Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements
  • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
  • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
  • G02B5/0215—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having a regular structure
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements
  • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
  • G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/0011—Working of insulating substrates or insulating layers
  • H05K3/0017—Etching of the substrate by chemical or physical means
  • H05K3/002—Etching of the substrate by chemical or physical means by liquid chemical etching
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
  • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
  • H05K3/467—Adding a circuit layer by thin film methods
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/805—Electrodes
  • H10K50/81—Anodes
  • H10K50/816—Multilayers, e.g. transparent multilayers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/85—Arrangements for extracting light from the devices
  • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/03—Conductive materials
  • H05K2201/032—Materials
  • H05K2201/0326—Inorganic, non-metallic conductor, e.g. indium-tin oxide [ITO]

Definitions

• the invention relates to a textured glass substrate having improved optical properties for optoelectronic device and a method of manufacturing such a textured glass substrate.
• optoelectronic device is meant any type of device that can emit or collect light. Such devices are for example organic electroluminescent devices known by the acronym OLED (OLED: Organic Light Emitting Device) or light collecting devices such as organic photovoltaic cells still called solar cells.
• OLED Organic Light Emitting Device
• the invention relates to a glass substrate with improved optical properties for an organic light emitting device (OLED).
• textured is meant the fact that the substrate comprises on at least one of its surfaces texturing. Texturing means a plurality of patterns creating a relief, concave or convex relative to the general plane of the face of the glass substrate.
• the two faces of the glass substrate may have such patterns. Thanks to its texturing, the glass substrate has improved optical properties.
• improved optical properties is meant an improved light transmission, in other words an increase in the amount of light transmitted, through the textured glass substrate.
• EP 1449017 B1 discloses a laminated textured glass plate having on at least one of its faces a plurality of pyramidal type patterns. The surface thus obtained has a better transmission of light.
• this is a process requiring a little flexible implementation.
• the texturing of the glass results from the printing of a pattern by making an impression by rolling the glass at its deformation temperature. Any modification of the texturing can only be achieved by changing the impression made which implies a change of the rolling roller used. This operation is long and tedious.
• the roller used also tends to wear out over time, which leads to a problem of reproducibility of the impression made.
• the invention particularly aims to overcome these disadvantages of the prior art.
• Another object of the invention in at least one of its embodiments, is to provide a textured glass substrate which makes it possible to reduce the angular dependence of the dominant wavelength and the purity of the color emitted by a light-emitting device. organic material incorporating said textured glass substrate.
• the invention relates to a glass substrate with improved optical properties for optoelectronic devices such that said substrate is textured by chemical etching, totally or partially on at least one of its faces by a set of geometric patterns such as :
• the general principle of the invention is based on the texturing by etching of a glass substrate, this texturing can be performed on at least one side of said substrate. Texturing can be done on the entire face or on a part of it. This texturing by etching leads to the formation of a set of geometric patterns such that their presence improves the optical properties of the glass substrate.
• the invention is based on a completely new and inventive approach based on a chemical texturing of the glass substrate.
• This chemical texturing of the glass makes it possible to dispense with the step of printing a pattern by making an impression by rolling the glass brought to its deformation temperature and the constraints related to this operation.
• this mode of texturing is more flexible and easily controllable.
• texturing mode more Soft means that the texturing of the surface, measured in the form of the roughness parameters R z and R Sm , can be modified by slight changes in the attack times or chemical compositions of the etching solutions.
• more easily controllable texturing mode it is meant that the control of the texturing is simply related to the control of the composition of the attack solutions and the attack times, this control being easier than a control of the wear of a rolling roll for printing a pattern.
• the glass substrate comprises at least one texturing of the surface by etching.
• This texturing comprising at least matting and / or etching, preferably matting.
• the chemical etching of the glass substrate can be advantageously carried out by a controlled acid attack, by using acidic solutions used in the manufacture of textured glass (for example by etching with hydrofluoric acid).
• the acid solutions are aqueous solutions of hydrofluoric acid having a pH ranging from 0 to 5.
• Such aqueous solutions may comprise, besides hydrofluoric acid, salts of this acid, other acids such as, for example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and their salts (eg Na 2 S0 4, K 2 S0 4, (NH 4) 2 S0 4, BaS0 4, ...) and optional additives in minor proportions (for example: acid / base buffer agents, wetting agents, .).
• Alkaline salts and ammonium salts are generally preferred, among these are especially sodium, potassium and ammonium hydrofluoride and / or ammonium biforide.
• Such solutions are, for example, aqueous solutions comprising from 0 to 600 g / l of hydrofluoric acid, preferentially from 150 to 250 g / l of hydrofluoric acid and also comprising from 0 to 700 g / l of NH 4 HF 2 , preferably from 150 to 300 g / l NH 4 HF 2 .
• the acid attack can be carried out in one or more steps. Attack times are at least 10s. Preferably, the attack times are at least 20 seconds Attack times do not exceed 30 minutes.
• R z By average height of the patterns, R z , we define the average distance between the top and the base of the patterns.
• vertex is meant the furthest point from the base of the patterns. This point is unique in the case of a peak but it can be multiple when the summit is in the form of a plateau.
• the distance Rs m is the distance separating the midpoints of said plateaus.
• the glass substrate is such that: the arctangent of the ratio between the average height of the patterns, R z , and half the mean distance separating the vertices of two contiguous patterns, Rs m , is at less than an angle of 35 °, the arctangent of the ratio between the height of the patterns, R z , and half of the distance separating the vertices of two contiguous motifs, Rs m , is not greater than an angle of 70 ° .
• the glass substrate is such that: the arctangent of the ratio between the average height of the patterns, R z , and half the mean distance separating the vertices of two contiguous patterns, Rs m , is at less equal to an angle of 35 ° • the arctangent of the ratio between the height of the patterns, R z , and half the distance separating the vertices of two contiguous patterns, Rs m , is at most equal to an angle of 60 °.
• the glass substrate according to the invention comprises at least total or partial texturing of the surface of the substrate opposite the surface intended to receive the optoelectronic device.
