Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • 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
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
  • H05B33/06—Electrode terminals
• • 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
• • 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
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/10—Details of semiconductor or other solid state devices to be connected
  • H01L2924/11—Device type
  • H01L2924/12—Passive devices, e.g. 2 terminal devices
  • H01L2924/1204—Optical Diode
  • H01L2924/12044—OLED

Definitions

• the present invention relates to a diffusing conductive support for an organic light-emitting diode device and an organic diode electroluminescent device incorporating it.
• the known organic electroluminescent systems or OLED comprise one or more organic electroluminescent materials electrically powered by electrodes generally in the form of two electroconductive layers surrounding this (s) material (s).
• Light emitted by electroluminescence uses the recombination energy of holes injected from the anode and electrons injected from the cathode.
• the front and rear emission devices that is to say with both a lower (semi) transparent electrode and an upper (semi) transparent electrode.
• the invention relates to backward-transmitting OLED devices.
• the transparent lower electrode is commonly used a layer based on indium oxide, generally indium oxide doped with tin better known under the abbreviation ITO or new electrode structures using a thin metal layer instead of ⁇ to make OLED devices emitting substantially white light for illumination.
• an OLED has a low light extraction efficiency: the ratio between the light that actually leaves the glass substrate and that emitted by the electroluminescent materials is relatively low, of the order of 0.25. This phenomenon is explained in particular by the fact that a certain amount of photons remains trapped in guided modes between the electrodes.
• the application WO2012007575A proposes in a first series of examples V.1 to V.3 in Table V, OLED devices each with a clear glass substrate of 1, 6mm, comprising successively:
• a diffusing layer for the extraction of light, of thickness 50 ⁇ , comprising a glass matrix (enamel obtained from molten glass frit) containing diffusing elements in zirconia, an electrode in the form of a stack of thin layers to money including:
• an overlay comprising:
• a 2.5 nm titanium sacrificial layer deposited by argon sputtering from a Ti target; a so-called insertion layer 7nm thick, titanium oxide Ti0 2 or aluminum doped zinc oxide (AZO) or ZnxSnyOz with x + y> 3 and z ⁇ 6 (preferably with 95% by weight of zinc on% by weight of all the metals present), deposited by sputtering under a reactive atmosphere Ar / O 2 from a target of the SnZn alloy;
• the resistance per square of this electrode is of the order of 4 ohm / square.
• the aim of the invention is to provide an electrode-diffusing medium for better light extraction from an OLED emitting in the white, thus suitable for lighting application.
• the first object of the invention is a diffusing conductive support for OLED, comprising (in this order):
• a transparent substrate preferably of mineral glass, in particular a substrate (glass) of refractive index n2 of less than or equal to 1, 6,
• a diffusing layer a layer (high index) reported, in particular deposited layer, (directly) on the substrate and / or formed by a diffused (rendered) surface of the substrate, in particular a layer of micron thickness and preferably mineral (enamel). .
• a high index layer (directly) on the diffusing layer, of refractive index nO greater than or equal to 1.8, preferably greater than or equal to 1.9, and preferably less than or equal to 2.2, especially of thickness of at least 0.2 ⁇ , 0.4 ⁇ or even at least 1 ⁇ , preferably mineral (enamel ...), high layer preferably distinct from the diffusing layer,
• the diffusing layer and high index layer preferably having a thickness at least micron, the high index layer participating or serving in particular to smooth / planarize the diffusing layer for example to avoid short circuits,
• a first transparent electrode (possibly structured), called lower electrode, (directly) on the high index layer, and which comprises the following stack of layers in this order (away from the substrate):
• a single metal layer with a (main) electrical conduction function which is based on silver, with a thickness e2 given less than 6 nm, a layer preferably arranged (directly) on the contact layer, or even on the underlayer , or even on a thin metal layer called sub-blocker less conductive than silver and less than 3 nm thick, especially partially oxidized metal, (sub-blocker on the contact layer or on the under layer);
• an overlayer, monolayer or multilayer for example thin, arranged (directly) on the single metal layer or even on a thin metal layer called overblocker less conductive than silver and with a thickness less than or equal to 3 nm, in particular metal partially oxidized, the overcoat being electroconductive, in particular metal oxide and / or metal nitride, and in particular comprises an output work adaptation layer which is preferably the last electrode layer to be in contact with the organic electroluminescent system.
• a maximum of white light emitted by electroluminescence is needed to reach the diffusing elements (particles and / or textured surface) which serve for the extraction of light.
• the guided mode plasmon, and other guided modes related to the presence of a layer of silver coexist, and these guided modes can trap the white light in a significant proportion making little light extraction.
