WO2013007488A1 - Composant optoélectronique organique et procédé de son fabrication - Google Patents

Composant optoélectronique organique et procédé de son fabrication Download PDF

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Publication number
WO2013007488A1
WO2013007488A1 PCT/EP2012/061847 EP2012061847W WO2013007488A1 WO 2013007488 A1 WO2013007488 A1 WO 2013007488A1 EP 2012061847 W EP2012061847 W EP 2012061847W WO 2013007488 A1 WO2013007488 A1 WO 2013007488A1
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WO
WIPO (PCT)
Prior art keywords
layer
radiation
organic
absorbing layer
electrode
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Application number
PCT/EP2012/061847
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German (de)
English (en)
Inventor
Richard Baisl
Original Assignee
Osram Opto Semiconductors Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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Publication of WO2013007488A1 publication Critical patent/WO2013007488A1/fr

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    • 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
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the invention relates to an organic optoelectronic component and to a method for producing the organic optoelectronic component.
  • Conventional organic optoelectronic components are generally not sufficiently resistant to UV radiation. UV radiation can irreversibly damage the active layer as well as other layers of the organic optoelectronic component, so that it is only reduced or no longer able to function. It is therefore desirable to develop organic optoelectronic devices having improved resistance to UV radiation.
  • a problem to be solved is to provide an organic optoelectronic component, which is characterized by a he ⁇ creased resistance to UV radiation.
  • organic optoelectronic component is specified. According to at least one embodiment, the organic optoelectronic component comprises:
  • first electrode disposed on the substrate, a second electrode, an organic layer stack, which includes at least one or ganic ⁇ active layer and is disposed between first and second electrodes, and
  • first UV radiation absorbing layer comprising a metal ⁇ oxide and which is transparent to visible light.
  • organic optoelectronic component is also referred to as "organic component" for short.
  • first layer, a first region or a first device is arranged or applied "on" a second layer, a second region or a second device can mean here and below that the first layer, the first region or the first one Vorrich ⁇ tion is arranged or applied directly in direct mechanical and / or electrical contact on the second layer, the second region or the second device or to the two other layers, regions or devices.
  • an indirect contact can also be designated, in which further layers, regions and / or devices are arranged between the first layer, the first region or the first device and the second layer, the second region or the second device or the two further layers, regions or devices are arranged.
  • the organic component may be adapted to emit sichtba ⁇ res light or radiation, particularly in the visible region of the spectrum to be received.
  • the at least one organic active layer is accordingly formed as an organic electroluminescent layer.
  • Layers stack can be more layers, such as Having hole injecting, transporting holes, electrons jifugde in ⁇ and / or electron transporting layers, said layers also can perform a plurality of functions.
  • An example of such an organic component is an organic light emitting diode (OLED).
  • OLED organic light emitting diode
  • An example of such a component is an organic solar cell.
  • the organic component may optionally have a housing.
  • the beam path of the organic component is understood to be possible paths through which visible light can pass from the organic active layer out of the organic component or from the outside to the active layer.
  • An electrode which is arranged in the beam path is performed in the transparent Appli ⁇ to the invention the organic component.
  • TCO Transparent condueting oxides
  • ITO In ⁇ diumzinnoxid
  • An electrode which is not arranged in the beam path of the organic component can also consist of non-transparent materials. Examples include metals such as aluminum, calcium, magnesium. If the substrate is arranged in the beam path, this is also made transparent. It can ⁇ example, of glass or a transparent plastic, for example egg ⁇ nem epoxy resin, may be formed. The beam path can also extend (additionally) through the second electrode.
  • Other materials for the electrodes, the organic layer stack, the substrate, a possible housing and other components of conventional organic components and the method of producing them are known per se and are therefore not listed here in detail.
  • a layer pel comprising the first and second electrodes and the orga ⁇ African stack of layers can be referred to herein as "optoelectronic layer stack".
  • a first UV-absorbing layer comprising a Me ⁇ talloxid
  • the underlying, that is following in the beam path layers of the organic component can be effectively protected from externally incident UV radiation.
  • the resistance of the organic component ge ⁇ genüber UV radiation is significantly improved, which is in particular ⁇ sondere by a longer service life or a longer lasting high efficiency of the organic component externa ⁇ ßert.
  • the first UV-absorbing layer oughtin- least visible light is transparent, the optical rule ⁇ properties of the organic component are hardly or not adversely affected.
  • the first UV radiation sublingually ⁇ -absorbing layer is especially important for the radiation emitted by the organic active layer or radiation received transparently.
  • the first UV-absorbing layer is arranged at least in the beam path of the component, but it can also be arranged in other regions of the organic component. According to the application, the first UV radiation absorbing
  • the first UV-absorbing layer can at least partially absorb UV radiation and / or also reflect back to the outside.
  • the first UV-absorbing layer may in particular be colorless or almost colorless.
