EP2130241A2

EP2130241A2 - Substrate bearing a discontinuous electrode, organic electroluminescent device including same and manufacture thereof

Info

Publication number: EP2130241A2
Application number: EP08762154A
Authority: EP
Inventors: Svetoslav Tchakarov
Original assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Current assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Priority date: 2007-02-23
Filing date: 2008-02-25
Publication date: 2009-12-09
Also published as: FR2913146B1; US20100117523A1; KR20090125095A; JP2010519699A; WO2008119899A3; CN101617418B; WO2008119899A2; JP5723529B2; FR2913146A1; CN101617418A; TW200904246A

Abstract

The invention relates to a substrate for an organic electroluminescent device (10) that bears a discontinuous electrode (2a-2c) with a metallic functional layer having an electric-conductivity intrinsic property between a contact layer and an upper layer, wherein the electrode has a square resistance lower than or equal to 5Ω/square for a functional layer thickness lower than 100 nm, the electrode being the form of at least one row of electrode areas, each electrode area having a first dimension (E) of at least 3 cm in the direction (X) of said row, the electrode areas of each row being separated from each other by a so-called intra-row distance (d1) lower than or equal to 0.5 mm. The invention also relates to an organic electroluminescent device (10) comprising the same, as well as to the manufacture of said electrode and said device.

Description

SUBSTRATE HAVING A DISCONTINUOUS ELECTRODE, ORGANIC ELECTROLUMINESCENT DEVICE INCORPORATING IT,

AND THEIR MANUFACTURING

The present invention relates to a carrier substrate of a discontinuous electrode for organic electroluminescent device, the organic electroluminescent device incorporating it and their fabrications.

The known organic electroluminescent systems or OLED (for "Organic Light Emitting Diodes" in English) comprise a material or a stack of organic electroluminescent materials supplied with electricity by electrodes flanking it in the form of electroconductive layers.

Typically, the upper electrode is a reflective metal layer, for example aluminum, and 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 150 nm. However, this ITO layer has a number of disadvantages. Firstly, the material and the high temperature deposition method (350 ^° C.) to improve the conductivity generate additional costs. The resistivity per square remains relatively high (of the order of 10 Ω parceled) unless the thickness of the layers is increased beyond 150 nm, which results in a decrease in the transparency and an increase in the surface roughness. creating spike effects that drastically reduce the life and reliability of the OLED.

In addition, to electrically separate the electrodes, the lower electrode is discontinuous, typically forming parallel strips of electrodes, each illuminating strip being connected in series. However, the Applicant has found that it is possible to have uniform illumination on illuminated strips of large areas. In addition, to obtain a filling factor ("fill factor" in English) satisfactory, corresponding to the illuminating surface ratio on the total surface of the device, it is necessary to drastically reduce the distance between the electrode strips using costly photolithography. The document EP1521305 thus proposes a lower electrode based on ITO in the form of zones of electrodes connected in series separated by etching lines invisible to the naked eye and filled with an insulating material, this by photolithography. In other known devices, the upper electrode is a continuous reflecting electrode and the lower electrode a continuous ITO layer surmounted by metal lines, generally made of aluminum and possibly organized in a grid, these metal lines aiming at improving the properties of Electroconductivity of the ITO layer for more uniform illumination over large areas. And to obtain a satisfactory filling factor, the lines are thin, of the order of 100 μm wide, and are obtained by photolithography with a masking in a photosensitive resin typically of thickness of about 400 nm. This photosensitive resin is retained on the lines for passivation purposes in order to avoid short circuits between the lower electrode and the upper electrode.

This lower electrode is expensive and unreliable because a single point of short circuit contaminates the entire surface, making the electroluminescent device defective.

The aim of the invention is to obtain a lower electrode which, while ensuring a uniformity of illumination over large areas, a satisfactory filling factor, is reliable, inexpensive and preferably easy to manufacture , especially on an industrial scale.

For this purpose, the subject of the present invention is a substrate for an organic electroluminescent device carrying, on a main surface, a discontinuous electrode comprising successively, from the substrate: a doped or non-doped metal oxide-based contact layer, single or mixed a metallic functional layer with intrinsic property of electrical conductivity, based on silver, having a functional layer thickness of less than 100 nm, an overlayer for the adaptation of the work function, in particular based on a metal oxide, doped or not, simple or mixed, the electrode having a square resistance of less than or equal to 5 Ω / square, or even less than or equal to 4 Ω / square, for a functional layer thickness of less than 100 nm, preferably less than or equal to 50 nm.

The discontinuous electrode according to the invention is further in the form of at least one row of electrode zones, with electrode zones (preferably all zones) having a first dimension of at least 3 cm in the direction of said row, preferably at least 5 cm, the electrode areas of the row being spaced apart by a so-called intraranged distance less than or equal to 0.5 mm. And insulating material fills the space between the electrode areas of the row (and preferably the space of any adjacent rows) and overflows over the electrode areas.

The electroconductive properties of the electrode according to the invention are made possible by the choice of a multilayer multilayer with a silver-based functional layer, which is also less expensive than an ITO functional layer because of the nature of the material used. electrode and manufacturing feasible at room temperature, for example, by spraying or evaporation.

The electrically conductive properties allow the uniformity of the illumination for each illuminating zone defined by the relatively large chosen electrode areas (at least 3 cm), this without penalizing the transparency nor generating roughness, the functional layer thickness being limited.

Typically, for one, of or each illuminating zone associated with an electrode zone, the ratio between the brightness (measured in Cd / m ² ) in the center and on any edge of this illuminating zone can thus be greater than or equal to 0 , 7, still more preferably greater than or equal to 0.8.

Passivation by the insulating material makes it possible to avoid short circuits between the electrodes of the OLED. In addition, the resin covers the possibly irregular edges of the electrode areas. These covered areas are therefore not illuminating which reinforces the possibility of uniform lighting. However, for a satisfactory filling factor, the width of each covered edge may preferably be less than 100 μm, or less or equal to 50 microns for example between 10 and 30 microns.

The higher limitation of the intraranged distance and the extent of each electrode zone provides a high fill factor without the need for photolithography to create the electrode areas. Since the electrode is organized in one or more rows, a defective electrode area does not interfere with the operation of the other electrode areas.

The thickness (total) of ITO, or even (mainly) oxide based on indium in the electrode may be less than or equal to 40 nm, or even 30 nm. The total thickness of the electrode may be less than or equal to 250 μm; even more preferably at 150 nm to promote the extraction of light.

The electrode according to the invention may be over a large surface, for example an area greater than or equal to 0.02 m ² or even 0.5 m ² or 1 m ² .

The intraranged distance can be at least 20 microns, to limit short circuits between the edges, preferably between 50 microns and 250 microns, especially between 100 and 250 microns.

Advantageously, the discontinuous electrode can be obtained without photolithography, for example:

by laser etching, typically forming beads, and / or by under-masking,

and / or by chemical screen printing of an etching paste, in particular an acid-based paste, typically forming irregular edges which are corrugated because of the screen printing screen meshes, techniques that are well mastered industrially and inexpensively. Sub-masking consists in depositing the discontinuous mask, typically parallel lines possibly in a grid. This mask is soluble material with a solvent (water, alcohol, acetone ...) neutral for the electrode. The mask can be deposited by screen printing, by ink jet. A full layer of electrode material is then deposited and the mask is dissolved, thereby creating the gaps between the electrode regions (preferably in the form of parallel lines).