• the invention via the adaptation of the stack based on a single silver layer minimizes the importance of these guided modes and optimizes the extraction of the integrated light via the diffusing layer.
• the amount of light trapped in the guided modes is an increasing function of the amount of total silver contained in the anode. In Therefore, to optimize the extraction it is first necessary to minimize this thickness of money as necessary. In practice, this silver thickness must be at least less than 6 nm to compete with a layer of ITO even to increase the square resistance.
• the patent WO2012007575A1 meanwhile only proposes an increase in light extraction at normal incidence but this is of little interest because the OLEDs manufacturers are interested in the light recovered from all angles .
• the luminance of these OLEDs is measured at normal and by spectroscopy.
• this patent focuses particularly on a monochromatic light that is to say centered on a wavelength (green, etc.).
• the Applicant has established a relevant criterion of optical performance evaluation which is the integrated extraction described later.
• n1 is the average index defined by the sum of the index products or the thickness ei of the layers divided by the sum of the respective thicknesses ei, following the classic formula n1
• a layer is dielectric as opposed to a metal layer, typically a metal oxide and / or metal nitride, including by extension silicon or even an organic layer.
• the expression based on indicates that the layer contains predominantly (at least 50% by weight) the indicated element.
• the single conduction metal layer or any dielectric layer may be doped. Doping is understood in a usual way as exposing a presence of the element in an amount of less than 10% by weight of metal element in the layer.
• a metal oxide or nitride may be doped in particular between 0.5 and 5%.
• Any metal oxide layer according to the invention may be a single oxide or a mixed oxide doped or not.
• Thin film according to the invention is understood to mean a layer at most 200 nm thick (in the absence of precision), preferably deposited under empty, in particular by PVD, in particular by sputtering (assisted magnetron), or even by CVD.
• the silver-based layer is the main layer of electrical conduction, that is to say the most conductive layer.
• the silver-based layer is preferably at least 2 nm thick or even 3 nm thick.
• 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.
• Amorphous layer means a layer which is not crystalline.
• diffusing layer is meant a layer capable of diffusing the light emitted by electroluminescence into the visible.
• indium tin oxide (or tin-doped indium oxide or ITO for the English name: Indium tin oxide) is understood to mean a mixed oxide or a mixture obtained from oxides.
• a typical mass proportion is about 90% by weight of ln 2 0 3 for about 10% by weight of Sn0 2 .
• a high index layer (in the absence of precision) has a refractive index greater than or equal to 1, 8 or even greater than or equal to 1, 9.
• the underlayer may have at least one of the following characteristics:
• the under layer is monolayer, bilayer, trilayer,
• At least the first layer or base layer is a metal oxide, or all the layers of the overcoat are made of metal oxide (excluding sub-blocker),
• the under layer is devoid of indium, or at least does not include a layer of IZO, ITO,
• n1 is greater than or equal to 1, 9 and preferably less than 2.7
• the underlayer is made of metal oxide and / or metal nitride and does not include a metal layer.
• n1 is greater than or equal to 2.2 and even 2.3 or 2.4 and for example less than 2.8.
• the contact layer is distinct from the sub-layer of non-zero thickness and is less than 15 nm thick.
• the underlayer may be relatively thick without being too absorbent, for example up to 200 nm or 150 nm, especially if it is based on silicon nitride or even tin oxide or a mixed layer of tin and zinc. preferably with at least 30% or majority tin.
• an underlayer with a thickness e1 of less than 100 nm or even 80 nm or even 50 nm is preferred. It is the same for the overlay.
• the electrode comprises an oxide layer, optionally doped, chosen from among ITO, IZO, the simple oxide ZnO, then the oxide layer is less than 100 nm thick, or even smaller, or equal to 50nm, and even less than or equal to 30 nm.
• the sub-layer is optionally doped in particular to increase its index.
• the undercoat can improve the bonding properties of the contact layer without significantly increasing the roughness of the electrode
• Si x N y (Si 3 N 4 in particular) layer alone or in a stack, of Sn0 2 alone or a Si x N y / SnO 2 stack,
• the high index layer (or even the diffusing layer on the substrate) preferably covers the main surface of the substrate, so it is not structured or structurable, even when the electrode is structured (in whole or in part).
• the first layer or bottom layer of the under layer that is to say a layer closest to the high index layer, preferably also covers the main face of the substrate, for example forming an alkali barrier (if necessary ) and / or an etch stop layer (s) (dry and / or wet).
• a primer layer there may be mentioned a layer of titanium oxide or tin oxide.