  • the first UV radiation-absorbing layer may be electrically non-conductive or be dielectric. If the first UV-absorbing layer is not is in electrically conductive contact with the optoelectronic layer stack, this may also be carried out electrically conductive, for example by being doped. In general, however, the first UV-absorbing layer is electrically non-conductive.
  • the first UV-absorbing layer is produced by means of atomic layer deposition or sputtering.
  • the first UV-absorbing layer can be made uniform and very thin. It is possible to adjust the layer thickness targeted.
  • the first UV-absorbing layer can be manufactured very inexpensively on these procedural ⁇ ren.
  • atomic layer deposition ALD is particularly suitable.
  • the methods used can be detected by very precise spectroscopic methods. For example, a focused ion beam (FIB), a scanning electron microscope (SEM) or a transmission electron microscope (TEM) can be used for this purpose.
  • FIB focused ion beam
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the first UV-absorbing layer has a
  • Transparency of at least 75% for visible light is obtained at least in a partial region of the visible region of the spectrum (about 400 to 800 nm wavelength).
  • the absorbent when entering and Austre ⁇ th of light in the first UV-radiation layer occur already included.
  • the transparency of the first UV-absorbing layer can be> 80% and especially> 85%.
  • the transparency can even be> 90%.
  • the trans- Parence can be determined by measuring radiation intensities with and without UV radiation absorbing layer. Due to the high transparency of the UV-absorbing layer hardly occur radiation losses in visible light, so that the efficiency of the organic component is hardly affected.
  • the first UV-absorbing layer has a higher transparency than so-called decoupling films which are occasionally used as UV protection in conventional organic optoelectronic components.
  • the organic component according to the application therefore has a higher efficiency than conventional organic components.
  • Said decoupling films are plastic films, the decoupling structures, at which light is strongly scattered and often have only a moderate transparency.
  • the application according to UV radiation absorbing layer is very long compared to conventional organic components to UV radiation resistant.
  • conventional organic components Auskoppelfolien often show aging ⁇ phenomena which lead to lower transparency of the film. As a result, the efficiency decreases and the visual and aesthetic impression of the conventional organic component deteriorates, which can advantageously be largely avoided in the component according to the application.
  • the first UV-absorbing layer is at least partially amorphous.
  • the first UV-absorbing layer may also be> 99% by weight be amorphous. Therefore, there are hardly any crystalline or partially crystalline regions in the first UV-absorbing layer. Thus, hardly visible light is scattered or absorbed by the first UV-absorbing layer, whereby the efficiency of the organic component is increased.
  • the first UV-absorbing layer is a metal oxide layer, that is, that the first UV radiation absorbie ⁇ Rende layer consists substantially of metal oxides.
  • Including in the absorbent ers ⁇ th layer is UV radiation according to the application, a content of metal oxides of Minim ⁇ least 75% by weight, in particular at least 80% by weight, understood. In general, the content amounts to 80 to 90% by weight, it can ever ⁇ but also be higher.
  • traces of the precursors used to prepare the first UV-absorbing layer by atomic layer deposition or sputtering or decomposition products thereof may optionally be detected.
  • the detection can be carried out by means of energy-dispersive X-ray spectroscopy (energy-dispersive X-ray spectroscopy, EDX). Based on said traces, the use of the above-mentioned production methods can also be detected.
  • energy-dispersive X-ray spectroscopy energy-dispersive X-ray spectroscopy, EDX
  • the metal oxide of the first UV radiation absorbing layer is selected from a group comprising: titanium oxide, zirconium oxide, zinc oxide, cerium oxide, silicon oxide, aluminum ⁇ oxide, hafnium oxide, tantalum oxide and combinations thereof.
  • the first UV radiation absorbing layer may comprise, in particular as metal oxides titanium oxide, zirconium oxide, zinc oxide and combi nations thereof ⁇ . By means of combinations of different metal oxides, the properties of the first UV-absorbing layer can be adjusted very selectively.
  • the first UV-absorbing layer has at least partially changing layers of different metal oxides. These layers can consist of individual atomic layers, so-called monolayers, or in each case comprise several atomic layers.
  • the first UV-absorbing layer alternating layers of titanium oxide and zinc oxide, zirconium oxide and zinc oxide ⁇ and mixtures of these three compounds umfas ⁇ sen.
  • the first UV radiation-absorbing layer can therefore be realized as a multilayer structure.
  • the first UV-absorbing layer has a
  • the layer thickness may also be 10 nm to 150 nm, in particular 15 nm to 100 nm.
  • layer thicknesses of, for example, 30 nm or 50 nm may already be sufficient.
  • the first UV-absorbing layer is therefore formed very thin, whereby unnecessary Ab ⁇ sorption of visible light is avoided.
  • the layer thicknesses blocks can be determined using a scanning electron microscope ⁇ by analysis of sections by the first UV radiation absorbing layer.
  • a main surface of the first UV-radiation-absorbing layer has a roughness with an RMS value of ⁇ 1 nm.
