposition of gate material), directly on the cavities (the bottom and preferably all or part of the flanks of the cavities) of the partially structured layer and preferably absent from the upper surface, preferably mineral bonding layer, in particular oxide (s), for example a transparent conductive oxide. It is of thickness e A less than 30 nm even at 10 nm. Naturally, the height of the cavity e c is preferably greater than e A and better e c - e A greater than 50 nm.
• This hooked layer is easily deposited by magnetron sputtering.
• the electroconductive support may comprise an electrically conductive coating that covers, preferably directly, electrically conductive areas 31 and not the metal grid 20, in particular electrically conductive coating of thickness e of 5 or less than 500 nm, resistivity p of less than 5 20Q.cm, same at 10 ⁇ .cm or at 1 ⁇ .cm and even at 10 " Q.cm and higher than the resistivity of the metal gate, and is of given refractive index n 5 of at least 1.55 better 1, 6 and even better 1, 7.
• ⁇ 1000 ⁇
• e 5 100nm
• a resistivity of less than 0.1 Ohm is preferred. cm.
• the electroconductive coating according to the invention by its resistivity, its cover of the grid and its thickness, contributes to a better distribution of the current.
• the surface of the electroconductive coating may preferably be intended to be in contact with the organic layers of the OLED: in particular the hole injection layer ("HIL” in English) and / or the hole transport layer (“HTL”). In English) or be part of H IL or HTL or play the role of HTL or HIL.
• HIL hole injection layer
• HTL hole transport layer
• the (outer) surface of the electroconductive coating may further have very large scale corrugations, typically of 0.1 mm or one or more millimeters.
• the substrate, and by the same the external surface, can be curved.
• the electroconductive coating is monolayer or multilayer.
• the coating may have (a last layer with) a higher output work than the metal grid.
• the coating may have an output work adaptation layer which may have, for example, an output work Ws from 4.5 eV and preferably greater than or equal to 5 eV.
• the electroconductive coating may thus comprise (or consists of) an inorganic layer of refractive index n is between 1, 7 and 2.3, preferably which is the last layer of the coating (furthest from the substrate), in particular for adjusting the output work, preferably of thickness less than 150 nm, based on an electroconductive transparent oxide, a single or mixed oxide, especially based on at least one of the following metal oxides, optionally doped: tin, indium oxide, zinc oxide, molybdenum oxide MoO 3 , tungsten oxide WO 3 , vanadium oxide V 2 O 5 , ITO, IZO, Sn x Zn y O z ,
• This mineral layer preferably has a thickness less than or equal to 50 nm or even 40 nm or even 30 nm and is easily resistivity less than 10 " Q.cm.
• a layer deposited by physical vapor deposition, in particular by magnetron sputtering, chosen from ITO, MoO 3 , and WO 3 of V 2 O 5 is chosen.
• the mineral layer of the electroconductive coating is preferably obtained by spraying or evaporation, in particular on a (last) grid material deposited by the same method.
• Is preferably meant indium tin oxide (or tin-doped indium oxide or ITO for the English name: Indium tin oxide) a mixed oxide or a mixture obtained from indium oxides ( III) (In 2 0 3 ) and tin (IV) (SnO 2 ), preferably in the mass proportions of between 70 and 95% for the first oxide and 5 to 20% for the second oxide.
• a typical mass proportion is about 90% by weight of ln 2 0 3 for about 10% by weight of Sn0 2 .
• the electroconductive coating may be made of the mineral layer having a refractive index n is between 1, 7 and 2.3, then equal to n 5.
• the electroconductive coating may comprise or consist, at least in the last layer (of the coating) farthest from the substrate, of an organic polymer layer (s) conductor (s), thickness e2 submicron, of refractive index n b of at least 1.55, better 1, 6, this polymeric layer being able to act as a Hole Transport Layer (HTL) or Hole Injection Layer (HIL) an electroluminescent organic system.
• the electroconductive coating may consist of the organic refractive index layer n b between 1.7 and 2.3, then equal to n 5 .
• it is a layer of one or more conducting polymers of the family of polythiophenes, such as PEDOT, that is to say 3,4-polyethylenedioxythiopene or PEDOT / PSS, that is, that is 3,4-polyethylenedioxythiopene mixed with polystyrene sulphonate.
• PEDOT polythiophenes
• PSS polystyrene sulphonate
• PEDOT or PEDOT PSS commercially, we can mention the company Heraeus:
• the conductive polymer is part of the electrode and optionally also serves as a hole injection layer (HIL).
• HIL hole injection layer
• the electroconductive coating may be multilayer and comprises (preferably directly) under the aforementioned mineral layer (in particular the last layer) or the aforementioned organic layer (in particular the last layer), a first layer directly on the metal grid (monolayer or multilayer grid), transparent electroconductive oxide, e'5 thickness less than 200 nm, of n'5 index between 1, 7 and 2.3, the absolute difference n'5- n 3 preferably being ⁇ 0, 1 in particular chosen from:
• a layer in particular amorphous
• zinc oxide and SnZnO tin preferably less than 100 nm thick
• IZO indium and zinc oxide
• ITZO indium, zinc and tin oxide
• the AZO or GZO layer may, for example, make it possible to reduce the thickness of the mineral layer, in particular of the ITO layer, to less than 50 nm.