In a preferred design of the invention, the insulating material also covers the edges of the (more) peripheral electrode areas. As an insulating material, for example, an acrylic or polyamide resin may be chosen, for example the Wepelan resins known as SD2154E and SD2954.

Preferably, to reduce (yet) the manufacturing costs; the insulating material, preferably organic, in particular polymeric material, is chosen from screen-printed insulating material, in particular an acrylic or polyamide resin, insulating material deposited by ink jet, for example the ink described in patent US 6 986 982, or still deposited by roll coating.

The silkscreened insulating material typically forms irregular edges, which are wavy due to the screen screen meshes. The inkjet deposited material typically has a profile in the form of "cup" ("coffee cups"), the edges being thickened.

Preferably, for a freedom of choice of the electrical connections, the electrode comprises a plurality of rows parallel to each other, the rows of electrode zones being spaced apart by a so-called interangular distance less than or equal to 0.5 mm, preferably between 100 μm and 250 μm.

These rows may preferably be electrically insulated from each other by an insulating resin such as already described, in particular screen-printed or ink-jet deposited. Like the intraranged spaces, the spaces between rows can be preferably manufactured by laser or under masking, by chemical screen printing with the etching paste.

Each electrode zone can be a solid geometric pattern (square, rectangle, round ...). From one row to another, the patterns can be shifted, for example for a staggered arrangement.

Within the same row, the electrode areas may be of substantially identical shape and / or size.

From one row to another, the electrode areas may be of substantially distinct shape and / or size. In the direction perpendicular to the row, the dimension of the electrode zone may be any, for example at least 3 cm, 5 cm or even about ten cm (10 cm and beyond). Advantageously, the electrode according to the invention can present:

a square resistor less than or equal to 5 Ω / square for a thickness of (each) functional layer less than or equal to 20 nm, and a light transmission TL of greater than or equal to 60%, even more preferentially at 70% and a factor of Absorption A

(given by 1-LR-TL) less than 10%, which makes its use as a transparent electrode particularly satisfactory, for a rear emission electroluminescent device ("bottom emission" in English), - a resistance square less than or equal to 3 Ω / square for a thickness of (each) functional layer from 20 nm, preferably less than or equal to 1.8 Ω / square, and a ratio TL on R _L between 0.1 and 0.7 and an absorption factor A of less than 10%, which makes its use as a semi-transparent electrode particularly satisfactory, for a rear-emitting and front-emitting light-emitting device,

a square resistor less than or equal to 1 Ω / square for a thickness of (each) functional layer from 50 nm, preferably less than or equal to 0.6 Ω / square, preferably combined with a light reflection RL greater than or equal to at 70%, even more preferably at 80%, which makes its use as a reflective electrode particularly satisfactory, for a light emitting device to emit from the front ("top emission" in English). The TL may preferably be measured on a thin substrate, for example of the order of one millimeter, and TL of the order of 90%, for example a silicosocalocalic glass.

The surface of the electrode may be of roughness RMS (otherwise called Rq) preferably less than or equal to 2 nm, and even more preferably less than or equal to 1, 5 nm or even less than or equal to 1 nm in order to avoid defects of spikes.

Roughness RM S stands for "Root Mean Square" roughness. It's about a measuring the value of the mean square deviation of the roughness. This roughness RM S, concretely, thus quantifies on average the height of the peaks and troughs of roughness, with respect to the average height. Thus, an RM S roughness of 2 nm means a double peak amplitude. It can be measured in various ways: for example, by atomic force microscopy, by a mechanical point system (using, for example, the measuring instruments marketed by VEECO under the name DEKTAK), by optical interferometry. on a square micrometer by atomic force microscopy, and on a larger surface, of the order of 50 micrometers to 2 millimeters for mechanical systems with tip.

This low roughness is particularly achieved when the substrate comprises between the bottom layer and the contact layer a non-crystallized smoothing layer of a mixed oxide, said smoothing layer being disposed immediately under said contact layer and being made of another material than that of the contact layer.

The smoothing layer is preferably an oxide-based mixed oxide layer of one or more of the following metals: Sn, Si, Ti, Zr, Hf, Zn, Ga, In and in particular is a layer mixed zinc oxide and optionally doped tin oxide or a mixed indium tin oxide (ITO) layer or a mixed indium zinc oxide layer (IZO).

The smoothing layer preferably has a geometric thickness between 0.1 and 30 nm and more preferably between 0.2 and 10 nm.

The functional layer is based on pure silver or alloy or doped with Au, Al, Pt, Cu, Zn, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn, Pd. There may be mentioned, for example, silver doped with Pd or a gold-copper alloy or a silver-gold alloy.

The functional layer may be deposited by a vacuum deposition technique, in particular by evaporation or preferably by magnetic field assisted sputtering, especially at room temperature.

If a high conductivity is particularly desired one can choose preferably a pure material. If mechanical properties remarkable are particularly sought, one can choose preferably a doped material or alloyed.

A silver-based layer is chosen for its conductivity and transparency. The thickness of the functional layer based on silver may be between 3 to 20 nm, preferably between 5 to 15 nm. In this range of thicknesses, the electrode remains transparent. The thickness of the silver-based functional layer may further be between 20 to 50 nm to switch from operation mainly in transmission, to operation mainly in reflection. The output work adaptation overlay can have a work output Ws from 4.5 eV and preferably greater than or equal to 5 eV.

The overlayer for adapting the output work may preferably be based on at least one of the following metal oxides: indium oxide, zinc oxide, molybdenum oxide and nickel oxide, which are preferably under stoichiometric for the adaptation of the output work, aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, tin oxide, silicon oxide.

The metal oxide can be doped typically between 0.5 and 5%. These are in particular S-doped tin oxide, or Al (AZO) doped zinc oxide, Ga (GZO), B, Sc, or Sb for a better stability of the deposition process, and or increase the electrical conductivity.

The overlayer may be based on a mixed oxide, in particular a mixed zinc oxide and tin oxide Sn _x Zn _y O _z generally non stoichiometric and under amorphous phase, or a mixed oxide of indium and tin (ITO), a mixed oxide of indium and zinc (IZO).

The overlay may be a monolayer or a multilayer. This layer is preferably of thickness (total) between 3 and 50 nm even more preferably between 5 and 20 nm.

An overcoat with an electrical conductivity greater than 10 ⁶ S. cm- ¹ , or even ICH S. cm- ¹ , an easy and / or rapid layer to be produced, which is transparent, in particular an overcoat, doped or otherwise, based on ITO, IZO, Sn _x Zn _y O _z, ZnO NiO ,, _x, MoO _x, In ₂ O _3. Since this overlayer may preferably be the last layer, a dTiO overcoat which is stable is more particularly preferred and it is moreover possible to retain the existing technologies for the manufacture and optimization of the OLED organic structure while controlling the costs. The substrate may be preferably planar.

The substrate may be transparent (especially for emission through the susbtrate). The substrate may be 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 with an electrode substantially occupying the surface (the structuring zones).

The substrate may be a plastic, for example polycarbonate, polyethylene terephthalate PET, polyethylene naphthalate PEN, polymethyl methacrylate PMMA.

The substrate is preferably glass, in particular of silicosodocalcic glass. 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). For example, silicosodocalcic glasses with less than

0.05% Fe III or Fe 2 O 3, especially Saint-Gobain Glass Diamond, Pilkington Optiwhite glass, Schott B270 glass. All the extraclear glass compositions described in WO04 / 025334 can be selected. In a chosen configuration of a transmission of the OLED system through the thickness of the transparent substrate (emission from the rear), a part of the emitted radiation is guided in the substrate.