• the texturing of the surface comprises at least the formation of polygonal base pyramids whose smallest angle formed between on the one hand the plane parallel to the base of said pyramids and on the other hand, the plane of at least one lateral face of said pyramids is at least 35 °.
• the angle formed between, on the one hand, a plane parallel to the base of said pyramids, and, on the other hand, the plane of at least one lateral face of said pyramids is at most 80 °, preferably at most 70 °, more preferably at most 60 °.
• the angle formed between, on the one hand, a plane parallel to the base of said pyramids, and, on the other hand, the plane of at least one lateral face of said pyramids is in the range of values ranging from 35 ° to 80 ° °, preferably in the range of values from 35 ° to 70 °, more preferably in the range of values from 35 ° to 60 °.
• the advantage offered by the partial or total texturing of the surface of the substrate is that it makes it possible to reduce the losses related to the internal reflections at the interfaces of this substrate.
• the glass substrate has a refractive index of at least 1.5. The use of a substrate having a higher refractive index makes it possible to obtain an equal optoelectronic system and equal texturing, a higher amount of transmitted light and thus a higher luminance.
• the glass substrate is advantageously chosen from amongst others AGC Matelux Clear glass, AGC Matelux Light glass, AGC Matelux Double Sided glass, AGC Matelux Clearvision glass, AGC Matelux Antislip glass, AGC Arctic White glass , AGC Matelux Stopsol Supersilver Clear Glass, AGC Glamatt Glass, AGC Matobel Glass, etc.
• the substrate is such that the geometric patterns comprise at least one pyramid-type structure with a polygonal base.
• walking pyramid is meant a pyramid of which at least one face has a stepped structure.
• This staircase structure is such that the dimensions of the steps and counter steps are not necessarily equal to each other and two by two.
• the angle formed by a plane comprising a step and a plane comprising a counter-step is not necessarily equal to 90 °.
• the angle "on-march" seen from within the pyramid is at least 100 °, more preferably at least 120 °, most preferably at least 145 °. This angle can vary from one "walk-to-walk” structure to another.
• the geometric patterns are as close together as possible.
• the textured glass substrate according to the invention is such that said substrate is textured totally or partially on the face of the substrate opposite to the face on which said transparent electrode is deposited, the face of the transparent electrode side substrate being able to to be textured or not, preferably the transparent electrode side is untextured.
• the textured glass substrate for optoelectronic devices is such that the transparent electrode comprises at least one conductive oxide layer based on at least one doped oxide, preferably selected from tin-doped indium (ITO), zinc oxide doped with at least one doping element selected from aluminum (AZO), gallium (GZO) or fluorine-doped tin oxide 'antimony,
• the textured glass substrate for optoelectronic devices is such that the transparent electrode comprises a stack comprising a single conduction metal layer and at least one coating having properties for improving the light transmission.
• said coating having a geometrical thickness at least greater than 3.0 nm and at most less than or equal to 200 nm, preferably less than or equal to 170 nm, more preferably less than or equal to 130 nm, said coating comprising at least least one light transmissive enhancement layer and being located between the conduction metal layer and the substrate on which said electrode is deposited, such as the optical thickness of the coating having light transmittance enhancing properties , T D i, and the geometrical thickness of the metallic layer conduction, T M E, are connected by the relation:
• TME T M E_O + [B * sin ( ⁇ * T D1 / T D i_o)] / (n S ubstrate) 3
• TME o, B and T D io are constants with T M E o having a value included in the range from 10.0 to 25.0 nm, B having a value in the range of 10.0 to 16.5 and TDI o having a value in the range of 23.9 * noi to 28, 3 * noi nm with noi representing the refractive index of the coating to improve the transmission of light at a wavelength of 550 nm, n su b trat s represents the refractive index of the glass constituting the substrate a wavelength of 550 nm.
• the constants T M E o, B and T D io are such that T M E o has a value in the range from 1 1, 5 to 22.5 nm, B has a value in the range from 12 at 15 and TDI where a value in the range of 24.8 * noi to 27.3 * n D i nm. More preferably, the constants T M E o, B and T D io are such that TME oa value in the range of 12.0 to 22.5 nm, B has a value in the range of 12 to 15 and T DI where a value in the range of 24.8 * noi to 27.3 * nm.
• the advantage offered by the substrate according to the invention is that it makes it possible to obtain an increase in the quantity of light emitted or converted by an optoelectronic device incorporating it, and this for a monochromatic radiation, more particularly the amount of light emitted in the case of an organic electroluminescent device (OLED).
• OLED organic electroluminescent device
• a coating having properties for improving the transmission of light is meant a coating whose presence in the stack constituting the electrode leads to an increase in the amount of light transmitted through the substrate, for example a coating having anti-reflective properties.
• an optoelectronic device incorporating the substrate according to the invention emits or converts a larger amount of light with respect to an optoelectronic device of the same nature but comprising a conventional electrode (for example: ITO) deposited on an identical substrate. to that of the substrate according to the invention. More particularly, when the substrate is inserted into an organic electroluminescent device, the increase in the amount of light emitted is characterized by a greater luminance value and whatever the color of the emitted light.
• the geometric thickness of the coating for improving the transmission of light advantageously has a thickness less than or equal to 200 nm, preferably less than or equal to 170 nm, more preferably less than or equal to 130 nm, the advantage offered by such thicknesses residing in the fact that the manufacturing process of said coating is faster.
• substrate is also intended to denote not only the glass substrate as such but also any structure comprising the glass substrate and at least one layer of a material having refractive index n & mat iau, near the glass refractive index constituting the substrate, n subs trat, in other words
• the substrate is the absolute value of the difference between the refractive indices.
• a layer of silicon oxide deposited on a glass substrate made of silicosodocalcic glass may be mentioned.
• the glass substrate preferably has a geometric thickness of at least 0.35 mm.
• geometrical thickness is meant the average geometrical thickness.