• a layer of a ZnO oxide is preferably doped Al (AZO) and / or Ga (GZO) with the sum of the weight percentages of Zn + Al or Zn + Ga or Zn + Ga + Al or Zn + other dopant of preferably selected from B, Se, or Sb or even from Y, F, V, Si, Ge, Ti, Zr, Hf and even by In which is at least 90% by total weight of metal better than at least 95 % and even at least 97.
• an AZO layer according to the invention that the percentage by weight of aluminum on the sum of the percentages by weight of aluminum and zinc, in other words AI / (AI + Zn), is less than 10% preferably less than or equal to 5%.
• a ceramic target of aluminum oxide and zinc oxide such that the percentage by weight of aluminum oxide on the sum of the percentages by weight of zinc oxide and aluminum oxide, typically Al 2 O 3 (Al 2 O 3 + ZnO), is less than 14%, preferably less than or equal to 7%.
• the percentage by weight of gallium over the sum of the percentages by weight of zinc and gallium in other words Ga / (Ga + Zn), is less than 10% and preferably less than 10%. or equal to 5%.
• a zinc oxide and gallium oxide ceramic target such as the percentage by weight of gallium oxide on the sum of the weight percentages of zinc oxide and gallium oxide, typically Ga 2 0 3 (Ga 2 O 3 + ZnO) is less than 1 1%, preferably less than or equal to 5%.
• the total weight percentage of Sn metal is preferably from 20 to 90% (and preferably from 80 to 10% for Zn) and 30 to 80% (and preferably 70 to 20% for Zn), in particular the weight ratio Sn / (Sn + Zn) is preferably from 20 to 90% and in particular from 30 to 80%.
• the electroconductive support may also include a temporary protective layer
• the substrate may be flat or curved, and further rigid, flexible or semi-flexible. Its main faces can be rectangular, square or even any other shape (round, oval, polygonal ). This substrate may be large, for example, top surface to 0.02 m 2, or even 0.5 m 2 or 1 m 2 and a lower electrode substantially occupying the surface (the structuring zones).
• the substrate may be substantially transparent, mineral or plastic such as polycarbonate PC or polymethyl methacrylate PMMA or PET, polyvinyl butyral PVB, PU polyurethane, polytetrafluoroethylene PTFE etc.
• the substrate is preferably made of mineral glass, in particular of silicosodocalcic glass obtained by the floating process (the so-called "float" process), of pouring the molten glass on a bath of molten tin.
• the substrate is preferably colorless and has (only) a light transmission factor of at least 80% or even 90% within the meaning of EN 410: 1998.
• the substrate may advantageously be a glass having an absorption coefficient of less than 2.5 m -1 , preferably less than 0.7 m -1 at the wavelength of the OLED radiation (s).
• silicosodocalcic glasses with less than 0.05% Fe III or Fe 2 O 3 are chosen, for example Saint-Gobain Glass Diamond, Pilkington Optiwhite glass, Schott B270 glass.
• the thickness of the glass substrate may be at least 0.1 mm, preferably in a range from 0.1 to 6 mm, in particular from 0.3 to 3 mm.
• the support as defined above may further comprise an organic electroluminescent system deposited (preferably directly) on the electroconductive coating optionally including HTL hole transport layer or HIL hole injection.
• the invention also relates to an organic electroluminescent device incorporating the support as defined above, the gate electrode forming the so-called lower electrode, the closest to the substrate.
• TCC transparent conductive coating
• the upper electrode may be an electroconductive layer advantageously chosen from metal oxides, in particular the following materials: doped zinc oxide, especially aluminum ZnO: Al or gallium ZnO: Ga, or else indium oxide doped, especially tin (ITO) or zinc doped indium oxide (IZO).
• metal oxides in particular the following materials: doped zinc oxide, especially aluminum ZnO: Al or gallium ZnO: Ga, or else indium oxide doped, especially tin (ITO) or zinc doped indium oxide (IZO).
• transparent electroconductive layer for example a “TCO” (“Transparent Conductive Oxide”) layer, for example of thickness between 20 and 1000 nm.
• TCO Transparent Conductive Oxide
• the OLED device can produce monochromatic light, especially blue and / or green and / or red, or be adapted to produce white light.
• mixture of compounds in a single layer, stack on the face of the electrodes of three organic structures (green red emission, blue) or two organic structures (yellow and blue), a series of three organic adjacent organic structures (emission red green, blue), on the face of the electrodes an organic structure in one color and on the other side suitable phosphor layers.
• the OLED device may comprise a plurality of adjacent organic electroluminescent systems, each emitting white light or, in a series of three, red, green and blue light, the systems being for example connected in series.
• Each row can for example emit according to a given color.
• OLEDs are generally dissociated into two major families depending on the organic material used. If the electroluminescent layers are small molecules, they are called SM-OLEDs ("Small Mollecule Organic Light Emitting Diodes").