• a basecoat forming an alkaline barrier (if necessary) and / or an etch stop layer (s) may be based on silicon oxycarbide (of general formula SiOC), based on silicon nitride (from general formula Si x N y ), especially based on Si 3 N 4 , based on silicon oxynitride (of general formula Si x O y N z ), based on silicon oxycarbonitride (of general formula If x O y N z C w ), or even based on silicon oxide (of general formula Si x O y ), for thicknesses of less than 10 nm,
• nitriding of the primer is slightly under stoichiometric.
• the underlayer can thus be a barrier to the alkalis underlying the electrode. It protects against any pollution or any overlying layers, including the contact layer under the metal conduction layer (pollution that can cause mechanical defects such as delamination); it also preserves the electrical conductivity of the conduction metal layer. It also prevents the organic structure of an OLED device from being polluted by alkalis, which can significantly reduce 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 sub-layer may preferably comprise an etching stop layer, essentially covering the high-index layer, in particular being the base layer, in particular a layer based on tin oxide, on titanium oxide, on zirconia oxide, or even silica or silicon nitride.
• the etch stop layer may be part of or be the bottom layer and may be:
• titanium oxide single or mixed oxide
• zirconia oxide single or mixed oxide
• mixed titanium oxide zirconia
• the etch stop layer serves to protect the basecoat and / or the high-index layer, in particular in the case of chemical etching or reactive plasma etching, for example is of thickness at least 2 nm or even 3 nm, or even 5 nm.
• the primer layer and / or the high index layer are preserved during an etching step, by liquid or dry route.
• the sub-layer comprises, or even consists of, a layer (optionally doped), preferably the base layer) based on titanium oxide, zirconium oxide, mixed titanium oxide and zirconium, especially layer thickness between 3 and 80nm or less than 50nm.
• the conduction metal layer may be deposited (directly) on the sub-layer for example (in the last layer), amorphous layer for example a layer based on silicon nitride optionally with a sub-blocker or based on titanium oxide or in amorphous SnZnO, typically very rich in Sn (close to SnO 2 ) or in Zn (close to ZnO).
• the (mono) crystallized contact layer is directly on the high index layer.
• a crystallized contact layer promotes the proper crystalline orientation of the silver-based layer deposited thereon.
• ITO contact layer One could choose as ITO contact layer. However, a contact layer devoid of indium and the most efficient possible for the growth of silver is preferred.
• the crystalline contact layer may preferably be based on zinc oxide and preferably doped in particular by at least one of the following dopants; Al (AZO), Ga (GZO), or even B, Se, or Sb for better deposition process stability.
• a zinc oxide layer ZnO x is preferably furthermore preferred, with preferably less than 1 x, even more preferably between 0.88 and 0.98, especially from 0.90 to 0.95.
• the thickness of the crystalline contact layer is preferably greater than or equal to 3 nm or even greater than or equal to 5 nm and may furthermore be less than or equal to 15 nm or even 10 nm.
• a crystalline sub-layer for example SnZnO or SnO 2 , is used, in particular under a layer which is monolayer, the crystalline contact layer as already described (ZnO, SnZnO, etc.)
• the under layer includes the crystalline contact layer, with e1 typically greater than 15 nm or 20 nm.
• the conduction metal layer may be pure or alloyed or doped with at least one other material chosen from: Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn, especially is based on a silver alloy and palladium and / or gold and / or copper, to improve the moisture resistance of silver.
• at least one other material chosen from: Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn, especially is based on a silver alloy and palladium and / or gold and / or copper, to improve the moisture resistance of silver.
• the substrate according to the invention coated with the lower electrode preferably has a low roughness so that the distance from the hollower place to the highest point ("peak to valley" in English) overcoat is less than or equal to 10 nm.
• the substrate according to the invention coated with the lower electrode preferably has on the overlayer an RMS roughness of less than or equal to 10 nm, or even 5 or 3 nm, preferably even less than or equal to 2 nm, to 1, 5 nm or even less than or equal to 1 nm, to avoid spike effects in English which drastically reduce the life and reliability of the OLED.
• the roughness RMS stands for Root Mean Square roughness. This is a measure of measuring the value of the mean square deviation of roughness. This RMS roughness concretely quantifies, on average, the height of the peaks and troughs of roughness, with respect to the average height. Thus, an RMS roughness of 2 nm means an average amplitude of double peak.
• the underlayer comprises a smoothing layer, in particular non-crystalline, said smoothing layer being disposed under the crystalline contact layer (directly or not) and being made of a material other than that of the coating layer. contact.