• the glasses are mineral or organic. The mineral glasses are preferred. Among these, the clear or colored silicosodocalcic glasses are preferred in the mass or on the surface. More preferably, they are extra clear silicosodocalcic glasses.
• extra-clear means a glass containing at most 0.020% by weight of the total Fe glass expressed in Fe 2 0 3 and preferably at most 0.015% by weight.
• the glass refractive index, n su b s trat preferably has a value between 1.4 and 1.6. More preferably, the refractive index of the glass has a value equal to 1.5.
• n su b s trat represents the refractive index of the glass constituting the substrate at a wavelength of 550 nm.
• the glass substrate according to the invention is such that the glass which constitutes it has a refractive index of between 1.4 and 1.6 at a wavelength of 550 nm and that the electrode it understands is such that the optical thickness of the coating with properties for improving the transmission of light, T D i, and the geometrical thickness of the conductive metal layer, T M E, are connected by the relation:
• TME T M E_O + [B * sin ( ⁇ * T D i / T D i_o)] / (nsubstrate) 3
• TME o, B and T D io are constants with T M E o having a value included in the range from 10.0 to 25.0 nm, preferably from 10.0 to 23.0 nm, B having a value in the range of 10.0 to 16.5 and TDI o having a value included in the range ranging from 23.9 to 28.3 * * noi noi nm with noi representing the refractive index of the transmission-improving coating light at a wavelength of 550 nm, n su b s trat represents refractive index of the glass constituting the substrate at a wavelength of 550 nm.
• the constants T M E 0, B and T D 10 are such that TME has a value in the range from 10.0 to 23.0 nm, preferably from 10.0 to 22.5 nm, most preferably From 1 to 5 to 22.5 nm, B has a value in the range of 1, 5 to 15.0 and TDI where a value in the range of 24.8 * noi to 27.3 * noi nm.
• the constants T M E 0, B and T D 10 are such that T M E o has a value in the range from 10.0 to 23.0 nm, preferably from 10.0 to 22.5 nm, most preferably from 1, 5 to 22.5 nm, B has a value in the range of 12.0 to 15.0 and T D 10a has a value in the range of 24.8 * noi to 27 , 3 * noi nm.
• the glass substrate according to the invention is such that the glass which constitutes it has a refractive index equal to 1.5 at a wavelength of 550 nm and that the electrode that comprises is such that the optical thickness of the coating with light transmissive enhancement properties, T D i, and the geometrical thickness of the conductive metal layer, T M E, are related by the relation:
• TME T M E_O + [B * sin ( ⁇ * T D i / T D i_o)] / (nsubstrate) 3
• T M E o, B and T D io are constants with T M E o having a value in the range of 10.0 to 25.0 nm, preferably 10.0 to 23.0 nm, B having a value in the range of 10.0 to 16.5 and TDI o having a value in the range of 23.9 * noi to 27.3 * noi nm with noi representing the refractive index of the coating of improvement of light transmission at a wavelength of 550 nm, n su b s trat represents the refractive index of the glass constituting the substrate at a wavelength of 550 nm.
• the constants T M E 0, B and T D 10 are such that T M E o has a value in the range from 10.0 to 23.0 nm, preferably from 10.0 to 22.5 nm, the more preferably from 1 to 5 to 22.5 nm, B has a value in the range of 1, 5 to 15.0 and TDI where a value in the range of 24.8 * n D i to 27.3 * n D i.
• the constants T M E 0, B and T D 10 are such that T M E o has a value in the range from 10.0 to 23.0 nm, preferably from 10 to 22.5 nm, the most preferably from 1, 5 to 22.5 nm, B has a value in the range of 12.0 to 15.0 and TDI where a value in the range of 24.8 * noi to 27.3 * noi nm.
• the glass substrate according to the invention is such that the geometric thickness of the conduction metal layer is at least equal to 6.0 nm, preferably at least 8.0 nm, more preferably at least 10.0 nm and at most equal to 22.0 nm, preferably at most equal to 20.0 nm, more preferably at most 18.0 nm and of which the geometric thickness of the light transmission enhancement coating is at least equal to 50.0 nm, preferably at least equal to 60.0 nm and at most equal to 130.0 nm, preferably at most equal to 1 10, 0 nm, more preferably at most equal to 90.0 nm.
• the glass substrate according to the invention is such that the glass which constitutes it at a refractive index value in the range of 1, 4 to 1, 6 and is such that the thickness geometric of the conductive metal layer is at least equal to 16.0 nm, preferably at least 18.0 nm, more preferably at least 20.0 nm and at most equal to 29.0 nm, preferably at most equal to at 27.0 nm, more preferably at most equal to 25.0 nm and in which the geometric thickness of the light transmission enhancement coating is at least 20.0 nm and at most equal to 40.0 nm .
• the use of a thick conduction metal layer combined with an optimized thickness of the light transmission enhancement coating makes it possible to obtain optoelectronic systems, more particularly OLEDs devices, having on the one hand a high luminance and secondly incorporating a glass substrate whose electrode has a surface resistance expressed in ⁇ / ⁇ lower.
• the glass substrate according to the invention is such that the refractive index of the material constituting the coating for improving the transmission of light (n D i) is greater than the refractive index glass substrate component 1 e (n su b trat s) 3 ⁇ 4> ⁇ > n su bstrat), preferably D i n> 1.2 * n su b trat s, more preferably n D i> 1.3 * n su b trat s, most preferably n D i> 1.5 * n su b s trat.
• the refractive index of the material constituting the coating (noi) has a value ranging from 1.5 to 2.4, preferably ranging from 2.0 to 2.4, more preferably ranging from 2.1 to 2.4 to wavelength of 550 nm.
• n D i is given by the relation:
• n x represents the refractive index of the material constituting the x th layer starting from the substrate
• 1 x represents the geometrical thickness of the x th layer
• i represents the geometrical thickness coating.
• the material constituting at least one layer of the light transmission enhancement coating comprises at least one dielectric compound and / or at least one electrically conductive compound.