• the organic electroluminescent material of the thin layer consists of evaporated molecules such as for example the complex of AIQ 3 (tris (8-hydroxyquinoline) aluminum), DPVBi (4,4 '- (diphenylvinylene biphenyl)), the DMQA (dimethyl quinacridone) or DCM (4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran) .
• the emitting layer can also be for example a layer of 4.4 f , 4 i '-tri (N-carbazolyl) TRIPHENYLAMINE (TCTA) doped with fac tris (2-phenylpyridine) iridium [lr (ppy) 3].
• an SM-OLED consists of a hole injection layer stack or "HIL” for "Hole Injection Layer” in English, hole transport layer or “HTL” for "Hole Transporting” Layer “in English, emissive layer, electron transport layer or” ETL “for” Electron Transporting Layer "in English.
• HIL hole injection layer stack
• HTL hole transport layer
• ETL Electron Transporting Layer
• organic electroluminescent stacks are for example described in US 6,645,645.
• organic electroluminescent layers are polymers, they are called PLED (Polymer Light Emitting Diodes).
• the electroconductive coating is resistant to the following OLED manufacturing steps:
• a light extraction means may also be located on the outer face of the substrate, that is to say the face which will be opposite to the first main face carrying the grid electrode. It may be a microlens array or micropyramid as described in the article in Japanese Journal of Applied Physics, Vol. 46, No. 7A, pages 4125-4137 (2007) or a satin, for example a frosted satin treatment with hydrofluoric acid.
• the invention finally relates to a method of manufacturing an electroconductive support as defined above which comprises the following steps in this order:
• the supply of the substrate comprising: the light extraction layer formed by the first diffusing surface of the substrate and / or formed by the additional diffusing layer (preferably directly) on the substrate, for example a diffusing surface,
• a so-called high index layer in the composition with said refractive index n 3 , which comprises said vitreous material, in particular free of diffusing particles and which optionally contains pore-type elements at a concentration volume less than 0.5%, preferably less than 0.2% and in particular less than 0.1%, and preferably covering the roughness profile of the diffusing surface, - the formation of blind openings called cavities in the high index layer 3a, thus forming the partially structured layer, comprising:
• the etching of the high-index layer through the through-openings of the mask (of width A m substantially equal to A, of distance between openings B m substantially equal to B), in particular straight (perpendicular to the substrate) or flared in the opposite direction of substrate,
• the formation of the metal grid (with the difference H between the so-called high surface of non-electroconductive domains and the surface of the metal gate) comprising:
• a first deposit said first deposit, of a first metallic material of the gate in the cavities, preferably the only deposit for the metal gate, directly on the bottom of the cavities or on a dielectric underlayer (non-metallic) lining in part of the cavity (under layer hooked), - a possible second deposit of a second metal material of the grid on the first metal material (at least partially in the cavities).
• Etching is preferably carried out by a wet etching process.
• the depth of the cavities is regulated by concentration of the solution, type of solution, etching time, temperature of the solution.
• the mask preferably (photo) resin and even positive photoresin, is then resistant to the etching solution.
• the cavities are on the right flank (perpendicular to the substrate) or flared in the opposite direction of the substrate.
• the section can be in bowl, even (type) semi-spherical.
• an acidic solution with a layer partially structured in vitreous material and preferably the mask is a (photo) resin, in particular photoresin positive.
• Etching with a particularly acidic wet solution is isotropic in the sense that the etching solution (especially acidic) attack (hollow) in all directions.
• the etching profile can be in bowl, semi-spherical type.
• the optional hook layer is then deposited before the first metal material.
• the mask (and preferably the majority of the cavities and better all) has a width greater than the width of the through opening of the mask in the plane of the interface between the mask and the high index layer, leaving portions of surfaces of the mask (preferably a (photo) resin) protruding from the upper surface and facing the cavity.
• the first deposit (preferably the only deposit for the metal gate) and is a silvering, and at least partially fills said cavity and the entire height of the sides of the cavity and all or part of said portions of surface (at least 50%, even at least 80%, or even at least 90% of the width of said surface portions) thereby forming laterally peripheral strand regions, smoother than the strand core area facing the opening .
• the removal of the mask is preferably liquid, in particular by ultrasound in a solvent (acetone etc.).
• the money deposited by silvering in the cavities also covers the mask (resin, same photoresist), the flanks of the mask (of the resin, same photoresist). It is preferred that the metal grid has a central zone opposite the opening under flush so that the removal of the mask (of the resin including photoresin) is easier, especially by ultrasound in a solvent (acetone etc.).
• the high index layer preferably comprises (better consists of) an enamel, in particular obtained from a first composition based on glass frit.
• the optional additional scattering layer comprises (better consists of) an enamel obtained from another composition based on glass frit, in particular identical to the first composition.