• the smoothing layer is preferably a single oxide or mixed oxide layer, doped or not, based on the oxide of one or more of the following metals: Sn, Si, Ti, Zr, Hf, Zn, Ga
• Sn, Si, Ti, Zr, Hf, Zn, Ga is a mixed oxide layer based on zinc and optionally doped tin or a layer of mixed indium tin oxide (ITO) or a mixed oxide layer of indium and zinc (IZO).
• the smoothing layer may in particular be based on a mixed oxide of zinc and tin Sn x Zn y O z under amorphous phase, in particular non-stoichiometric, optionally doped, in particular with antimony
• This smoothing layer may preferably be on the bottom layer or directly on the high index layer.
• the sub-layer comprises or consists of:
• under layer preferably surmounted by a crystalline layer based on ZnO.
• the overlay may have at least one of the following characteristics:
• At least the first layer (excluding the overblocker) is a metal oxide, or all the layers of the overcoat are made of metal oxide, all the layers of the overcoat have a thickness of less than or equal to 120 nm, or even 80 nm ,
• the overcoat consists of layer (s) (excluding the thin layer of blocking described later) of electrical resistivity (in solid state, as known in the literature) less than or equal to 10 7 ohm. cm, preferably less than or equal to 10 6 ohm. cm, or even less than or equal to 10 4 ohm. cm.
• the overlayer is preferably based on thin layer (s), in particular mineral (s).
• the overcoat according to the invention is preferably based on a single or mixed oxide, based on at least one of the following metal oxides, optionally doped: tin oxide, indium oxide, zinc oxide (optionally stoichiometric), molybdenum oxide, tungsten oxide, vanadium oxide.
• This overlayer may in particular be tin oxide optionally doped with F, Sb, or zinc oxide optionally doped with aluminum, or may be optionally based on a mixed oxide, especially a mixed oxide of indium and aluminum oxide.
• tin (ITO) a mixed oxide of indium and zinc (IZO), a mixed oxide of zinc and tin Sn x Zn y O z .
• This overlayer may preferably have a thickness e3 less than or equal to 50 nm, or 40 nm, or even 30 nm, for example between 10 or 15 nm and 30 nm.
• ITO is preferentially over-stoichiometric in oxygen to reduce its absorption (typically less than 1%).
• the overlay may comprise a ZnO-based layer which is crystalline (AZO, SnZnO.) Or amorphous (SnZnO) which is not the last layer and for example is the same layer as the underlayer.
• ZnO-based layer which is crystalline (AZO, SnZnO.) Or amorphous (SnZnO) which is not the last layer and for example is the same layer as the underlayer.
• the silver-based layer is covered with an additional thin layer having a typically higher output work of ⁇ .
• An adaptation layer of the output work can have for example an output work Ws from 4.5 eV and preferably greater than or equal to 5 eV.
• the overlayer comprises, preferably in the last layer, in particular for adjusting the output work, a layer which is based on a single or mixed oxide, based on at least one of the following metal oxides, optionally doped: oxide of indium, zinc oxide optionally under stoichiometric, molybdenum oxide MoO 3 , tungsten oxide WO 3 , vanadium oxide V 2 O 5, ITO, IZO, Sn x Zn y O z , and overcoat preferably has a thickness less than or equal to 50nm or 40nm or even 30nm.
• the overlayer may comprise a final layer, in particular for adapting the output work, which is based on a thin metallic layer (less conductive than silver), especially based on nickel, platinum or palladium, for example thickness less than or equal to 5 nm, in particular from 1 to 2 nm, and preferably separated from the conduction metal layer (or an overblocker) by a single layer of simple or mixed metal oxide.
• a thin metallic layer less conductive than silver
• nickel, platinum or palladium for example thickness less than or equal to 5 nm, in particular from 1 to 2 nm, and preferably separated from the conduction metal layer (or an overblocker) by a single layer of simple or mixed metal oxide.
• the overlay may comprise, in the last dielectric layer, a layer with a thickness of less than 5 nm or even 2.5 nm and at least 0.5 nm or even 1 nm chosen from a nitride, an oxide, a carbide, an oxynitride and an oxycarbide in particular Ti, Zr, Ni, NiCr.
• the lower electrode according to the invention is easy to manufacture in particular by choosing materials for the stack that can be deposited at room temperature. Even more preferably, most or all of the layers of the stack are deposited under vacuum (preferably successively), preferably by cathodic sputtering possibly assisted by magnetron, allowing significant productivity gains. To further reduce the cost of the lower electrode, it may be preferred that the total thickness of the material containing (preferably predominantly, that is, with a mass percentage of indium greater than or equal to 50%) of the indium of this electrode is less than or equal to 60 nm, or even less than or equal to 50 nm, 40 nm, or even 30 nm. For example, ITO, IZO may be mentioned as a layer (s) whose thicknesses are preferable.