• dielectric compound is meant at least one compound chosen from:
• nitrides of at least one element selected from boron, aluminum, silicon, germanium and their mixture;
• conductor is intended to denote at least one compound chosen from: oxides under stoichiometric oxygen and doped oxides of at least one element selected from Ti, Zr, Hf, V, Nb, the Ta, Cr, Mo, W, Zn, Ai, Ga, In, Si, Ge, Sn, Sb, Bi and the mixture of at least two of between them ;
• the dopants comprise at least one of the elements chosen from Al, Ga, In, Sn, P, Sb, and F.
• the dopants comprise B , Ai and / or Ga.
• the conduction metal layer of the electrode forming part of the glass substrate according to the invention mainly ensures the electrical conduction of said electrode. It comprises at least one layer comprising a metal or a mixture of metals.
• the generic term "metal mixture” refers to combinations of two or more metals in alloy form or doping of at least one metal with at least one other metal; the metal and / or the mixture of metals comprising at least one element selected from Pd, Pt, Cu, Ag, Au, Al.
• the metal and / or the mixture of metals comprises at least one element selected from Cu, Ag, Au, Al. More preferably, the conduction metal layer comprises at least Ag in pure form or alloyed with another metal.
• the other metal comprises at least one element selected from Au, Pd, Al, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn. More preferably, the other metal comprises at least Pd and / or Au, preferentially Pd.
• the coating for improving light transmission of the electrode constituting a part of the substrate according to the invention comprises at least one additional crystallization layer, said crystallization layer being, relative to the substrate , the layer furthest from the stack constituting said coating.
• This layer allows a preferential growth of the metal layer, for example silver, constituting the metal conduction layer and thereby obtain good electrical and optical properties of the metal conduction layer.
• It comprises at least one inorganic chemical compound.
• the inorganic chemical compound constituting the crystallization layer does not necessarily have a high refractive index.
• the inorganic chemical compound comprises at least ZnO x (with x ⁇ 1) and / or Zn x Sn y O z (with x + y> 3 and z ⁇ 6).
• the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer.
• the crystallization layer is ZnO. Since the layer having the property of improving light transmission has a thickness generally greater than that usually encountered in the field of conductive multilayer coatings (for example: low emissive type coating), the thickness of the crystallization layer must be be adapted and augmented to provide a conductive metal layer having good conduction and very little absorption.
• the geometric thickness of the crystallization layer is at least equal to 7% of the total geometrical thickness of the coating for improving the transmission of light, preferably at 11%, more preferably at 14%. %.
• the geometric thickness of the enhancement layer of the Light transmission shall be reduced if the geometric thickness of the crystallization layer is increased so as to respect the relationship between the geometrical thickness of the conduction metal layer and the optical thickness of the light transmission enhancement coating.
• the crystallization layer is merged with at least one light transmission enhancement layer constituting the light transmission enhancement coating.
• the improvement coating for the light transmission of the transparent electrode comprises at least one additional barrier layer, said barrier layer being relative to the face of the substrate on which the electrode is deposited, the layer closest to the stack constituting said coating.
• This layer makes it possible in particular to protect the electrode against any pollution by migration of alkalis from the glass substrate, for example of silicosodocalcic glass, and therefore an extension of the lifetime of the electrode.
• the barrier layer comprises at least one compound selected from: titanium oxide, zirconium oxide, aluminum oxide, yttrium oxide and a mixture of at least two of them; the mixed oxide of zinc-tin, zinc-aluminum, zinc-titanium, zinc-indium, tin-indium; silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum nitride, aluminum oxynitride and the mixture of at least two of them; this barrier layer being optionally doped or alloyed with tin.
• the barrier layer is merged with at least one light transmission enhancement layer constituting the light transmission enhancement coating.
• barrier and crystallization layers at least one of these two additional layers is merged with at least one layer for improving the light transmission of the coating for improving the transmission of light.
• the glass substrate according to the invention is such that the electrode comprises a thin film of uniformity of the surface electrical properties located, with respect to the face of the substrate on which the electrode is deposited, at top of the multilayer stack constituting said electrode.
• the main function of the thin film of uniformity of surface electrical properties is to enable a uniform charge transfer to be obtained over the entire surface of the electrode. This uniform transfer results in an equivalent emitted or converted light flux at any point on the surface. It also increases the life of the optoelectronic devices since this transfer is the same at each point, eliminating the possibility of hot spots.
• the uniformization layer has a geometric thickness of at least 0.5 nm, preferably at least 1.0 nm.
• the uniformization layer has a geometric thickness of at most 6.0 nm, preferably at most 2.5 nm, more preferably at most 2.0 nm. More preferably, the uniformization layer is equal to 1.5 nm.
• the uniformization layer comprises at least one layer comprising at least one inorganic material selected from a metal, a nitride, an oxide, a carbide, an oxynitride, an oxycarbide, a carbonitride or an oxycarbonitride.
• the inorganic material of the uniformization layer comprises a single metal or a mixture of metals.
• the generic term “mixture of "metals” means combinations of two or more metals in alloy form or doping of at least one metal with at least one other metal.
• the uniformization layer comprises at least one element selected from Li, Na, K, Be, Mg, Ca, Ba, Se, Y, Ti, Zr, Hf, Ce, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb.
• Metal and / or the mixture of metals comprises at least one element selected from Li, Na, K, Mg, Ca, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, C. More preferably, the metal or the mixture of metals comprises at least one element selected from C, Ti, Zr, Hf, V, Nb, Ta, Ni, Cr , Al, Zn.
• the metal mixture preferably comprises Ni-Cr and / or Zn doped with Al.
• the advantage offered by this particular embodiment is that it makes it possible to obtain the best possible compromise between, on the one hand, the electrical properties resulting from the effect of the uniformity layer of the surface electrical properties and, on the other hand, the optical properties obtained through the improvement coating.
• the use of a uniformization layer having the lowest possible thickness is fundamental. Indeed, the influence of this layer on the amount of light emitted or converted by the optoelectronic device is even lower than its thickness is low.
• This uniformization layer when it is metallic is thus distinguished from the conduction layer by its thinner thickness, this thickness being insufficient to ensure a conductivity.