• the high index layer comprising a vitreous material is preferably an enamel obtained by a process in which:
• a glass frit of index n 3 is mixed with an organic medium so as to form a so-called planarization paste, preferably without adding diffusing particles,
• said paste is deposited, for example by screen printing, - preferably directly on the mineral glass sheet (diffusing surface) or on a mineral barrier layer on the mineral glass sheet (diffusing surface) or on the additional diffusing layer,
• the additional diffusing layer comprising a vitreous material is preferably an enamel obtained by a process in which:
• a glass frit is mixed with an organic medium and preferably with diffusing particles so as to form a so-called diffusion paste
• said paste is deposited, preferably directly, on the mineral glass sheet (flat, polished or textured, diffusing) or on a mineral barrier layer on the mineral glass sheet,
• the additional diffusing layer can be formed by annealing the diffusion paste prior to the deposition of the planarization paste or the two pastes can be annealed together (one step in less annealing).
• the diffusion paste and the planarization paste have the same composition, especially the same glass frit, and differ only in the presence or absence of diffusing particles.
• the organic medium is typically selected from alcohols, glycols, terpineol esters.
• the mass proportion of medium is preferably in a range from 10 to 50%.
• the deposition of the dough can be carried out in particular by screen printing, by roll coating, by dipping, by knife application, by spraying, by spinning, by vertical lapping, or by means of a coating. die-shaped die (slot die coating).
• a screen made of textile or metal mesh, layering tools and a doctor blade the control of the thickness being ensured by the choice of the mesh of the screen and its tension, by the choice of the distance between the glass sheet (or the additional diffusing layer) and the screen, by the pressures and speeds of movement of the doctor blade.
• the deposits are typically dried at a temperature of 100 to 150 ° C by infrared or ultraviolet radiation depending on the nature of the medium.
• the glass frit (70-80% by weight) is mixed with 20-30% by weight of an organic medium (ethyl cellulose and organic solvent).
• an organic medium ethyl cellulose and organic solvent.
• the dough can be heat-treated at a temperature in the range of 120 to 200 ° C, for example to freeze the dough. Then the paste can undergo a heat treatment ranging from 350 to 440 ° C to remove the organic medium.
• the Baking to form the enamel is above the Tg typically at a temperature below 600 ° C, preferably below 570 ° C.
• the first deposit is unique (the only metallic deposit for the grid) and is liquid, and preferably silver,
• the first deposit is by physical vapor phase of the first silver-based metal material or is preferably a liquid silver liquid and the second deposit is by electrodeposition preferably a second silver-based metal material .
• the solution for the silvering step may contain a silver salt, a silver ion reducer and even a chelating agent.
• the silvering step may be carried out according to standard procedures commonly used in the field of the manufacture of mirrors and described for example in Chapter 17 of the book "Electroless Plating - Fundamentals and Applications", published by Mallory, Glenn O.; Hajdu, Juan B. (1990) William Andrew Publishing / Noyes.
• the silvering step comprises (dip in a bath or spraying) contacting the substrate having the light extraction layer, the partially structured layer and the through-hole mask (from preferably a resin photo) with a mixture of two aqueous solutions, one containing the metal salt, for example silver nitrate, and the other containing the reducing agent for metal ions (Ag + ions), for example sodium , potassium, aldehydes, alcohols, sugars.
• aqueous solutions one containing the metal salt, for example silver nitrate, and the other containing the reducing agent for metal ions (Ag + ions), for example sodium , potassium, aldehydes, alcohols, sugars.
• the most commonly used reductants are Rochelle salt (KNaC 4 H 4 O 6 , 4H 2 0 sodium and potassium double tartrate), glucose, sodium gluconate and formaldehyde.
• the silvering step comprises a sensitization step (of the surface of the cavities) preferably comprising a treatment with tin salt and / or an activation step (of the surface of the cavities). cavities) preferably comprising a treatment with a palladium salt.
• These treatments have the main function of promoting the subsequent metallization (silver) and increase the thickness and adhesion of the formed silver metal layer (in the cavities).
• the silvering may be carried out by dipping the substrate having the light extraction layer, the partially structured layer and the through-hole mask, preferably photoresist) into trays, each with one of the three solutions in this order:
• a third which is a mixture of the silver salt solution preferably of silver nitrate and the solution of the silver reducing agent, preferably of sodium gluconate, preferably with stirring (preferably for less than 15min and even 5minutes, for example 1 min), then rinsing with water (distilled).
• the coated and thus silvery substrate is then removed from the last bath and rinsed with water (distilled).
• Another embodiment consists of spraying the three preceding solutions in the same order as before rather than plunging the substrate having the light extraction layer, the partially structured layer and the through-hole mask, preferably (photo) resin.
• the silver layers can be distinguished by their properties, in particular by discernable interface.
• the second deposit is made before removing the mask, thus keeping the mask.
• Polishing of the upper surface and the grid before deposition of the electroconductive coating or after deposition of the electroconductive coating is possible.
• the method may furthermore comprise, after the removal of the mask (resin, photoresist in particular), generally covered by the grid material or materials, a deposition step, directly on the grid and (directly) on the partially structured layer, electroconductive coating, monolayer or multilayer coating:
• liquid means for example, of a conductive polymer, preferably a single deposit of the electroconductive coating chosen monolayer.