• blocking coating One or even two very thin coating (s) called “blocking coating” may also be provided, arranged directly under, on or on each side of the metallic silver layer.
• the underblocking coating underlying the metallic silver layer, towards the substrate, or subblocker is a bonding, nucleation and / or protection coating.
• It serves as a protective coating or "sacrificial" to prevent alteration of the silver layer by etching and / or oxygen migration of a layer that surmounts it, or even by migration of oxygen if the layer which overcomes it is deposited by cathodic sputtering in the presence of oxygen.
• the silver metal layer can thus be disposed directly on at least one underlying blocking coating.
• the silver metal layer may also be alternatively or directly under at least one overlying blocking coating, or on blocking each coating having a thickness of preferably between 0.5 and 5 nm.
• At least one blocking coating preferably an overblocker
• 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, preferably based on Ni, or Ti, based on an Ni alloy based on a NiCr alloy.
• a blocking coating (preferably an overblocker) 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 an alloy of nickel-chromium.
• a thin blocking layer (preferably an overblocker) forms a protective layer or even a "sacrificial" layer which makes it possible to avoid the alteration of the metal of the metallic silver layer, in particular in one and / or the other of the following configurations:
• the layer which overcomes the conduction metal layer is deposited using a reactive plasma (oxygen, nitrogen, etc.), for example if the oxide layer which surmounts it is deposited by cathodic sputtering,
• composition of the layer which overcomes the metal conduction layer is likely to vary during industrial manufacture (evolution of the deposition conditions, wear of a target, etc.), especially if the stoichiometry of an oxide-type layer and / or nitride evolves, then modifying the quality of the silver metal layer and therefore the properties of the electrode (square resistance, light transmission, etc.),
• a thin blocking layer (preferably onblocker) based on 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).
• This type of layer based on at least one metal has a particularly important effect of entrapment ("getter" effect).
• a thin metal blocking layer (preferably an overblocker) can easily be manufactured without altering the metal conduction layer.
• This metal layer may preferably be deposited in an inert atmosphere (that is to say without voluntary introduction of oxygen or nitrogen) consisting of noble gas (He, Ne, Xe, Ar, Kr). It is not excluded or annoying that on the surface this metal layer is oxidized during the subsequent deposition of a metal oxide layer.
• the thin metal blocking layer (preferably onblocker) also makes it possible to obtain excellent mechanical strength (resistance to abrasion, especially to scratches).
• the thin blocking layer (preferably onblocker) can be partially oxidized 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 of the MNO x type for an oxide of two materials. M and N (or more).
• MO x metal blocking layer
• M represents the material
• x is a number less than the stoichiometry of the oxide of the material or of the MNO x type for an oxide of two materials.
• M and N (or more).
• TiO x , NiCrO x may be mentioned.
• x is preferably between 0.75 and 0.99 times the normal stoichiometry of the oxide.
• x is preferably between 0.75 and 0.99 times the normal stoichiometry of the oxide.
• x is preferably between 0.5 and 0.98 and for a x-dioxide between 1.5 and 1.98.
• the thin blocking layer (preferably onblocker) is based on TO x and x can be in particular such that 1, 5 ⁇ x ⁇ 1, 98 or 1, 5 ⁇ x ⁇ 1, 7, even 1, 7 ⁇ x ⁇ 1, 95.
• the thin blocking layer (preferably onblocker) 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.
• the thin blocking layer (preferably onblocker) can also be partially oxynitrided.
• This thin, preferably oxidized and / or nitrided blocking layer (preferably an overblocker) 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).
• noble gas He, Ne, Xe, Ar, Kr
• the thin blocking layer (preferably onblocker) may preferably be nitride and / or substoichiometric oxide for even more reproducibility of the electrical and optical properties of the electrode.
• the thin blocking layer (preferably onblocker) chosen for stoichiometric oxide and / or nitride may preferably be 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.
• a layer (preferably an onblocker) based on an oxide or oxynitride of a metal chosen from niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel Ni or a 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).
• a metal chosen from niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel Ni or a 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).
• the substoichiometric metal nitride it is also possible to choose a layer of silicon nitride SiN x or aluminum AlX or chromium Cr N x , or titanium Ti x or nitride of several metals such as NiCrN x .
• the thin blocking layer (preferably onblocker) may have an oxidation gradient, for example M (N) O xj with x ( variable, the part of the blocking layer in contact with the metal layer is less oxidized than the part of this layer furthest from the metal layer by using a particular deposition atmosphere.