• the uniformization layer when it is metallic that is to say composed of a single metal or mixture of metals, preferably has a geometric thickness of at most 5.0 nm.
• the inorganic material of the uniformization layer is present in the form of at least one chemical compound selected from carbides, carbonitrides, oxynitrides, oxycarbides, oxycarbonitrides and mixtures of at least two of them.
• the oxynitrides, oxycarbides and oxycarbonitrides of the uniformization layer may be in non-stoichiometric form, preferably substoichiometric with respect to oxygen.
• Carbides are carbides of at least one element selected from Be, Mg, Ca, Ba, Se, Y, Ti, Zr, Hf, Ce, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Rh, Ir , Ni, Pd, Pt, Cu, Au, Zn, Cd, B, Al, Si, Ge, Sn, Pb, preferably of at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Si, more preferably at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Zn, Al.
• the oxycarbonitrides are oxycarbonitrides of at least one element selected from Be, Ti, Zr, Hf, V, Nb, Cr, Mo, W, Mn, Zn, B, Al, Si, Ge, preferably of at least one element selected from Ti, Zr, Hf, V, Nb, Cr, Mo , W, Mn, Zn, Al, Si, more preferably at least one element selected from Ti, Zr, Hf, V, Nb, Cr, Zn, Al.
• Carbides, carbomtrides, o xynitrides, oxycarbures, oxycarbonitrides of the uniformity layer of the electrical surface properties optionally comprise at least one doping element.
• the uniformizing thin film comprises at least one oxynitride comprising at least one element selected from Ti, Zr, Cr, Mo, W, Mn, Co, Ni, Cu, Au, Zn, Al, Si More preferably, the thin film of uniformization of Surface electrical properties comprise at least one oxynitride selected from Ti oxynitride, Zr oxynitride, Nioxynitride, NiCr oxynitride.
• the uniformization layer comprises at least one nitride of an element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si.
• the nitride comprises at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Ni, Cr, Al, Zn.
• the thin film of uniformity of the surface electrical properties comprises at least Ti nitride, Zr nitride, Ni nitride, NiCr nitride.
• the inorganic material of the uniformization layer is present in the form of at least one metal oxide of at least one element selected from Be, Mg, Ca, Sr, Ba, Se, Y , Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B , Al, Ga, In, Si, Ge, Sn, Pb.
• the thin film of uniformity of the surface electrical properties comprises at least the Ti oxide and / or the Zr oxide and / or the Ni oxide and / or the NiCr oxide and / or TITO and / or the doped Cu oxide, the dopant being Ag, and / or the doped Sn oxide, the dopant being at least one element selected from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from Al, Ga, Sn, Ti.
• the glass substrate according to the invention is such that the electrode comprises at least one additional insertion layer located between the conduction metal layer and the thinning uniform layer.
• the layer inserted between the conduction metal layer and the uniformization layer comprises at least one layer comprising at least one dielectric compound and / or at least one electrically conductive compound.
• the insertion layer comprises at least one layer comprising at least one conductive compound.
• This insertion layer has the function of constituting part of an optical cavity making it possible to make the metal conduction layer transparent.
• dielectric compound is meant at least one compound chosen from:
• the dielectric compound preferably comprises an yttrium oxide, a titanium oxide, a zirconium oxide, a hafnium oxide, a niobium oxide, a tantalum oxide, a zinc oxide, a tin oxide, aluminum oxide, aluminum nitride, silicon nitride and / or silicon oxycarbide.
• conductor is intended to denote at least one compound chosen from: oxides under stoichiometric oxygen and doped oxides of at least one element selected from ⁇ Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Zn, Al, Ga, In, Si, Ge, Sn, Sb, Bi and the mixture of at least two of them, the doped nitrides of at least one element selected from boron, aluminum, silicon, germanium and their mixture,
• the dopants comprise at least one of the elements chosen from Al, Ga, In, Sn, P, Sb and F.
• the dopants include B, Al and / or Ga.
• the conducting compound comprises at least ⁇ and / or doped Sn oxide, the dopant being at least one element chosen from F and Sb, and / or doped Zn oxide, the dopant being at least one element selected from Al, Ga, Sn, Ti.
• the inorganic chemical compound comprises at least ZnO x (with x ⁇ 1) and / or Zn x Sn y O z (with x + y> 3 and z ⁇ 6).
• the Zn x Sn y O z comprises at most 95% by weight of zinc, the weight percentage of zinc is expressed relative to the total weight of the metals present in the layer.
• E org Ei n -C makes it possible to use the geometrical thickness of the first organic layer of the organic device electroluminescence to optimize the optical parameters (geometric thickness and refractive index) of the insertion layer and thus optimize the amount of light transmitted while keeping an insertion layer thickness compatible with electrical properties to avoid voltage fluctuations. ignition for a second maximum of luminance.
• the metal conduction layer of the electrode comprises on at least one of its faces at least one sacrificial layer.
• sacrificial layer is meant a layer that can be oxidized or nitrided in whole or in part. This layer makes it possible to avoid deterioration of the metallic conduction layer, in particular by oxidation or nitriding.
• the sacrificial layer comprises at least one compound chosen from metals, nitrides, oxides and sub-stoichiometric oxygen oxides.
• the metals, nitrides, oxides and sub-stoichiometric metal oxides comprise at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al.
• the sacrificial layer comprises at least Ti, Zr, Ni, Zn, Al.
• the sacrificial layer comprises at least Ti, TiO x (with x ⁇ 2), NiCr, NiCrO x , TiZrO x (TiZrO x indicates a layer of titanium oxide at 50% by weight d zirconium oxide), ZnA10 x (ZnA10 x indicates a layer of zinc oxide at 2 to 5% by weight of aluminum oxide).
• the thickness of the sacrificial layer comprises a geometric thickness of at least 0.5 nm.
• the thickness of the sacrificial layer comprises a thickness of at most 6.0 nm. More preferably, the thickness is equal to 2.5 nm.