Also, in an advantageous design of the invention, the thickness of the selected glass substrate may be at least 0.35 mm, preferably at least 1 mm, for example. This reduces the number of internal reflections and thus extract more radiation guided in the glass, thus increasing the luminance of the light zone. The edges of the wafer, may also be reflective, and preferably comprise a mirror, to ensure optimum recycling of the guided radiation and edges, forms with the main face associated with the OLED system an external angle greater than or equal to 45 ° and less than 90 °, preferably greater than or equal to 80 °, to redirect the radiation over a larger extraction zone. The slice can be thus beveled.

The electrode may comprise, under the functional layer, preferably a base layer, capable of forming an alkaline barrier

The basecoat may be a barrier to the alkali underlying the electrode. It protects from any pollution the contact layer or any other layer above (pollution that may cause mechanical defects such as delamination), further preserves the electrical conductivity of the functional metal layer. It also prevents the organic structure of an OLED device from being polluted by alkalis, thereby significantly reducing the life of the OLED.

The alkali migration can occur during the manufacture of the device, causing unreliability, and / or subsequently reducing its life.

The primer improves the bonding properties of the contact layer without significantly increasing the roughness of the stack of layers, even when one or more layers are interposed between the primer layer. and the contact layer.

The primer is preferably strong, easy and fast to deposit according to different techniques. It can be deposited, for example by a pyrolysis technique, especially in the gas phase (a technique often referred to by the abbreviation of CVD, for "Chemical Vapor Deposition"). This technique is interesting for the invention because appropriate settings of the deposition parameters make it possible to obtain a very dense layer for a reinforced barrier. The primer may be optionally doped with aluminum to make its vacuum deposit more stable. The bottom layer (monolayer or multilayer, optionally doped) may be between 10 and 150 nm thick, more preferably between 20 and 100 nm. The bottom layer may preferably be:

based on silicon oxide (of general formula SiO),

based on silicon oxycarbide (of general formula SiOC), based on silicon nitride (of general formula SiN), in particular with

based on silicon oxynitride (of general formula SiON),

based on silicon oxycarbonitride (of general formula SiONC).

It is possible that the nitriding of the primer is slightly under stoichiometric.

It can be based on silicon oxycarbide and with tin to enhance the properties of anti acid etching in the case of a chemical screen printing.

A bottom layer (essentially) of silicon nitride SiβN / t, which may or may not be doped, may be particularly preferred. Silicon nitride is very fast to deposit and forms an excellent barrier to alkalis. In addition, thanks to its high optical index relative to the carrier substrate makes it possible to adapt the optical properties of the electrode by preferably playing on the thickness of this base layer. This thus makes it possible, for example, to adjust the color in transmission when the electrode is transparent or in reflection when the opposite face of the carrier substrate is a mirror.

The electrode may preferably comprise an etching stop layer, in particular a chemical layer, under the contact layer (or even on the optional and distinct primer), in particular a layer based on tin oxide, this layer of etching stop being in particular of thickness between 10 and

100 nm, even more preferably between 20 and 60 nm.

The etch stop layer may protect the substrate and / or the primer, particularly in the case of chemical screen printing etching.

Thanks to the etching stop layer, the base layer remains present even in the engraved areas ("patterned" in English)). Also, the alkali migration, by edge effect, between the substrate in an etched area and an adjacent electrode portion (or even an organic structure) can be stopped. In particular, for the sake of simplicity, the etch stop layer may be part of or be the bottom layer: it may preferably be based on silicon nitride or it may be a layer which is based on silicon dioxide. silicon oxide or based on silicon oxynitride or on the basis of silicon oxycarbide or based on silicon oxycarbonitride and with tin to enhance by anti-etch property, layer of general formula SnSiOCN.

One can particularly prefer a bottom layer / stop of (mainly) etching silicon nitride SiβN / t, doped or not. Silicon nitride is very fast to deposit and forms an excellent barrier to alkalis, as already indicated. In addition, thanks to its high optical index relative to the carrier substrate, it allows to adapt the optical properties of the electrode by preferably playing on the thickness of the base layer / etch stop.

This thus makes it possible, for example, to adjust the color in transmission when the electrode is transparent or in reflection when the opposite face of the carrier substrate is a mirror.

The contact layer may preferably be directly under the silver-based functional layer (excluding any thin blocking layer) and serve as an adhesion and / or wetting layer of the functional layer.

The contact layer may preferably be based on at least one of the following metal oxides stoichiometric or not: chromium oxide, indium oxide, zinc oxide, aluminum oxide, titanium oxide, molybdenum oxide, zirconium oxide, antimony oxide, tantalum oxide, silica oxide or even tin oxide.

The metal oxide can be doped typically between 0.5 and 5%. It is in particular zinc oxide doped with Al (AZO), Ga (GZO), or even with B, Sc, or Sb for a better stability of deposition process or even tin oxide doped with F or S.

The contact layer may be based on a mixed oxide, in particular a mixed oxide of zinc and tin Sn _x Zn _y O _{z which is} generally non-stoichiometric and in an amorphous phase, or of a mixed oxide of indium and of tin (ITO), a mixed oxide of indium and zinc (IZO). The contact layer may be a monolayer or a multilayer. This layer is preferably of thickness (total) between 3 and 30 nm, more preferably between 5 and 20 nm.

A layer which is not toxic is preferably chosen, an easy and / or rapid layer to be produced, possibly transparent if necessary, in particular a doped or non-doped layer based on ITO, IZO, Sn _x Zn _y O _z , ZnO _x .

A layer of crystalline nature is preferably more preferably selected in a preferred growth direction to promote heteroepitaxy of the functional silver-based metal layer. A ZnOx zinc oxide layer is preferably preferred, with preferably less than 1 x, even more preferably between 0.88 and 0.98, especially from 0.90 to 0.95. This layer can be pure or doped with Al or Ga as already indicated.

In a preferred embodiment of the invention, to further prevent corrosion of the functional layer, the electrode may comprise, between the functional layer and the overcoat layer, a metal oxide-based protective layer against oxygen and / or or water, especially when the overlayer is thin (less than or equal to 20 nm).

The protective layer may preferably be based on at least one of the following metal oxides: indium oxide, zinc oxide, aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, silicon oxide , tin oxide.

The metal oxide can be doped typically between 2 and 5%. It is in particular S-doped tin oxide, or Al-doped ZnO doped zinc oxide (AZO) for a better stability, Ga (GZO) to increase the conductivity, or even B , Sc, or Sb.

The protective layer may be based on a mixed oxide, in particular a zinc and tin oxide Sn _x Zn _y O _{z that is} generally non-stoichiometric and in an amorphous phase, or a mixed oxide of indium and aluminum oxide. tin (ITO), a mixed oxide of indium and zinc (IZO). The protective layer may be a monolayer or a multilayer This layer is preferably of thickness (total) between 3 and 90 nm even more preferably between 5 and 30 nm.

Naturally, the addition of this layer dedicated to the protection allows a greater freedom in the choice of the overlayer only chosen to have optimal surface properties including surface work adaptation for OLEDs.

A protective layer which is easy and / or fast to produce is preferably transparent, in particular a layer, doped or non-doped, based on ITO, IZO, Sn _x Zn _y O _z , ZnO _x .

In particular, a layer based on ZnOx zinc oxide is preferably used, with x preferably less than 1, preferably between 0.88 and 0.98, especially from 0.90 to 0.95. This layer can be pure or doped as already indicated. This layer is particularly adapted to be directly on the functional layer without degrading its transparency or its electrical conductivity.