• M (N) O xj with x variable, the part of the blocking layer in contact with the metal layer is less oxidized than the part of this layer furthest from the metal layer by using a particular deposition atmosphere.
• All layers of the electrode are preferably deposited by a vacuum deposition technique, but it is not excluded that one or more layers of the stack may be deposited by another technique. for example by a pyrolysis type thermal decomposition technique.
• the diffusing layer is an added layer, for example deposited, on the preferably non-textured substrate, with a high index matrix (n3 greater than 1, 8 or even greater than or equal to 1, 9) and elements diffusers in particular of mineral type of refractive index n d td the difference in absolute value between n d and n 3 is greater than 0.1 typically.
• the high index layer can be:
• this diffusing layer for example monolayer, for example a layer of at least 1 ⁇ or even 5 ⁇ , for example of thickness eO greater than 0.2 ⁇ , 0.5 ⁇ or even 1 ⁇ , region devoid of diffusing elements (for example no scattering particles) or at least less than an underlying region,
• the diffusing layer and / an additional layer deposited on the diffusing layer, for example with a thickness eO greater than 0.2 ⁇ or even 1 ⁇ and even more, devoid of diffusing elements (for example no addition of diffusing particles) or at least in less than the diffusing layer.
• a diffusing layer in the form of a polymeric matrix comprising diffusing particles for example described in EP 1 06474 is possible.
• the diffusing layer is a mineral layer on the substrate, in particular glass, with a high-index mineral matrix (the index n3), for example oxide (s) including an enamel, and elements diffusers, in particular of the mineral type (pores, precipitated crystals, hollow or solid particles, for example oxides or non-oxide ceramics) of refractive index n d td the difference in absolute value between n d and n 3 is greater than 0 1.
• the index n3 for example oxide (s) including an enamel
• elements diffusers in particular of the mineral type (pores, precipitated crystals, hollow or solid particles, for example oxides or non-oxide ceramics) of refractive index n d td the difference in absolute value between n d and n 3 is greater than 0 1.
• the high index layer is mineral, for example oxide (s), especially glass, and in particular an enamel.
• the high index layer is preferably identical in matrix to that of the diffusing layer.
• the interface between the scattering layers and the high index layer is not "marked” / observable even if deposited one after the other.
• enamel layers are known in the art and are described for example in EP2178343 and WO2011 / 089343 or in the prior art application already described.
• the chemical nature of the scattering particles is not particularly limited, they are preferably selected from the ⁇ 2 and SiO 2 particles. For optimum extraction efficiency, they are present in a concentration of between 10 4 and 10 7 particles / mm 2. The larger the size of the particles, the more their optimal concentration is located towards the lower limit of this range.
• the diffusing enamel layer generally has a thickness of between 1 ⁇ and 100 ⁇ , in particular between 2 and 30 ⁇ .
• the scattering particles dispersed in this enamel preferably have a mean diameter, determined by dynamic light scattering (DLS), of between 0.05 and 5 ⁇ , in particular between 0.1 and 3 ⁇ .
• an alkali barrier layer deposited on the mineral glass substrate, or a moisture barrier layer on the plastic substrate, a layer based on silicon nitride, silicon oxycarbide, oxynitride, silicon oxycarbonitride, or silica, alumina, titanium oxide, tin oxide, aluminum nitride, titanium nitride, for example with a thickness of less than or equal to 10 nm and preferably greater than or equal to 3 nm or even 5 nm, may be a multilayer, in particular for a moisture barrier layer.
• the diffusing layer is formed by a non-periodic, preferably random, surface texturing for the white light application.
• the mineral or organic glass substrate is textured or a textured layer is deposited (deposited) on a mineral or organic glass, (then forming a composite substrate).
• the high index layer is on top.
• Rough interfaces for extracting the light emitted by organic layers of OLEDs are also known and described for example in WO2010 / 112786, WO02 / 37568 and WO2011 / 089343.
• the surface roughness of the substrate can be obtained by any known suitable means, for example by acid etching (hydrofluoric acid), sanding or abrasion.
• the high index layer is preferably inorganic, based on oxide (s), in particular an enamel. It is preferably at least 1 ⁇ or even 5 ⁇ or even 10 ⁇ .
• a light extraction means may also be located on the outer face of the substrate, that is to say the face which will be opposite to that facing the lower electrode. It may be a microlens array or micropyramid as described in the article in Japanese Journal of Applied Physics, Vol. 46, No. 7A, pages 4125-4137 (2007) or a satin, for example a frosted satin treatment with hydrofluoric acid.