• a sacrificial layer is deposited on the face of the metal conduction layer furthest from the substrate.
• the glass substrate according to the invention is such that it comprises at least one diffusing layer, said diffusing layer being located between the transparent electrode and the substrate.
• diffusing layer is described in published documents WO2009 / 017035, WO2009 / 1 1653 1, WO2010 / 084922, WO2010 / 084925, WO201 1/046156, WO2011 / 046190 and PCT / JP201 1/074358, all incorporated herein. by reference.
• this diffusion layer has a thickness of more than 5 ⁇ and is not considered as a coherent optical system.
• the textured glass substrate according to the invention essentially has the following structure:
• the geometric thickness of the coating with properties of improving the transmission of light and the geometric thickness of the conduction metal layer are related by the relation:
• TME T M E_O + [B * sin ( ⁇ * T D i / T D i_o)] / (nsubstrate) 3
• T ME o, B and T D io are constants with T ME o having a value included in the ranging from 10.0 to 25.0 nm, preferably from 10.0 to 23.0 nm, B having a value in the range of 10.0 to 16.5 and T DI o having a value in the range of range from 23.9 * n D i to 28.3 * n D i with n D i representing the refractive index of the coating for improving light transmission at a wavelength of 550 nm, n substrate represents the refractive index of the glass constituting the substrate at a wavelength of 550 nm.
• the constants T ME o, B and T D io are such that T ME oa a value in the range from 10.0 to 23.0 nm, preferably from 10.0 to 22.5 nm, most preferably from 1 1.5 to 22.5 nm, B has a value in the range of 11.5 to 15.0 and T DI where a value in the range of 24.8 * noi to 27.3 * noi nm.
• the constants T ME o, B and T D io are such that T ME oa a value in the range from 10.0 to 23.0 nm, preferably from 10.0 to 22.5 nm, the most preferably from 1 1.5 to 22.5 nm, B has a value in the range of 12.0 to 15.0 and T DI oa value in the range of 24.8 * noi to 27.3 * noi nm.
• Sacrificial layer geometric thickness 1.0-3.0 nm in Ti • Insertion layer: geometrical thickness 3.0-20.0 nm in Zn x Sn y O z (with x + y> 3 and z ⁇ 6)
• Standardization layer geometric thickness 0.5-3.0 nm in X, nitride of X, oxynitride of X with X: Ti, Zr, Hf, V, Nb, Ta, Ni, Pd, Cr, Mo, Al , Zn, Ni-Cr or Zn doped with Al.
• the textured glass substrate according to the invention essentially has the following structure:
• Light transmission enhancement coating o Ti0 2 light transmission enhancement layer (confused with the barrier layer) o ZnO or Zn x Sn y O z crystallization layer (with x + y > 3 and z ⁇ 6) the geometric thickness of the coating for improving the transmission of light is at least 50.0 nm, preferably at least 60.0 nm, more preferably at least 70.0 nm and at most equal to 100 nm, preferably at most equal to 90.0 nm, more preferably at most equal to 80.0 nm, • Ag conduction metal layer, the geometric thickness of the metal conduction layer is at least equal to 6.0 nm, preferably at least 8.0 nm, more preferably at least 10.0 nm and at least more than 22.0 nm, preferably at most 20.0 nm, more preferably at most 18.0 nm.
• Sacrificial layer geometric thickness 1.0-3.0 nm in Ti
• Light transmission enhancement coating o Ti0 2 light transmission enhancement layer (confused with the barrier layer) o ZnO or ZnxSnyOz crystallization layer (with x + y> 3 and the geometric thickness of the light transmission enhancement coating is at least 20.0 nm and at most 40.0 nm.
• the geometric thickness of the metal conduction layer is at least 16.0 nm, preferably at least 18.0 nm, preferably at least 20.0 nm and at most equal to 29.0 nm, preferably at most equal to 27.0 nm, more preferably at most equal to 25.0 nm.
• Insertion layer geometrical thickness 3.0-20.0 nm in Zn x Sn y O z (with x + y> 3 and z ⁇ 6)
• Embodiments of the textured glass substrate are not limited to the modes discussed above but may also result from a combination of two or more of them.
• the process for producing the textured substrate according to the invention is a method in which the uniformization layer and / or a set of layers comprising the electrode are deposited on the glass substrate that has been previously chemically textured.
• Examples of such processes are sputtering techniques, possibly assisted by a magnetic field, plasma deposition techniques, CVD (Chemical Vapor Deposition) and / or PVD (Physical Vapor Deposition) deposition techniques.
• the deposition process is carried out under vacuum.
• under vacuum refer to a pressure of less than or equal to 1.2 Pa.
• the process under vacuum is a cathodic sputtering technique assisted by a magnetic field.
• the method of manufacturing the textured glass substrate comprises continuous processes in which any layer constituting the electrode is deposited immediately following the layer underlying it in the multilayer stack (for example: depositing the stack constituting the electrode according to the invention on a substrate which is a ribbon scrolling or deposition of the stack on a substrate which is a panel).
• the manufacturing process also includes discontinuous processes in which a lapse of time (for example in the form of a storage) separates the deposition of a layer and the layer underlying it in the stack constituting the electrode.
• the oxidation can be natural (for example: an interaction with an oxidizing compound present during the manufacturing process or during the storage of the electrode before complete manufacture of the optoelectronic device) or result from a post-treatment (for example: a treatment to ozone under ultraviolet).
• the glass substrate according to the present invention is incorporated in an optoelectronic device emitting or collecting light.
• the optoelectronic device is an organic electroluminescent device comprising at least one textured glass substrate according to the invention described above.
• almost white light is meant a light whose chromatic coordinates at 0 °, for radiation perpendicular to the surface of the substrate, are included in one of the eight quadrilaterals of chromaticity, including quadrilaterals. These quadrilaterals are defined on pages 10 to 12 of the standard ANSI_NEMA_ANSLG C78.377-2008. These quadrilaterals are represented in FIG. A1, entitled “Graphical representation of the chromaticity specification of SSL products in Table 1, on the CIE (X, Y) chromaticity diagram".