In a preferred embodiment of the invention, the contact layer and the protective layer are identical in nature, in particular pure zinc oxide, doped or even alloyed, and preferably the overcoat is ITO.

The total thickness (with the primer) can be between 30 nm and 250 nm, or even 150 nm.

The stack of thin layers producing the electrode coating is preferably a functional monolayer coating, that is to say a single functional layer; however, it can be multi-layer functional and in particular two-layer functional. Between the silver-based functional layer and the overcoat, the electrode may comprise successively: a metal oxide-based separating layer optionally comprising said protective layer, said smoothing layer, a second contact layer (in particular similar to the contact layer or at least the materials already mentioned), a second functional layer based on silver (in particular similar to the functional layer), and a possible blocking coating (in particular similar to the possible coating overblocking or to at least in the materials already mentioned). The electrode can be obtained by a succession of deposits made by a technique using vacuum such as cathodic sputtering possibly assisted by magnetic field. Can also be provided one or even two very thin coating (s) called "blocking coating", arranged (s) directly under, on or on each side of each functional metal layer including a base silver, the coating underlying the functional layer, towards the substrate, as a bonding, nucleation and / or protective coating, and the coating overlying the functional layer as a protective coating or "Sacrificial" in order to avoid the alteration of the functional metallic layer by etching and / or migration of oxygen of a layer which overcomes it, or even by oxygen migration if the layer which surmounts it is deposited by cathodic sputtering in the presence of oxygen.

The functional metal layer can thus be disposed directly on at least one underlying blocking coating and / or directly under at least one overlying blocking coating, each coating having a thickness of preferably between 0.5 and 5 nm.

Within the meaning of the present invention when it is specified that 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.

At least one blocking coating preferably comprises a metal layer, nitride and / or metal oxide, 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.

For example, a blocking coating 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 blocking layer forms a protective layer or even a "sacrificial" layer which makes it possible to avoid the deterioration of the metal of the functional metallic layer, in particular in one and / or the other of the following configurations: if the layer which overcomes the functional layer is deposited using a reactive plasma (oxygen, nitrogen, etc.), for example if the oxide layer which surmounts it is deposited by cathodic sputtering, if the composition of the layer which overcomes the functional layer is likely to vary during industrial manufacture (evolution of deposition conditions such as wear of a target, etc.), especially if the stoichiometry of a layer of oxide and / or nitride type evolves, thus modifying the quality of the layer functional and therefore the properties of the electrode (square resistance, light transmission, ...), - if the electrode coating undergoes subsequent heat treatment.

This protective or even sacrificial layer significantly improves the reproducibility of the electrical and optical properties of the electrode. This is very important for an industrial approach where only a low dispersion of electrode properties is acceptable.

In particular, a thin blocking 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 is particularly preferred. metals, including niobium and tantalum (Nb / Ta), niobium and chromium (Nb / Cr) or tantalum and chromium (Ta / Cr) or nickel and chromium (Ni / Cr) alloys . This type of layer based on at least one metal has a particularly important effect of entrapment ("getter" effect).

A thin metal blocking layer can be easily manufactured without altering the functional 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.

Such a thin metal blocking layer also makes it possible to obtain excellent mechanical strength (resistance to abrasion, especially to scratches).

This is especially true for stacks that are undergoing treatment thermal, and therefore a significant diffusion of oxygen or nitrogen during this treatment.

However, for the use of metal blocking layer, it is necessary to limit the thickness of the metal layer and thus the light absorption to maintain a sufficient light transmission for the transparent electrodes.

The thin blocking layer can be partially oxidized. This layer is deposited in non-metallic form and is thus not deposited in stoichiometric form, but in sub-stoichiometric form, of the MO _x type, where M represents the material and x is a number less than the stoichiometry of the oxide of the material or type MNO _x for an oxide of two materials M and N (or more). For example, TiO _x , NiCrO _x may be mentioned. x is preferably between 0.75 and 0.99 times the normal stoichiometry of the oxide. 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.

In a particular variant, the thin blocking layer is based on TiO _x and x can be in particular such that 1, 5 ≤ x ≤ 1, 98 or 1, 5 <x <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 y is a number less than the stoichiometry of the nitride of the material, y is preferably between 0 , 75 times and 0.99 times the normal stoichiometry of nitride.

In the same way, the thin blocking layer can also be partially oxynitrided.

This thin oxidized and / or nitrided blocking layer can be easily manufactured without altering the functional layer. It is preferably deposited from a ceramic target, in a non-oxidizing atmosphere preferably consisting of noble gas (He, Ne, Xe, Ar, Kr). The thin blocking layer may be preferably nitride and / or substoichiometric oxide for further reproducibility of electrical and optical properties of the electrode. The thin blocking layer chosen under stoichiometric oxide and / or nitride may be preferably based on a metal chosen from at least one of the following metals: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, W, or an oxide of a stoichiometric alloy based on at least one of these materials.

Particularly preferred is a layer based on an oxide or oxynitride of a metal selected from niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel Ni or an alloy from at least two of these metals, 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).

As the substoichiometric metal nitride, it is also possible to choose a silicon nitride SiN _x or aluminum AlNx or chromium Cr N _x layer, or TiN _x titanium or nitride of several metals such as NiCrN _x . The thin blocking layer may have an oxidation gradient, for example M (N) OH with variable X ₁ , the part of the blocking layer in contact with the functional layer is less oxidized than the part of this layer furthest away of the functional layer using a particular deposition atmosphere. The blocking coating may also be multilayer and in particular comprise: on the one hand an "interface" layer immediately in contact with said functional layer, this interface layer being made of a material based on oxide, nitride or non-stoichiometric metal oxynitride, such as those mentioned above, on the other hand, at least one layer of a metallic material, such as those mentioned above, layer immediately in contact with said "interface" layer.

The interface layer may be an oxide, nitride, or oxynitride of a metal or metal that is or is present in the eventual adjacent metal layer. The invention also relates to an organic electroluminescent device comprising at least one carrier substrate, in particular a glass substrate, provided with:

a discontinuous lower electrode as defined above, thus forming at least one lower electrode zone row, at least one discontinuous layer of organic electroluminescent material (s) in the form of zones electroluminescent layers arranged on the electrode areas,

a discontinuous upper electrode with an electroconductive layer in the form of electrode zones arranged on the electroluminescent layer areas.

And for serial row connection, the electroluminescent layer areas are shifted from the lower electrode areas in the row direction and the lower electrode areas are shifted from the electroluminescent electrode areas in the row direction. . It is recalled that in a serial connection, the current flows from an upper electrode area to the adjacent lower electrode area.

The lower electrode may form a single row of lower electrode areas, and in the direction perpendicular to that row, the upper electrode and the electroluminescent layer may be discontinuous to form a plurality of parallel rows.

Thus, advantageously, the device can be organized into a plurality of substantially parallel electroluminescent rows spaced apart by less than 0.5 mm, each row being capable of being connected in series. The distance between the electroluminescent zones of distinct rows may be greater than the distance between the zones of the same row, preferably from 100 μm, in particular between 100 μm and 250 μm.

Each row can thus be independent. If one of the zones in each row is defective, the entire row still works. And the adjacent rows are intact. Alternatively, the lower electrode may comprise a plurality of rows of lower electrode zones and the electroluminescent layer and the upper electrode reproduce these rows (offset in the row direction).

Various types of connections are possible: - a single serial connection of all the electroluminescent zones, a set of serial and parallel connections, serial connections specific to each row.