• the substrate may be flat or curved, and further rigid, flexible or semi-flexible.
• This substrate may be of large size, for example with an area greater than 0.02 m 2 or even 0.5 m 2 or 1 m 2 and with a lower electrode (optionally divided into several zones called electrode surfaces) occupying substantially the surface (to areas of structuring near and / or near edge areas)
• the substrate is substantially transparent. It may have a light transmission T L greater than or equal to 70%, preferably greater than or equal to 80% or even 90%.
• the substrate may be inorganic or plastic, such as polycarbonate PC or polymethyl methacrylate PMMA or a polyethylene naphthalate PEN, a polyester, a polyimide, a PES polyester sulfone, a PET, a polytetrafluoroethylene PTFE, a sheet of thermoplastic material for example polyvinyl butyral PVB, polyurethane PU, ethylene vinyl acetate EVA, or resin plu ri or mono-components, thermally crosslinkable (epoxy, PU) or ultraviolet (epoxy, acrylic resin) etc.
• inorganic or plastic such as polycarbonate PC or polymethyl methacrylate PMMA or a polyethylene naphthalate PEN, a polyester, a polyimide, a PES polyester sulfone, a PET, a polytetraflu
• the substrate may preferably be glass, of mineral glass, of silicate glass, in particular of soda-lime or silicosodium-calcium glass, a clear glass, extraclear, a float glass. It can be a high index glass (in particular index greater than 1, 6).
• 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.
• silicosodocalcic glasses with less than 0.05% Fe III or Fe 2 O 3 are chosen, for example Saint-Gobain Glass Diamond, Pilkington Optiwhite glass or Schott B270 glass. All the extraclear glass compositions described in WO04 / 025334 can be selected.
• the thickness of the selected glass substrate may be at least 1 mm, preferably at least 5 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 OLED device can be emission from the bottom and possibly also from the top depending on whether the upper electrode is reflective or semi-reflective, or even transparent (in particular TL comparable to the anode typically from 60% and preferably higher or equal to 80%).
• mixture of compounds green red emission, blue
• stack on the face of the electrodes of three organic structures green red emission, blue
• two organic structures yellow and blue
• the OLED device can be adapted to output a light (substantially) white, as close as possible to coordinates (0.33, 0.33), or coordinates (0.45, 0.41), especially at 0 °.
• White light can be defined in the CIE XYZ color chart by ANSI C78.377-2008 in the specification sheet entitled “Specifications for the Chromaticity of Solid State Lighting Products", pages 11-12.
• OLEDs are generally dissociated into two major families depending on the organic material used.
• SM-OLED Small Molecule Organic Light Emitting Diodes
• an SM-OLED consists of a stack of hole injection layers or "HIL” for "Hole Injection Layer” in English, hole transport layer or “HTL” for "Hole Transporting” Layer "in English, emissive layer, electron transport layer or” ETL “for” Electron Transporting Layer "in English.
• HIL hole injection layers
• HTL hole transport layer
• ETL Electron Transporting Layer
• organic electroluminescent stacks are for example described in the document entitled "oven wavelength white organic light emitting diodes using 4, 4'-bis- [carbazoyl- (9)] - stilbene as a deep blue emissive layer" of C H Jeong et al., Published in Organics Electronics 8 (2007) pages 683-689.
• organic electroluminescent layers are polymers, it is called PLED ("Polymer Light Emitting Diodes" in English).
• the OLED organic layer or layers are generally index from 1, 8 or even higher (1, 9 even more).
• the final object of the invention is an OLED device incorporating the diffusing conductive support as defined above and an OLED system, above the lower electrode and emitting polychromatic radiation, preferably a white light.
• the OLED device may comprise a more or less thick OLED system for example between 50 and 350 nm or 300 nm, in particular between 90 and 130 nm, or even between 100 and 120 nm.
• OLED devices comprising a heavily doped "HTL” (Hole Transport Layer) layer as described in US7274141.
• HTL Hole Transport Layer
• OLEDS systems of thickness between 100 and 500 nm, typically 350 nm or thicker OLED systems for example 800 nm as described in Philip Wellmann's article, "Novaled PIN OLED® Technology for High Performance OLED Lighting,” related to the Lighting Korea conference, 2009.
• the present invention further relates to a method of manufacturing the diffusing conductive support according to the invention and the OLED according to the invention.
• the process comprises, of course, the deposition of the diffusing layer and of the high-index layer (preferably distinct from the diffusing layer), preferably mineral, in particular to form enamel (glass-melted glass frit), for example using screen-printing.