• the method may comprise a step of heating the electrode before depositing the electroconductive coating at a temperature greater than 180 ° C., preferably between 250 ° C. and 450 ° C., in particular between 250 ° C. and 350 ° C., during a period of preferably between 5 minutes and 120 minutes, in particular between 15 and 90 minutes.
• And / or the process may comprise a heating step after deposition of the electroconductive coating in a mineral layer, preferably ITO, heating to a temperature above 180 ° C., preferably in the range 250 ° C. to 450 ° C., in particular 250 ° C. ° C and 350 ° C, for a period preferably between 5 minutes and 120 minutes, in particular between 15 and 90 minutes.
• a mineral layer preferably ITO
• the heating makes it possible to improve the gate area of the grid and / or to lower the absorption of the ITO-type mineral layer.
• FIG. 1 is a diagrammatic sectional view of an electroconductive support for OLED according to a first embodiment of the invention
• FIG. 1a illustrates a detailed view of the figure
• FIG. 1b shows a schematic view from above of the grid used in the support of FIG. 1 and in FIG. 1c a variant of a grid
• FIG. 1 d illustrates a detailed view of a section of a cavity of the partially-structured layer of FIG. 1,
• FIG. 2 is a diagrammatic sectional view of an electroconductive support for OLED according to a second embodiment of the invention
• FIG. 3 is a diagrammatic sectional view of an electroconductive support for OLED according to a third embodiment of the invention.
• FIGS. 1a to 1d are photographs taken under a scanning electron microscope, seen from above and in detail, of an electroconductive and diffusing support for OLED in an example No. 1 according to the invention
• FIG. 1 e shows the external quantum yield of an OLED made with the example No. 1 and an OLED of comparison as a function of the thickness of HTL
• FIGS. 2'a, 2'b and 6 are photos taken under a scanning electron microscope (SEM), in top view and in detail, of an electroconductive support for OLED (without electroconductive coating), showing the top surface and the grid strands in an example n ° 2 according to the invention
• FIGS. 4a to 4g are schematic views of the method of manufacturing the electroconductive support of FIG. 1,
• FIGS. 4'a to 4'g are schematic views of the manufacturing process of FIG.
• FIGS. 5a to 5b are pictures taken under a scanning electron microscope showing a partially structured layer with a cavity.
• FIG. 1 voluntarily very schematic, shows in lateral section an electroconductive and scattering support 100 for organic electroluminescent device OLED emission through the substrate (or "bottom emission” in English).
• This support 100 comprises a planar or curved glass substrate, organic or inorganic glass, 1 of refractive index n s of 1.3 to 1.6 - plane or even textured to be diffusing - with a first main face 1 1, so-called first surface, carrying in this order away from the substrate:
• an optional alkali barrier layer (not shown) if mineral glass, or moisture barrier if organic glass, such as silicon nitride or Ti (Zr) O 2 ,
• an electrically insulating light extraction layer 41 formed by an additional diffusing layer with diffusing elements 4 '(particles, etc.) and preferably a mineral layer, in particular made of glassy material with a high index of refractive index n 4 of 1 , 7 to 2.3, preferably from 1.80 to 2, 10 and in particular from 1.85 to 2.00, vitreous materials containing diffusing elements of the diffusing particles 4 'and possibly 4 "pores, thick layer e 4 preferably micron data,
• lower region 30 a region (continuous, non-textured) called lower region 30, which is here directly on the additional diffusing layer of thickness e 3 given preferably micron, covering the surface of the additional diffusing layer,
• an electrode 2 comprising a layer arranged in a grid 20, referred to as a metal grid, made of metallic material (s), preferably silver, the gate being here a monolayer formed of strands - in other words, tracks - anchored in ( all) the cavities, the strands having a width A less than 50 ⁇ , better less than or equal to 30 ⁇ (and at least 1 ⁇ ) and being spaced apart by a distance B less than or equal to 5000 ⁇ , grid of thickness e2 of at least 100 nm and preferably less than 1500 nm, the grid having a resistance per square smaller than 20 ⁇ / a, and even less than 10 ⁇ / ⁇ , or 5 ⁇ / ⁇ ,
• an electrically conductive coating 5 in this single layer, of thickness e of 5 or less than 500 nm, resistivity p 5 20Q.cm less than and greater than the resistivity of the metal grid, and refractive index n d given 5 at least 1, 55, consisting of a mineral layer 51, in conductive transparent oxide on the grid and the upper surface.
• Figure 1a (detail view of Figure 1), is defined as the width A c at the bottom of the cavity and B c the distance between two neighboring cavity funds.
• e c is the central height from the center of the bottom of the cavity.
• the gap H between the upper surface 32 and the surface of the metal gate 2 (in the center of the cavity) is, in absolute value, less than or equal to 100 nm, better than 30 nm.
• the grid may protrude from the top surface or be below (as shown in Figure 1a or 1d).
• the partially structured layer 3 is preferably planar locally, does not contain scattering particles.