• the organic electroluminescent device is integrated in a glazing unit, a double glazing unit or a laminated glazing unit. It is also possible to integrate several electroluminescent organic devices, preferably a large number of organic electroluminescent devices.
• the organic electroluminescent device is enclosed in at least one encapsulating material made of glass and / or plastic.
• the different embodiments of organic electroluminescent devices can be combined.
• the various organic electroluminescent devices have a wide field of use.
• the invention is particularly directed to the possible uses of these organic electroluminescent devices for producing one or more light surfaces.
• the term luminous surface includes, for example, illuminated slabs, illuminated panels, light partitions, worktops, greenhouses, flashlights, wallpapers, drawer bottoms, illuminated roofs, touch screens, lamps, photo flashes, display backgrounds, safety signs, shelves.
• the textured glass substrate according to the invention will now be illustrated with the aid of the following figures.
• the figures show in a nonlimiting manner a number of substrate structures, more particularly layer stack structures constituting the electrode included in the substrate according to the invention. These figures are purely illustrative and do not constitute a presentation at the scale of the structures.
• the performance of organic electroluminescent devices comprising the textured glass substrate according to the invention will also be presented in the form of figures.
• Fig. 1 Schematic representation of the structure of texturing
• Fig. 3 Example of stair-shaped pyramid texturing patterns
• Fig. 4 Example of stair-shaped pyramid texturing patterns
• Fig. 5 Example of stair-shaped pyramid texturing patterns
• Fig. 6 Example of stair-shaped pyramid texturing patterns
• Fig. 7 Electron Micrograph of a Textured Glass Substrate According to the Invention
• Fig. 8 Schematic representation of the experimental setup to determine electro-luminescence evolution, dominant wavelength, and color purity versus angle of view.
• Fig. 9 Evolution of the dominant wavelength and purity of color according to the angle of observation.
• Fig. 10 Cross section of a textured glass substrate according to the invention according to a preferred embodiment.
• Fig. 11 Cross section of a textured glass substrate comprising at the level of the transparent electrode a minimum number of layers.
• Fig. 12 Cross section of a textured glass substrate according to the invention according to a second embodiment.
• Fig. 13 Cross section of a textured glass substrate comprising at the level of the transparent electrode a minimum number of layers having a different effect.
• Fig. 14 Evolution of the luminance of an organic electroluminescent device emitting an almost white light and comprising a support having a refractive index at 1.4 at a wavelength equal to 550 nm as a function of the geometric thickness of the coating. improvement of light transmission, having a refractive index of 2.3 at a wavelength of 550 nm, and the geometric thickness of a metal conduction layer in Ag.
• Fig. 15 Evolution of the luminance of an organic electroluminescent device emitting an almost white light and comprising a support having a refractive index of 1.5 at a wavelength equal to 550 nm as a function of the geometric thickness of the coating. improvement of light transmission, having a refractive index of 2.3 at a wavelength of 550 nm, and the geometric thickness of a metal conduction layer in Ag.
• Fig. 16 Evolution of the luminance of an organic electroluminescent device emitting an almost white light and comprising a support having a refractive index of 1.6 at a wavelength equal to 550 nm as a function of the geometric thickness of the coating of improvement of light transmission, having a refractive index of 2.3 at a wavelength of 550 nm, and the geometrical thickness of a conductive metal layer in Ag.
• FIG. 2 represents the evolution of the percentage of green light ( ⁇ : 550 nm) coming out frontally (perpendicular to the average plane of the surface of the substrate) of an organic electroluminescent device comprising texturing of the surface according to the invention relative to the light emitted by this device when a current of 1 mA is applied.
• these calculations show that the amount of light transmitted is a function of angle ⁇ .
• the transmitted light / transmitted light ratio is 12.5%. It can be observed that when the angle ⁇ is between 15 ° and 80 °, the transmitted light / transmitted light ratio is at least 25%, which corresponds to a 2-fold increase in the luminance seen frontally of the organic electroluminescent device. .
• the transmitted light / transmitted light ratio is at least 30%>, which corresponds to a 2.4-fold increase in luminance viewed frontally of the organic electroluminescent device.
• the transmitted light / transmitted light ratio is at least 34%, which corresponds to a 2.7-fold increase in the luminance seen frontally of the organic device.
• a transparent electrode comprising ITO
• the inventors have determined that a surface texturing that makes it possible to obtain geometric patterns such that the arctangent of (R z / (Rs m / 2)) corresponds to a value of the angle ⁇ of between 15 ° and 80 °. preferably between 25 ° and 70 °, more preferably between 35 ° and 60 ° could be carried out by etching.
• the etching can be carried out using acid solutions or concentrated alkaline solutions.
• the alkaline solutions are used at high concentrations and applied to the glass substrate having a temperature of at least 350 ° or brought after application to at least this temperature.
• the chemical etching of the substrate can be advantageously carried out by a controlled acid attack, by using acidic solutions commonly used in the manufacture of textured glass (for example by etching with acid
• alkaline salts and the ammonium salts are generally preferred, among these mentioning especially sodium, potassium and ammonium hydrofluoride and / or ammonium bifluoride.
• Such solutions are, for example, aqueous solutions comprising from 0 to 600 g / l of hydrofluoric acid, preferably from 150 to 250 g / l of hydrofluoric acid and also comprising from 0 to 700 g / l of NH 4 HF 2 , preferably from 150 to 300 g / l NH 4 HF 2 .
• the acid attack can be carried out in one or more steps. Attack times are at least 10s. Preferably, the attack times are at least 20 seconds. Attack times do not exceed 30 minutes.
• This chemical attack makes it possible to obtain a substrate such that the geometric patterns comprise at least one structure polygonal based step pyramid type.
• walking pyramid is meant a pyramid of which at least one face has a stepped structure. This staircase structure is such that the dimensions of the steps and counter steps are not necessarily equal to each other and two by two.
• the angle formed by a plane comprising a step and a plane comprising a counter-step is not necessarily equal to 90 °.