• the diffusing layer and of the high-index layer preferably mineral, in particular to form enamel (glass-melted glass frit), for example using screen-printing.
• the process of course also includes the deposition of the successive layers constituting the lower electrode.
• the deposition of most or all of these layers is preferably by magnetron sputtering.
• the method according to the invention furthermore preferably comprises a step of heating the lower electrode at a temperature greater than 180 ° C., preferably greater than 200 ° C., in particular between 230 ° C. and 450 ° C., and ideally between 300 and 350 ° C for a period preferably between 5 minutes and 120 minutes, in particular between 15 and 90 minutes.
• the electrode of the present invention sees a remarkable improvement in electrical and optical properties.
• the diffusing layer + high index layer assembly is hereinafter referred to as EL
• a lower electrode is deposited by sputtering, forming a transparent anode comprising:
• a dielectric underlayer here a bi layer
• a contact layer a crystalline layer, called a contact layer
• the organic layers (HTL / EBL (electron blocking layer) / EL / BL (hole blocking layer) / ETL) are deposited by evaporation under vacuum so as to produce an OLED which emits a white light.
• a metal cathode made of silver and / or aluminum is deposited by vacuum evaporation directly on the stack of organic layers.
• the deposit conditions for each of the layers are as follows:
• the layer based on Si 3 N 4 Al is deposited by reactive sputtering using an aluminum-doped silicon target under a pressure of 0.25 Pa in an argon / nitrogen atmosphere,
• Sb x is deposited by reactive sputtering using a target of zinc and antimony-doped tin containing in bulk by Example 65% of Sn, 34% of Zn and 1% of Sb, or alternatively comprising in mass 50% of Sn, 49% of Zn and 1% of Sb, under a pressure of 0.2 Pa and in an argon atmosphere. oxygen,
• the layer of ZnO: Al is deposited by reactive sputtering using an aluminum doped zinc target, at a pressure of 0.2 Pa and in an argon / oxygen atmosphere, or alternatively with a ceramic target,
• the silver layer is deposited using a silver target, at a pressure of 0.8 Pa in a pure argon atmosphere,
• the Ti layer is deposited using a titanium target under a pressure of 0.8 Pa in a pure argon atmosphere;
• the overlay of ITO is deposited using a ceramic target 90% by weight of Indium oxide and 10% by weight of tin oxide in an argon / oxygen atmosphere, ⁇ being on stoichiometric oxygen.
• the overblocking layer Ti may be partially oxidized after deposition of ⁇ over.
• the diffusing conductive support is advantageously annealed at 230 ° C. or even at 300 ° C. in order to further improve the electrical and optical properties.
• the duration of the annealing is typically at least 10 min and for example less than 1 h 30.
• underlayer As alternative examples as underlayer include:
• SiO2 for example, with e1 of 2 to 32 nm or 24 nm or 14 nm,
• Sn0 2 or SiNx or SnZnO amorphous or crystalline, for example with e1 of 2 to 30 nm,
• Zr0 2 for example with e1 of 2 to 50nm or even 2 to 15nm, or (Ti) ZrOx,
• ⁇ 2 for example from 2 to 50nm or 2 to 25nm
• the lower electrode may alternatively comprise an underlying blocking coating including, in particular, as the overlying blocking coating, a metal layer preferably obtained by a metal target with a neutral or nitride and / or oxide plasma of one or more metals such as Ti, Ni, Cr, preferably obtained by a ceramic target with a neutral plasma.
• an underlying blocking coating including, in particular, as the overlying blocking coating, a metal layer preferably obtained by a metal target with a neutral or nitride and / or oxide plasma of one or more metals such as Ti, Ni, Cr, preferably obtained by a ceramic target with a neutral plasma.
• - IZO (preferably in the last layer replacing ITO) with a thickness of less than 50 nm or even less than or equal to 35 nm or even 20 nm,
• a textured glass is chosen, for example a glass whose roughness is obtained for example with hydrofluoric acid.
• the high index layer planarizes the textured glass.

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• 2012
  • 2012-08-08 FR FR1257713A patent/FR2994509A1/fr not_active Withdrawn
• 2013
  • 2013-07-18 US US14/420,095 patent/US20150207105A1/en not_active Abandoned
  • 2013-07-18 EP EP13756569.3A patent/EP2883258A1/de not_active Withdrawn
  • 2013-07-18 WO PCT/FR2013/051738 patent/WO2014023886A1/fr active Application Filing
  • 2013-07-18 JP JP2015525919A patent/JP2015528628A/ja active Pending
  • 2013-07-18 KR KR20157005652A patent/KR20150041030A/ko not_active Application Discontinuation
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