• the partially structured layer preferably does not contain pores, at least no or few surface-open pores, at the very least no pores capable of diffusing light and / or creating too much surface roughness locally.
• an OLED device is added an organic electroluminescent system, single or multiple junction (tandem etc), a reflective upper electrode (or semi reflective), especially metal including silver or aluminum base.
• FIG. 1b shows a schematic view from above of the grid used in the support 100 of FIG. 1.
• the grid is formed of linear strands, disjoint (thus in cavities forming linear furrows, disjoint) of width A at the level of the upper surface and distance B at the level of the upper surface.
• the distance between patterns B corresponds to the maximum distance between neighboring strands.
• Figure 1c is a grid variant with interconnected strands forming meshes or closed patterns for example in honeycomb or any other geometric form (square etc) or not, so in interconnected cavities forming meshes or closed patterns for example honeycomb or any other geometric shape or not .
• the distance between patterns B corresponds to the maximum distance between two points of a mesh.
• the cavities may have oblique flanks for example because of the process of etching a layer during the formation of the partially structured layer.
• FIG. 1 d illustrates a detail view of a section of a cavity of the partially-structured layer of FIG. 1.
• the flanks are flared away from the substrate, a horizontal distance L between X and Y is defined such that L ⁇ 1, 4e c X being the highest point of the flank and Y being the point at the end of the bottom of the flange. the cavity.
• a sputtered strand is anchored and is flush with the upper surface. It has side areas in bowl.
• the distance H is calculated between the upper surface and the gate surface in the center of the cavity.
• the glass is flat, with a blur of less than 1%, made of clear silico-soda-lime glass, for example float glass, of index 1, approximately 5, for example 0.7 mm thick, and T L less 90%.
• the thickness e c is 400 nm.
• the cavities of the enamel layer are obtained by etching with acid as detailed later.
• the partially structured layer 3 is locally flat.
• the roughness of the upper surface 31 is defined by Ra less than 1 nm.
• Baking above Tg is for example made only once after the deposition of the dough based on glass frit and diffusing particles (and possible drying) and after the deposition of the same glass frit paste without diffusing particles.
• the T L of the glass assembly, diffusing layer, and partially structured layer is 57%, the blur of 85%, the absorption of less than 2%.
• the gate 2 is a silver monolayer (optionally oxidized surface) deposited by magnetron sputtering under argon at a pressure of 8 10 -3 mbar with a silver target, deposit directly into the cavities 32 '.
• the money is entirely in the cavities, with e 2 is 350nm. H is therefore less than 100 nm.
• the pattern of the grid is hexagonal.
• the width A equal to 6 ⁇ and the maximum distance B of 280m.
• the coverage rate T is 4.5%.
• the electroconductive coating 5 consists of an indium oxide layer and tin ITO 70nm 2 refractive index of about, resistivity p 5 less than 10 "Q.cm.
• the ITO is deposited by magnetron sputtering under a mixture of argon and oxygen 0 2 / (Ar + O 2 ) at 1% at a pressure of 2 10 ⁇ 3 mbar with a ceramic target made of indium oxide ( 90% by weight) and tin oxide (10% by weight).
• the amount of the assembly after annealing at 600 ° C. for 20 minutes as measured by the conventional 4-point method is 2.6 ohms / square.
• 1 'a to 1' are photos taken under a scanning electron microscope, in top view and in section, of an electroconductive and diffusing support for OLED in an example No. 1 according to the invention.
• the grid is multilayer, for example bilayer, with an overcoating protection against corrosion (water and / or air), for example metallic, distinct from silver, titanium or nickel, chromium, molybdenum for example, less than 1 nm thick and even 3 nm thick.
• the overlay is deposited by vacuum deposition, in the same deposition frame preferably.
• FIG. 1 e shows the external quantum efficiency measured in the air EQE air as a function of the thickness of the HTL layer of an OLED made with the example n ° 1. (curve 8) and a comparison OLED (curve 8 ').
• the OLED of comparison is made by the Applicant from the same glass and the same additional diffusing layer, surmounted by an unstructured layer of material and of identical thickness to the partially structured layer and with as electrode a layer of ITO identical to that of the coating 5 and of thickness equal to 100 nm and R square of 50ohm / square so much higher.
• the electroluminescent system comprises:
• an HTL layer of variable thickness (between 200 and 600 nm approximately)
• EBL electron blocking layer
• HBL hole blocking layer
• ETL layer electron transport layer
• the cathode is an aluminum layer of 100 nm.
• EQE air is measured inside an integrating sphere.
• EQE air OLED according to the invention is satisfactory (between 1 1% and 12%), and is almost equal to that of the comparison OLED.
• the difference of the order of 3 to 5% is due to the concealment of the surface by the silver grid.
• This OLED has a much higher efficiency than an OLED made from a glass and an ITO-based electrode whose EQE air is around 7.5 to 8%.
• the deposition of the silver by sputtering is replaced by a deposit by silvering and the size (height) of the cavities is equal to About 180nm.
• the width A remains at 6 ⁇ and B at 280 ⁇ .
• the square is 3.5ohm / square.