• the angle "on-march" seen from inside the pyramid is at least 100 °, more preferably at least 120 °.
• FIG. 7 shows an electron microscopy of a substrate according to the invention obtained using an acid texturing whose geometric patterns are patterns of type "pyramid walk” and whose texturing described in terms of roughness measurements, is R z : 14 ⁇ .
• Figure 8 shows a 3D image obtained by interferometry microscopy. Two linear profiles, one according to X and one according to Y, taken randomly on the 3D image of the sample (without necessarily going through the vertices of the profiles) to determine the average distance between the profiles (Rsm) are represented in FIG. 9.
• the organic electroluminescent device (1) used consists of the following stack from the emitting surface:
• a transparent electrode comprising: Optical optimization coating comprising a 60 nm Ti0 2 optical optimization layer and a Zn x Sn y O z crystallization layer (with x + y> 3 and z ⁇ 6) (combined with the barrier layer 9.0 nm thick
• Ti sacrificial layer geometric thickness 6.0 nm
• Insertion layer Zn x Sn y O z (with x + y> 3 and z ⁇ 6): geometric thickness 9.0 nm
• FIG. 10 represents an example of a textured glass substrate according to the invention, this substrate comprising a transparent electrode.
• the general structure of the glass substrate according to the invention is the following: a sheet of clear or extra-clear glass textured by chemical attack, totally or partially on at least one of its faces by a set of geometric patterns such as the arctangent of the ratio between the average height of the patterns, R z , and half the average distance separating the vertices of two contiguous patterns, Rs m , is equal to a value in the range of 35 ° to 80 °, preferably having a value in the range of 35 ° to 70 °, most preferably having a value in the range of 35 ° to 60 ° (1).
• an optical optimization coating (2) comprising an optical optimization layer (20) o
• FIG. 11 represents an alternative example of a glass substrate according to the invention, this substrate comprising a transparent electrode.
• the general structure of the glass substrate according to the invention is the following: a sheet of clear or extra-clear glass textured by chemical attack, totally or partially on at least one of its faces by a set of geometric patterns such as the arctangent of the ratio between the average height of the patterns, R z , and half the average distance separating the vertices of two contiguous patterns, Rs m , is equal to a value in the range of 35 ° to 80 °, preferably having a value in the range of 35 ° to 70 °, most preferably having a value in the range of 35 ° to 60 ° (1).
• An optical optimization coating (2) comprising an optical optimization layer (21) o A conduction layer (3) o An insertion layer (4) o A uniformization layer (5)
• FIG. 12 represents another alternative example of a glass substrate according to the invention, this substrate comprising a transparent electrode.
• the general structure of the glass substrate according to the invention is as follows:
• a sheet of clear or extra-clear glass textured by chemical etching, totally or partially on at least one of its faces by a set of geometric patterns such as the arctangent of the ratio between the average height of the patterns, R z , and half the average distance separating the vertices of two contiguous units, Rs m , is equal to a value in the range from 35 ° to 80 °, preferably having a value in the range of 35 ° to 70 °, most preferably having a value in the range of 35 ° to 60 ° (1).
• An optical optimization coating (2) comprising: a barrier layer (20) an optical optimization layer (21) a crystallization layer (22)
• FIG. 13 represents another alternative example of a substrate according to the invention, this substrate comprising a transparent electrode.
• the general structure of the stack from the substrate according to the invention (1) is as follows:
• An optical optimization coating (2) comprising an optical optimization layer (21)
• the organic part of the organic electroluminescent device is such that it has the following structure: a hole transport layer or HTL for "Hole Transporting Layer” in English having a geometrical thickness equal to 25.0 nm, a blocking layer electrons or EBL for "Electron Blocking Layer” in English having a geometrical thickness equal to 10.0 nm, o an emitting layer emitting a Gaussian spectrum of white light corresponding to illuminant A and having a geometrical thickness equal to 16, 0 nm, o a hole blocking layer or HBL for "Hole Blocking Layer” in English having a geometrical thickness equal to 10.0 nm, o an electron transport layer or ETL for "Electron Transporting Layer” in English having a geometric thickness equal to 43.0 nm.
• the luminance was calculated using the SETFOS version 3 program (Semiconducting Emissive Thin Film Optics Simulator) of the company Fluxim. This luminance is expressed in arbitrary units.
• the inventors have determined that, surprisingly, the selected domain is not only valid for an organic device emitting almost white light, but also for any type of color emitted (for example: red, green, blue).
• Table I shows the effect of the roughness of the support on the light extraction efficiency or OCE of the English Out-coupling Coefficient Effiency.
• the OCE is a factor that defines the amount of light that can be extracted in comparison with a reference.
• the reference used is an OLED device of identical structure (anode, organic part of the OLED and cathode) but whose glass sheet is not textured. OCEs are measured on OLEDs with the following structure: • Extra-clear textured glass sheet with a geometric thickness of 4 mm
• a transparent electrode comprising:
• the OCE is obtained by dividing the luminous flux value obtained by the luminous flux value measured for the reference.
• Table II shows the angular dependence of the colorimetric coordinates in the CIE diagram (x, y) for a reference OLED device, said reference sample being identical to that used to determine the OCE values presented in Table I and a device of identical structure (anode, organic part of the OLED and cathode) whose glass sheet has a roughness R z of 14 ⁇ and R Sm of 28-34 ⁇ . It is observed that less angular dependence of the colorimetric coordinates is obtained with a textured glass sheet.
• ⁇ ° "80 represents the difference between the highest value of x measured between 0 ° and 80 ° and the lowest value of x measured between 0 ° and 80 °
• Ay ° " 80 represents the difference between the highest y value measured between 0 ° and 80 ° and the lowest value of x measured between 0 ° and 80 °.
• the optical measurements were carried out using a multichannel spectroscope of commercial name C l 0027 marketed by Hamamatsu Photonics KK.
• the measurement angle is defined by the angle formed between the perpendicular to the glass sheet on the one hand and the line perpendicular to the measuring surface of the spectroscope on the other hand.

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