In a preferred embodiment, electrical junction pads in the form of an electroconductive layer of material identical to the upper electrode material are connected to peripheral edges of lower electrode areas, possibly covering an underlying insulating resin. .

The organic electroluminescent device according to the invention can be supplied with or without the current leads.

Two continuous or discontinuous current feed strips forming a portion of a collector or a current distributor may respectively be electrically connected to peripheral edges of lower electrode regions, preferably via junction regions. , and with peripheral edges of upper electrode areas.

These current feed strips may preferably be between 0.5 to 10 μm thick and 0.5 mm wide and may be in various forms:

a metal monolayer of one of the following metals: Mo, Al, Cr, Nd or of a metal alloy such as MoCr, AlNd,

a metal multilayer from the following metals: Mo, Al, Cr, Nd, such as MoCr / Al / MoCr,

- Preferably enamel conductive for example silver and screen printed, - preferably conductive material or charged with conductive particles and deposited by inkjet, for example silver ink such as ink TEC PA 030 ™ of InkTec Nano Silver Paste Inks, - Conductive polymer doped or not with metals, silver for example.

It is also possible to use a thin metallic layer known as "TCC" (Transparent Conductive Coating in English), for example in Ag, Al, Pd, Cu, Pd, Pt In or Mo, and typically having a thickness between 5 and 50 nm. function of the transmission / light reflection desired.

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).

One can use more generally any type of transparent electroconductive layer, for example a so-called TCO layer (for Transparent Conductive Oxide in English), for example with a thickness between 20 and 1000 nm.

The OLED device can produce monochromatic light, especially blue and / or green and / or red, or be adapted to produce white light.

To produce white light several methods are possible: mixture of compounds (emission red green, blue) 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.

The device can be part of a multiple glazing, including a vacuum glazing or with air knife or other gas. The device can also be monolithic, to understand a monolithic glazing to gain compactness and / or lightness.

The OLED system may be glued or preferably laminated with another flat substrate said cover, preferably transparent such as a glass, using a lamination interlayer, in particular extraclair.

The laminated glazings usually consist of two rigid substrates between which is disposed a sheet or a superposition of polymer sheets of the thermoplastic type. The invention also includes so-called "asymmetrical" laminated glazings using a particularly rigid carrier substrate of the glass type and as a substrate covering one or more protective polymer sheets.

The invention also includes laminated glazings having at least one interlayer sheet based on a single or double-sided adhesive polymer of the elastomer type (that is to say not requiring a lamination operation in the conventional sense of the term, laminating imposing heating generally under pressure to soften and adhere the thermoplastic interlayer sheet).

In this configuration, the means for securing the cover and the carrier substrate may then be a lamination interlayer, in particular a sheet of thermoplastic material, for example polyurethane (PU), polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), or resin multi-component or multi-component thermally crosslinkable (epoxy, PU) or ultraviolet (epoxy, acrylic resin). It is preferably (substantially) of the same size as the cover and the substrate.

The lamination interlayer may make it possible to prevent bending of the bonnet, particularly for devices of large dimensions, for example with an area greater than 0.5 m ² .

In particular, EVA offers many advantages:

- it is not or little loaded with water in volume,

it does not necessarily require a high pressurization for its implementation.

A thermoplastic lamination interlayer may be preferred to a cast resin cover because it is both easier to implement, more economical and is possibly more watertight.

The interlayer optionally comprises a network of electroconductive son embedded in its so-called internal surface facing the upper electrode, and / or an electroconductive layer or electroconductive strips on the inner surface of the cover.

The OLED system can be preferably placed inside the double glazing, with a particularly inert gas blade (argon for example).

In addition, it may be advantageous to add a coating having a given functionality on the opposite side of the carrier substrate of the electrode according to the invention or on an additional substrate. It may be an anti-fog layer (using a hydrophilic layer), anti-fouling (photocatalytic coating comprising at least partially crystallized TiCb in anatase form), or an anti-reflection stack of type for example

Si3N4 / SiO2 / Si3N4 / SiC> 2 or a UV filter such as a titanium oxide layer (TiCb). It may also be one or more phosphor layers, a mirror layer, at least one scattering zone light extraction.

The invention also relates to the various applications that can be found in these OLEDS devices, forming one or more transparent and / or reflecting light surfaces (mirror function) arranged both outside and inside.

The device can form (alternative or cumulative choice) an illuminating, decorative, architectural, (etc.) system, a signaling display panel - for example of the drawing, logo, alphanumeric signage type, in particular an emergency exit sign .

The OLED device can be arranged to produce a uniform light, especially for uniform illumination, or to produce different light areas of the same intensity or distinct intensity.

Conversely, one can seek a differentiated lighting. The organic electroluminescent system (OLED) produces a direct light region, and another light zone is obtained by extraction of OLED radiation which is guided by total reflections in the thickness of the selected glass substrate. To form this other light zone, the extraction zone may be adjacent to the OLED system or on the other side of the substrate. The extraction zone (s) can be used, for example, to reinforce the illumination provided by the direct light zone, in particular for an architectural type of lighting, or to signal the luminous panel. The extraction zone or zones are preferably in the form of band (s) of light, in particular uniform (s), and preferably arranged (s) on the periphery of one of the faces. These strips can for example form a very bright frame.

The extraction is obtained by at least one of the following means arranged in the extraction zone: a diffusing layer, preferably based on mineral particles and preferably with a mineral binder, the substrate made diffusing, in particular texture or rough.

The two main faces may each have a direct light area. When the electrodes and the organic structure of the OLED system are chosen to be transparent, an illuminating window can in particular be produced. Improved lighting of the room is not achieved at the expense of light transmission. By also limiting the light reflection, especially on the outside of the illuminating window, this also makes it possible to control the level of reflection, for example to comply with the anti-glare standards in force for building facades.

More generally, the device, in particular transparent by part (s) or entirely, can be

- intended for the building, such as an external luminous glazing, an internal light partition or a part (part of) luminous glass door in particular sliding,

- intended for a transport vehicle, such as a luminous roof, a (part of) side window light, an internal light partition of a land vehicle, aquatic or aerial (car, truck train, plane, boat etc),

- intended for urban or professional furniture such as a bus shelter panel, a wall of a display, a jewelery display or of a window, a wall of a greenhouse, an illuminating slab, - intended for interior furnishing, a shelf or furniture element, a facade of a piece of furniture, an illuminating slab, a ceiling lamp, an illuminating tablet refrigerator, an aquarium wall, - for the backlighting of electronic equipment, including display screen or display, possibly dual screen, such as a television or computer screen, a touch screen. For example, it is possible to design a backlighting of a double-sided screen with different sizes, the small screen being preferably associated with a Fresnel lens to focus the light.

To form an illuminating mirror, one of the electrodes may be reflective or a mirror may be disposed on the opposite side of the OLED system, if it is desired to favor illumination of only one side in the direct light region. It can also be a mirror. The illuminated panel can be used for lighting a bathroom wall or a kitchen worktop, to be a ceiling lamp.

OLEDs are generally dissociated into two major families depending on the organic material used. If the electroluminescent layers are small molecules, we speak of

SM-OLED (Small Mollecule Organic Light Emitting Diodes). The organic electroluminescent material of the thin layer consists of evaporated molecules such as, for example, AlQ_3 complex (tris (8-hydroxyquinoline) aluminum), DPVBi (4,4 '- (diphenylvinylene biphenyl)), 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 ', 4 ^! Tris (2-phenylpyridine) -tri (N-carbazolyl) triphenylamine (TCTA) doped with iridium [Ir (ppy) 3].