• the coverage rate T is 4%.
• the silver layer is deposited in the partially structured layer 3 according to the following procedure for a thickness e2 of about 200 nm:
• FIGS. 2'a and 2'b are photographs taken with a scanning electron microscope, in plan view and sectional view respectively of example No. 2 according to the invention, showing the upper surface 31 of the layer 3 and the grid anchored in layer 3.
• FIG. 2 voluntarily very schematic, shows in lateral section an electroconductive and scattering support 200 for organic OLED emitting device through the substrate (or "bottom emission” in English) in a second embodiment of the invention in which the layer silver is bilayered with a first layer of silver 21 deposited by silvering (or sputtering) and a second layer of thicker silver 22 deposited by electroplating (or silvering).
• the conductive coating is bilayer and includes under the ITO layer 51 a first layer 51 ', directly to the metal grid, AZO, e'5 of thickness equal to 80 nm, refractive index No. 5 of about 1.95.
• the first metallic layer, the anchoring layer 21, made of silver, of 80 nm, is deposited by silvering.
• the first silver layer is deposited in the partially structured layer according to the following procedure for about 80 nm:
• the second metal layer 22, in silver, of 350 nm, is deposited by electroplating.
• the electrolysis solution (bath) consists of an aqueous solution of
• FIG. 3 which is deliberately very schematic, represents in lateral section an electroconductive and diffusing support 300 for an organic OLED emitting device through the substrate (or "bottom emission” in English) in a fourth embodiment of the invention.
• the light extraction layer 42 is formed by the first surface of the glass which is diffusing, rough.
• the partially structured layer 3 is directly on the first diffusing surface of the glass.
• the electroconductive coating is a conductive polymer 52 and high index.
• the first surface 42 is diffusing.
• the roughness of the first surface 11 is obtained by a frosting of the glass, for example with hydrofluoric acid.
• An example of a rough substrate is the glass called Satinovo® Mate produced by the company La Veneciana de Saint-Gobain.
• the protuberances of the ground substrate are, for example, substantially pyramidal, randomly distributed, diffusing the light isotropically.
• the enamel is chosen as described for the layer of Example 1 and having a thickness e 3 of 20 ⁇ m.
• the electroconductive coating 52 made of PEDOTV PSS, is deposited by a liquid route and has a resistivity p1, for example of the order of 10 -1 ohm cm, with a thickness of the order of 100 nm or more.
• FIGS. 4a to 4g are a schematic view of the method of manufacturing the partially structured layer by photolithography and by acid etching, and of manufacturing the grid in relation to FIG.
• the first step illustrated in FIG. 4a consists, from the glass 1 coated with the light extraction layer 4 formed by the additional layer diffusing onto the substrate, which is a mineral material with diffusing particles:
• a layer 3a high index which comprises the vitreous material (enamel preferably) with said refractive index n 3 , - to apply a layer 60 of a masking material to the liquid state, here a positive photo-sensitive resin, classic resin AZ1505, on the layer 3a.
• the resin is then fired at 100 ° C for 20 minutes in a convection oven.
• the thickness of the mask is 800nm.
• the second step illustrated in FIG. 4b consists of the generation of the photoresist pattern.
• a photogravure mask 70 with discontinuities 71 is applied to the resin 60 and the resin 60 is irradiated with UV light (10 seconds at approximately 50 W / cm 2 ) through the discontinuities, in the zones intended to become through apertures. in an irregular or regular arrangement, one-dimensional (Figure 1c) or two-dimensional ( Figure 1d).
• the third step illustrated in FIG. 4c consists in the creation of the through-openings in the photoresist 60.
• the irradiated zones are eliminated, being soluble in a specific specific solution (here MIF developer for "metal iron free”) for 50 seconds and rinsed at deionized water, thereby forming through apertures 61 through the photoresist.
• a specific specific solution here MIF developer for "metal iron free”
• a negative photoresist and a reverse photogravure mask can be used (removal of non-irradiated areas to form the apertures).
• the fourth step illustrated in FIG. 4d consists in creating the cavities in the continuous layer 3a. It is preferred to form the partially structured layer by wet rather than dry etching, for example etching, at room temperature. The selected resin is therefore resistant to the etching solution which is acetic acid ph 2, 1. The etching depth is then controlled by the etching time here at 35nm.min "1 .
• the fifth step illustrated in FIG. 4e consists of the deposition of the gate material 2, preferably a deposit of silver by vacuum deposition, by magnetron sputtering, or alternatively by a liquid route such as silvering.
• Deposition is performed through openings 61 of photoresist 60 (etching mask), in the cavities to fill at least partially.
• the silver is also deposited on the surface of the mask (and is absent from the upper surface of the layer 3).
• the sixth step illustrated in FIG. 4f consists of the removal of the mask for example by liquid film (acetone solvent and use of ultrasound).
• the seventh step illustrated in FIG. 4g consists of the deposition of the electroconductive coating 5.
• FIGS. 4'a to 4'g are a schematic view of a variant of the method of manufacturing the partially structured layer by photolithography and by acid etching, and of manufacturing the grid in relation with FIG.