In general, the structure of an SM-OLED consists of a hole injection layer stack or "HIL" for "HoIe Injection

Layer "in English, hole transport layer or" HTL "for" HoIe Transporting Layer "in English, emissive layer, electron transport layer or" ETL "for" Electron Transporting Layer "in English.

An example of a hole injection layer is copper phthalocyanine (CuPC), the hole-transporting layer may be, for example, N, N'-Bis (naphthalenyl) -N, N'-bis ( phenyl) benzidine (alpha-NPB).

The electron transport layer may be composed of tris- (8-hydroxyquinoline) aluminum (Alqβ) or bathophenanthroline (BPhen). The upper electrode may be an Mg / Al or LiF / Al layer. Examples of organic electroluminescent stacks are for example described in US6645645.

If the organic electroluminescent layers are polymers, it is called PLED (Polymer Light Emitting Diodes in English).

The organic electroluminescent material of the thin layer consists of these polymers (pLEDs), for example PPV for poly (pαra-phenylene vinylene), PPP (poly (pαrα-phenylene), and DO-PPP (poly (2 decyloxy-1,4-phenylene), MEH-PPV (poly [2- (2'-ethylhexyloxy) -5-methoxy-1,4-phenylene vinylene)]), CN-PPV (poly [2,5] -bis (hexyloxy) -1,4-phenylene- (1-cyanovinylene)]) or PDAF (poly (dialkylfluorene), the polymer layer is also associated with a layer which promotes the injection of holes (HIL) constituted by example of PEDT / PSS (poly (3,4-ethylene-dioxythiophene / poly (4-styrene sulfonate)).

An example of PLED consists of a following stack:

a layer of poly (2,4-ethylene dioxythiophene) doped with poly (styrenesulphonate) (PEDOT: PSS) of 50 nm, and a layer of phenyl poly (p-phenylenevinylenene) PH-PPV of 50 nm.

The upper electrode may be a layer of Ca.

The invention also relates to the method of manufacturing the discontinuous lower electrode as defined previously comprising:

an etching step without photolithography, to form the lower electrode zones in one or more parallel rows, an insulating resin filling step (organic material, polymeric being preferred) by screen printing and / or ink jet, between the electrode zones and projecting over the edges of the electrode zones,

This process is fast, inexpensive and reliable. The etching step without photolithography, may comprise (consist of):

laser etching or sub-masking,

and / or chemical screen printing with an acid etching paste, for example with HiperEtch ™ 04S isishape ™ ink sold by Merck.

Laser ablation etching may be used preferably when the minimum distance is greater than or equal to 150 μm. Sub-masking by screen printing is preferred if the areas to be etched are wider than 100 μm. Ink-jet masking is preferred if the areas to be etched are narrower than 100 μm. The method may also include a step of manufacturing current supply tape (s), for example by screen printing and / or by ink jet as already indicated.

The invention also relates to the method of the organic electroluminescent device comprising: - a step of forming said discontinuous lower electrode, in one or more parallel rows, as defined above,

a step of forming the electroluminescent zones by deposition of the electroluminescent material (s) on a mask in the form of an organized network of lines, for example metallic, in particular aluminum or ferroelectric (chromium, nickel, etc.), following first and second directions crossed, the lines in the second direction being thicker.

This mask can be manufactured for example from a metal sheet which is made for example by electrogravure. The thick lines reinforce the rigidity of the thin lines intended to create the intra-row spaces. This facilitates alignment and limits the risk of short circuits. Advantageously, during the step of forming the upper electrode areas, the method may comprise forming the electrical bonding pads at the lower peripheral peripheral electrode regions of the separate array by depositing the at least one upper electrode material. The invention will now be described in more detail using non-limiting examples and figures:

FIG. 1 is a diagrammatic sectional view of an organic electroluminescent device, which comprises a lower electrode according to the invention; - FIG. 2 is a diagrammatic view from above of the device of FIG.

It is specified that for the sake of clarity the various elements of objects (including angles) shown are not reproduced to scale.

FIG. 1, voluntarily very schematic, shows in section an organic electroluminescent device 10 (emission through the substrate or "bottom emission" in English). FIG. 2 illustrates a schematic view from above of the device 10.

The organic electroluminescent device 10 comprises a plane substrate of clear or extraclear silica-soda-lime glass 1 of 0.7 mm thick, provided on one of its main faces successively:

a multilayer lower electrode 2a at 2 "c, of total thickness between 50 and 100 nm, discontinuous electrode in the form of three parallel rows in a direction X each having three electrode zones 2a to 2c, 2'a to 2'c, 2 "a to 2" c in a geometric pattern, for example squares, of 3 cm by 3 cm, the distance dl (along X) between adjacent lower electrode areas of the same row being order of 150 .mu.m, the distance of 1 (along Y) between adjacent lower electrode zones of distinct rows being for example identical to d1, of the order of 150 .mu.m, these spaces being obtained preferably by laser etching of d. a homogeneous electrode,

- an organic electroluminescent system 4a at 4 "c, 100 nm thick, discontinuous system in the form of three rows X-directional parallels each having three electroluminescent layer regions 4a to 4c, 4a to 4c, 4a to 4c in squares of about 3 cm per 3 cm (or more depending on Y to limit the effects of edges, for example 10 to 20 μm more), the distance d2 (along X) between adjacent electroluminescent layer areas of the same row being less than 50 microns, for example of the order of 25 microns, for a factor of satisfactory filling,

a discontinuous top reflecting electrode 5a to 5c, 200 nm thick, discontinuous in the form of three parallel rows in the X direction each having three upper electrode regions 5a to 5c, 5 'to 5'c, 5 "to 5" c, in squares of approximately 3 cm by 3 cm, the distance d3 (along X) between adjacent upper electrode zones of the same row being less than 50 μm, for example of the order of 25 μm, for a satisfactory filling factor. The space between the lower electrode areas 2a to 2 "c and the edges of the lower electrode zones 2a to 2" c are passive by an insulating resin 3, such as an acrylic resin, polyamide, a few microns of thickness, width L1 along X (within the same row) and the following 1 Y (between two distinct rows) respectively greater than or equal to dl and 1, for example of the order of 250 microns, resin deposited by screen printing.

The distance of 2 (along Y) between zones of adjacent electroluminescent layers of distinct rows is less than or equal to L'1, for example between 100 μm and 250 μm.

The distance of 3 (along Y) between adjacent upper electrode zones of distinct rows being less than or equal to L'1, for example between 100 μm and 200 μm.

Each row is connected in series. Also, the electroluminescent squares 4a to 4c, 4'a to 4'c, 4 "to 4" c are shifted from 25 to 60 microns along X relative to the lower electrode squares 2a to 2c, 2 'to 2 c, 2 "a to 2" c and the upper electrode squares 5a to 5c, 5'a to 5'c, 5 "to 5" c are shifted from 25 to 60μm along X in relation to the electroluminescent squares 4a to 4c, 4a to 4c, 4 to 4c. The current thus passes from an electrode zone greater than the adjacent lower electrode region 5a to 2b, 5b to 2c.

A simple and reliable way to make the electroluminescent squares consists in arranging on the lower electrode, in particular by means of markings on the 4 corners of the glass 1, a metal mask in the form of first and second perpendicular lines. The first lines are thin, of width less than 50 microns (giving d2), for example of the order of 25 microns, and are positioned parallel to Y near the passive edges.

The second lines are thicker in width (giving 2) between 100 μm and 250 μm and are positioned parallel to X. These thick lines reinforce the first lines, tend them, the spaces between electroluminescent zones of the same row are thus lines sharp and straight.

A simple and weak way of producing the upper electrode squares consists in arranging on the electroluminescent squares the mask already used, shifted along X from 25 to 60 μm. In this example, the fill factor is about 0.98. The ratio between the brightness (measured in Cd / m ² ) in the center of each illuminating square and on any edge of this illuminating square is of the order of 0.8. The brightness of the device 10 may be at least 1000 Cd / m ² .

The device is powered with a low voltage, for example 24 V or 12 V (automotive applications, etc.) and the current is of the order of 50 mA and fluctuates little within a row.

On one side of the glass 1, the peripheral lower electrode edges 2a, 2 'a, 2 "a are not covered by the electroluminescent squares and are in electrical connection with electrical junction strips 5a to 5d, for example of width of the order of cm following X and of the order 3 cm following Y. These bands of junctions 5a to 5d can be made at the same time as the upper electrode, especially in the same material (s). For serial and parallel connections:

on said junction strips 5a to 5d, a first current feed band 61 is formed, preferably having a thickness of between 0.5 and 10 μm, for example 5 μm, with a width of X of 5 cm and under form for example of a metal layer in one of the metals following: Mo, Al, Cr, Nd or alloy such as MoCr, AlNd or multilayer such as MoCr / Al / MoCr,

- On the other side of the glass is formed on the peripheral edges of the upper electrode areas 5c, 5'c, 5 "c, a second current supply strip 62 similar.

For these serial and parallel connections, 1 can be zero. For a series connection of all the rows, the first current supply band 61 is discontinuous between 2a and 2'a and the second current supply band 62 is discontinuous between 5'c and 5'c. series specific to each row, the first current supply band 61 is discontinuous between 2a and 2'a, 2'a and 2 "a and the second current supply band 62 is discontinuous between 5c and 5'c, 5'c and 5 "c.

The lower electrode 2 has 2 "c discontinuous, chosen transparent, comprises a stack of layers of the type - a contact layer (adhesion) selected from ZnOx doped or not,

SnxZnyOz, ITO or IZO,

a functional layer of silver, preferably pure,

a protective layer chosen from ZnOx, SnxZnyOz, ITO or IZO, the contact layer and the protective layer against water and / or oxygen being of identical nature,

an overlay of adaptation of the output work, preferably the ZnO: Al / Ag / ZnO: Al / ITO stack of respective thicknesses 5 to 20 nm for the ZnO: A1, 5 to 15 nm for the silver , 5 to 20 nm for ZnO: A1, 5 to 20 nm for ITO, the lower electrode 2a at 2 "c has the following characteristics:

a square resistance less than or equal to 5 Ω / square,

a light transmission TL greater than or equal to 70% (measured on a full layer, before structuring), and a luminous reflection RL less than or equal to 20%, a roughness RMS (or Rq) less than or equal to 3 nm measured by optical interferometry, on a square micrometer by atomic force microscopy. A silicon nitride bottom layer of thickness between 10 nm and 80 nm and may be between the lower electrode 2a at 2 "c and the substrate 1.

For the stack 20 nm Si ₃ N ₄ / ZnO: A1 20nm / Ag _n i ₂ m / ZnO: Al ₄ onm / ITO 20nm, a TL of 75% is obtained, a RL = 15%, a sheet resistance of 4.5 Ohm / square, an RMS roughness of 1.2 nm.

For a SiaN ₄ 20 nm / SnZnSb stack: Ox5nm / ZnO: A1 5nm / Ag i2nm / Ti i _nm / ZnO: A1 20 nm / ITO 20 nm, a TL of 85% is obtained, a RL = 8%, a square resistance 3.3 Ohm / square, an RMS roughness of 0.7 nm.

For a Si3N ₄ 20 nm / SnZnSb stack: Ox5nm / ZnO: A1 5nm / Ag i2nm / Ti o, 5nm / ITO 20 nm, a TL of 65% is obtained, a RL = 29%, a square resistance of 3.3 Ohm / square, an RMS roughness of 0.7 nm.

The layers based on SnZn: SbO _x are deposited by reactive sputtering using a target of zinc and antimony-doped tin containing by weight 65% Sn, 34% Zn and 1% Sb. at a pressure of 0.2 Pa and in an argon / oxygen atmosphere.

The Ti layers are deposited using a titanium target under a pressure of 0.8 Pa in a pure argon atmosphere.

The lower electrode 2 to 2 "may alternatively also be a semitransparent electrode For Si ₃ N _{4 2} onm / ZnO: A1 20nm / Ag ₃ onm / ZnO: Al ₄₀ nm / ITO 20 nm, one obtains a TL of 16%, a RL = 81%, a square resistance of 0.9 Ohm / square.

The organic electroluminescent system 4a at 4 "c discontinuous is for example a SM-OLED of following structure

an alpha-NPD layer,

a TCTA + Ir (ppy) 3 layer, a BPhen layer,

a layer of LiF.

The reflective top electrode 5a to 5c discontinuous, may be in particular metal including silver or aluminum base.

The set of layers 2, 4 and 5 was deposited by magnetic field assisted sputtering at room temperature.

An EVA type sheet can be used to flick the glass 1 to another glass preferably with the same characteristics as the glass 1. Optionally, The face of the glass turned towards the EVA sheet is provided with a given stack of functionality.

It goes without saying that the invention applies in the same way to the use of other organic electroluminescent systems than those described in the example.

Claims

1. Substrate, for organic electroluminescent device, carrying on a main surface of a discontinuous electrode (2a to 2 "c) successively comprising, from the substrate:

a contact layer based on a metal oxide,

a functional metallic layer with intrinsic property of electrical conductivity, based on silver, having a functional layer thickness of less than 100 nm,

an overlayer for the adaptation of the output work, the electrode having a square resistance of less than or equal to 5 Ω / square, the electrode being in the form of at least one row of electrode zones, with zones of an electrode having a first dimension (t) of at least 3 cm in the direction (X) of said row, the electrode areas of the row being spaced apart by a distance (d1) less than or equal to 0.5 mm, and insulating material (3) filling the space between the electrode areas and overflowing the electrode areas.

2. Substrate for organic electroluminescent device according to one of the preceding claims characterized in that the insulating material (3), preferably polymeric, is screen printed, in particular an acrylic resin, polyamide, or is an insulating ink is deposited by jet of ink and preferably the insulating material covers the edges of the peripheral electrode areas.

3. Substrate for organic electroluminescent device according to one of the preceding claims characterized in that the discontinuous electrode (2a to 2 "c) is obtained without photolithography, in particular by laser etching, by chemical screen printing with an etching paste, or by under masking, preferably with a screen-printed or ink-jet mask.

4. Organic electroluminescent device substrate according to one of the preceding claims, characterized in that the resistance per square is less than or equal to 5 Ω / square for a functional layer thickness. less than or equal to 20 nm and a light transmission TL greater than or equal to 60% and an absorption factor A less than 10%.

5. Organic electroluminescent device substrate according to one of the preceding claims, characterized in that the metal functional layer based on pure silver, alloyed or doped with Au, Pd, Al, Pt, Cu, Zn, Cd,

In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn, especially a gold and silver or gold and copper alloy.