• the first step illustrated in FIG. 4a consists, from the glass 1 coated with the light extraction layer 4 formed by the additional layer diffusing onto the substrate which is a mineral material with diffusing particles: forming, on the light extraction aperture, a high index layer 3a, which comprises the vitreous material (enamel preferably) with said refractive index n 3 ,
• a layer 60 of a masking material in the liquid state here a positive photo-sensitive resin, conventional resin AZ1505, on the layer 3a.
• the resin is then fired at 100 ° C for 20 minutes in a convection oven.
• the thickness of the mask is 800nm.
• the second step illustrated in FIG. 4b consists of generating the photoresist pattern.
• a photogravure mask 70 with discontinuities 71 is applied to the resin 60 and the resin 60 is irradiated with UV light (10 seconds at approximately 50 W / cm 2 ) through the discontinuities, in the zones intended to become through apertures. according to an irregular or regular arrangement, one-dimensional or two-dimensional.
• the third step illustrated in FIG. 4c consists of the creation of the through openings in the photoresist.
• the irradiated areas are removed, being soluble in a conventional specific solution (MIF developer for "metal iron free") for 50 seconds and rinsed with deionized water, thereby forming through openings 61 through the photoresist.
• MIF developer for "metal iron free”
• flanks of the photoresist may be straight and perpendicular to the glass 1 or as here oblique and flared away from the glass.
• a negative photoresist and a reverse photogravure mask can be used (removal of non-irradiated areas to form the apertures).
• the fourth step illustrated in FIG. 4'd consists of the creation of the cavities in the continuous layer 3a. It is preferred to form the partially structured layer by wet rather than dry etching, for example etching, at room temperature. The selected resin is therefore resistant to the etching solution which is acetic acid ph 2, 1. The etching depth is then controlled by the etching time here at 35nm.min "1 .
• the etching forming cavities depth e c with flanks 32 oblique, curved.
• the etching is isotropic so that the etching solution here acid etches (digs) in all directions.
• the cavity profile is in a bowl, the cavities W are wider than the width W 0 of the openings through the mask in the plane of the interface between the mask and the high index layer, leaving portions of the mask surfaces 63, 63 'of positive photoresist protruding from the upper surface and facing the cavity.
• the oblique flanks 32 are each of horizontal distance L ⁇ 1, 4 e c as shown in Figures 5a to 5b.
• the bottom 32 ' is flat.
• the fifth step illustrated in FIG. 4e is the deposition of the gate material 2 by silvering.
• the deposit is made through the openings 61 of the photoresist 60 (acid etching mask), in the cavities to fill them at least partially.
• the silver is also deposited on the outermost surface of the mask (and is absent from the upper surface of layer 3).
• the silvering at least partially fills said cavity and the entire height of the sidewalls of the cavity and the protruding surface portions 63, 63 'opposite the vavity. This thus forming side peripheral zones of strand 23, 23 'flush with the upper surface, flat, smoother than the strand central zone 24 opposite the opening.
• the maximum width A of the strand is here the width at the surface of the strand.
• the width L1 of each peripheral lateral zone is approximately equal to L.
• Figure 4e (like the following ones) is not to scale in the sense or for example e2 is generally (well) superior to H.
• the sixth step illustrated in FIG. 4 is the removal of the mask preferably by liquid film with an acetone solvent and use of ultrasound.
• the seventh step illustrated in FIG. 4'g consists of the deposition of the electroconductive coating 5.
• FIG. 6 which is a photograph taken at the SEM, shows an example of a quasi-flush metallic grid obtained by silvering with a strand 20 in an oblique-cavity cavity 32 of the layer. 3.
• the central zone 24 is rougher than the peripheral lateral zones 23 which are further flush with the upper surface.

Landscapes

• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Electroluminescent Light Sources (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=49231582

Family Applications (1)

Country Status (10)

Families Citing this family (11)

Family Cites Families (29)

• 2013
  • 2013-03-08 FR FR1352131A patent/FR3003084B1/fr not_active Expired - Fee Related
• 2014
  • 2014-03-10 MY MYPI2015702968A patent/MY191607A/en unknown
  • 2014-03-10 WO PCT/FR2014/050535 patent/WO2014135817A1/fr active Application Filing
  • 2014-03-10 TW TW103108186A patent/TWI620362B/zh not_active IP Right Cessation
  • 2014-03-10 US US14/773,145 patent/US10181566B2/en not_active Expired - Fee Related
  • 2014-03-10 KR KR1020157027440A patent/KR20150130356A/ko active IP Right Grant
  • 2014-03-10 CN CN201480012981.XA patent/CN105027315B/zh not_active Expired - Fee Related
  • 2014-03-10 JP JP2015560755A patent/JP6542677B2/ja not_active Expired - Fee Related
  • 2014-03-10 EP EP14715349.8A patent/EP2965367A1/fr not_active Withdrawn
  • 2014-03-10 RU RU2015142817A patent/RU2645793C9/ru not_active IP Right Cessation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events