6. Substrate for organic electroluminescent device according to one of the preceding claims characterized in that the overlay is based on at least one of the following metal oxides, optionally doped: chromium oxide, indium oxide, zinc oxide optionally stoichiometrically, aluminum oxide, titanium oxide, molybdenum oxide, zirconium oxide, antimony oxide, tin oxide, tantalum oxide, silicon oxide and in that the overlayer preferably has a thickness between 3 and 50 nm.

7. Substrate for organic electroluminescent device according to one of the preceding claims characterized in that the overlay is ITO thickness less than or equal to 30 nm.

8. A substrate for an organic electroluminescent device according to one of the preceding claims characterized in that the doped metal oxide contact layer or not, in particular based DTTOs, IZO, Sn _x Zn _y O _z or preferably based of ZnOx.

9. Substrate for organic electroluminescent device according to one of the preceding claims characterized in that the functional metal layer (32) is disposed directly on at least one locking coating (31) underlying which is on the contact layer and / or directly under at least one overlying locking layer (32).

10. Substrate according to the preceding claim, characterized in that at least one blocking coating comprises a metal layer, nitride and / or metal oxide, 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.

1. The substrate as claimed in any one of the preceding claims, characterized in that it comprises a non-crystallized smoothing layer made of a mixed oxide, said smoothing layer being disposed immediately under said contact layer and being made of a material other than that of the contact layer.

12. Substrate according to the preceding claim, characterized in that the smoothing layer is an oxide-based mixed oxide layer of one or more of the following metals: Sn, Si, Ti, Zr, Hf, Zn, Ga, In and in particular is a mixed oxide layer based on zinc and optionally doped tin or a layer of indium tin mixed oxide (ITO) or a layer of indium mixed oxide and of zinc (IZO).

13. Substrate according to any one of the preceding claims, characterized in that it comprises, under the contact layer, a primer, in particular capable of forming an alkaline barrier, preferably chosen on the basis of silicon oxide, silicon oxycarbide, based on silicon nitride, silicon oxynitride, silicon oxycarbonitride, the material of said bottom layer being optionally doped and said bottom layer preferably having a thickness of between 10 and 150 nm.

14. Substrate according to any one of the preceding claims, characterized in that it comprises under the contact layer, an etching stop layer, in particular based on tin oxide.

15. Substrate according to any one of the preceding claims, characterized in that, between the functional layer and the overcoat, it comprises successively: a separating layer based on metal oxide optionally comprising said protective layer, said smoothing layer, a second contact layer, a second functional layer based on silver, and a possible blocking coating.

16. Substrate according to any one of the preceding claims, characterized in that electrical junction areas (5d to 5 "d), in the form of an electroconductive layer of material identical to the upper electrode material, are connected with peripheral edges of lower electrode areas

(2a, 2'a, 2 "a).

17. Substrate according to any one of the preceding claims, characterized in that the substrate is plane, especially glass, plastic, preferably of silicosodocalcique glass (1), especially clear or extraclair.

18. An organic electroluminescent device (10) comprising at least one carrier substrate, in particular a glass substrate, provided with: a discontinuous lower electrode (2a to 2 "c) according to one of the preceding claims, thus forming at least one row of zones d lower electrode, at least one discontinuous electroluminescent layer (4a-4c) of organic electroluminescent material (s) in the form of electroluminescent layer regions arranged on the electrode areas, electroconductive layer discontinuous upper electrode in the form of electrode areas (5a-5 "c) arranged on the electroluminescent layer areas, and, for series connection of the array, the electroluminescent layer areas are shifted from the lower electrode in the row direction (X) and the lower electrode areas are shifted from the electroluminescent layer areas in the direction of the row (X).

19. An organic electroluminescent device (10) according to claim 18 characterized in that the device is organized in a plurality of substantially parallel light-emitting rows and spaced from each other by less than 0.5 mm, each row being capable of being connected in series. .

20. Organic electroluminescent device (10) according to the preceding claim characterized in that the distance between the electroluminescent layer areas (2) of distinct rows is greater than the distance (d2) between the zones of the same row, preferably between 100 microns and 250 microns.

21. Organic electroluminescent device (10) according to one of claims 18 to 20 characterized in that for each illuminating zone associated with an electrode zone the ratio between the brightness (measured in Cd / m ² ) in the center and on a any edge of this illuminating area is greater than or equal to 0.7.

22. Organic electroluminescent device (10 ⁵ ) according to one of claims 18 to 21 characterized in that electrical junction ranges (5d to 5 "d), under form of an electroconductive layer of material identical to the upper electrode material, are connected with peripheral edges of lower electrode areas (2a, 2 'a, 2 "a).

23. Organic electroluminescent device (10) according to one of claims 18 to 22 characterized in that the device is a single glazing, double glazing, multiple glazing, or laminated glazing.

24. The organic electroluminescent device (10) according to one of claims 18 to 23, characterized in that it forms one or more transparent and / or reflective luminous surfaces, in particular an illuminating, decorative, architectural system, a display panel of signaling for example of the type drawing, logo, alphanumeric signaling, the system producing uniform light or differentiated light areas including guided light extraction in the glass substrate.

25. The organic electroluminescent device (10) according to one of claims 18 to 24 characterized in that it is: intended for the building, such as an external light glazing, an internal light partition or a (portion of) lighted glass door particularly sliding, intended for a transport vehicle, such as a bright roof, a (part of) side window light, an internal light partition of a land vehicle, aquatic or aerial (car, truck, train, plane, boat etc.) ). intended for urban or professional furniture such as a bus shelter panel, a wall of a display, a jewelery display or a showcase, a wall of a greenhouse, an illuminating slab, - intended for the interior furnishings, a shelf or furniture component, a furniture facade, an illuminating tile, a ceiling lamp, a refrigerator lighting tablet, an aquarium wall, for the backlighting of electronic equipment, in particular a display or display screen possibly double screen, such as a television or computer screen, a touch screen, a lighting mirror, especially for lighting a bathroom wall or a work plan kitchen, or to be a ceiling light.

26. A method of manufacturing the discontinuous electrode (2a to 2 "c) according to one of claims 1 to 17 comprising: an etching step without photolithography to form the lower electrode areas in one or more parallel rows, an insulating resin filling step (3) by screen printing or ink jet between the electrode areas and projecting over the edges of the electrode areas.

27. A method of manufacturing the discontinuous electrode according to the preceding claim characterized in that the etching step comprises a screen printing of an etching paste with the acid.

28. A method of manufacturing the discontinuous electrode according to one of claims 26 to 27 characterized in that the etching step comprises a laser etching.

29. A method of manufacturing the discontinuous electrode according to one of claims 26 to 28 characterized in that it comprises a step of manufacturing tape (s) supply current (61) by screen printing.

30. A method of manufacturing an organic electroluminescent device (10) characterized in that it comprises: a step of forming said discontinuous lower electrode (2 a to 2 "c), along one or more parallel rows, according to the one of claims 26 to 29, a step of forming the electroluminescent layer areas (4a to 4 "c) by depositing the electroluminescent material or materials on a mask in the form of an organized network of lines along first and second crossed directions ( X, Y), the lines in the second direction (Y) being thicker.

31. A method of manufacturing the device according to the preceding claim characterized in that it comprises a step of forming the upper electrode zones by deposition of the upper electrode material or on said mask offset in the first direction (X).

32. A method of manufacturing the device according to one of claims 30 or 31 characterized in that it comprises, during the step of forming the upper electrode areas (5a to 5 "c), the formation of the junction areas electric (5d to 5 "d) at the lower peripheral electrode areas (2a, 2 'a, 2" a) of a separate row, by deposition of the upper electrode material (s).