  • the RMS value can be ⁇ 0.5 nm and especially ⁇ 1 nm.
  • the RMS value of the height variations of a surface is given, which is defined as the root of the mean quad ⁇ ratischen distance of a height profile of a surface of ner mean height of the surface.
  • the heights ⁇ profile of the surface can be determined for example by means of a terkraftmikroskops Ras by within one or more sections of the surface profile height will be ⁇ taken. From the height profile of the surface obtained, for example, by means of scanning force microscopy, an average height can be determined, which represents the arithmetic mean of the height profile. Use the middle Hö ⁇ he and the height profile determined the RMS value can be determined as the value of the roughness of the surface.
  • the first UV-absorbing layer on said sub strate ⁇ is arranged.
  • the first UV-absorbing radiation can be arranged on the side of the substrate facing or facing away from the first electrode.
  • the substrate and the first electrode may be made transparent, so that at least part of the beam path passes through the substrate.
  • An example of such an embodiment is a substrate-emitting OLED (so-called bottom emitter).
  • the layers of the OLED in particular the active ones Layer, UV radiation, which could occur through the transparent Sub ⁇ strat into the OLED, protected.
  • the second electrode may be reflective, in which it is made of aluminum, for example.
  • the first UV-absorbing layer according to at least one embodiment of the present application is transparent and has little or no crystalline or partially crystalline Be ⁇ rich on which visible light is scattered, this OLED has a visually and aesthetically advantageous reflective impression for the viewer on.
  • Such an advantageous, in particular metallic reflecting impression can not be obtained in conventional organic components, in which a so-called decoupling film for UV protection is used, because of the moderate transparency or only very limited.
  • the first UV-radiation absorbing layer is arranged on the second electrode.
  • the first UV-absorbing layer can also be arranged directly on the second electrode.
  • the UV radiation absorbing layer can also be arranged above or below egg ⁇ ner encapsulation.
  • the second electrode is then transparent so that the beam path is absorbed by the second electrode and the first UV radiation
  • the first electrode and the substrate may each comprise or consist of non-transparent materials.
  • non-transparent substrates are metal foils or metal-containing foils.
  • the first electrode is connected as the anode and the second electrode as the cathode.
  • a protective layer is arranged ⁇ .
  • the protective layer may be disposed directly on the first UV-absorbing layer.
  • the protective layer is transparent and scratch-resistant, so that the first UV-absorbing layer is protected against mechanical abrasion and against moisture and other environmental influences.
  • the organic component can therefore also be used prob ⁇ lemlos outside of enclosed spaces.
  • the protective layer can be transparent resins or lacquers, for
  • Example include or consist of an epoxy resin.
  • the protective layer has good resistance ge ⁇ gen UV radiation in general.
  • the protective layer may be formed on the UV-absorbing layer regardless of whether a UV-absorbing layer is disposed on the sub-start and / or on the second electrode.
  • the first UV-absorbing layer is arranged between the substrate and the first electrode.
  • the first UV-absorbing layer can be arranged directly on the substrate.
  • a protective layer as described above may be disposed between the first electrode and the first UV-absorbing layer. This may protect the first UV radiation absorbie ⁇ Governing layer, for example during the manufacture of the component against mechanical influences.
  • a second UV-absorbing layer is arranged on the second electrode.
  • the second UV-absorbing layer environmentally also summarizes a metal oxide or mixtures of various ⁇ Dener metal oxides, and is generally on the side facing away from the active layer of the second electrode.
  • typically the second electrode is also shown transparent so that the Strah ⁇ beam path passes through both the first electrode and the substrate and through the second electrode.
  • An example of such an organic component is a fully transparent OLED.
  • the properties of the second UV-absorbing layer may correspond to those of a first UV-absorbing layer according to the application as already described above. It may have the same but also different properties relative to the first UV-radiation absorbing layer, which in this embodiment is arranged on the substrate.
  • the first and second UV-absorbing layers may also have identical properties, for example if they are produced simultaneously in one process step.
  • the two UV-absorbing layers may or may not be in contact with each other.
  • the organic component can correspond to one of the embodiments described above.
  • the method comprises the method steps: A) generating an optoelectronic layer stack on a substrate,
  • the optoelectronic layer stack a first electrode, a second electrode and an organic layer stack, the at least one organic active
  • Layer comprises and is disposed between the first electrode and the second electrode
  • the process steps may be performed in the above order. If necessary, a different order can be adhered to. It is possible, for example , initially to produce a first UV-absorbing layer on a provided substrate and only then to produce the other layers of the optoelectronic layer stack.
  • the first UV-absorbing layer is generated so that it is arranged in the finished orga ⁇ African component at least in the beam path.
  • the step A) should also include the completion of an optoelectronic ⁇ African layer stack, for example, when a substrate coated with an electrode is used.
  • the first UV radiation is absorbed in process step B)
  • a first UV-radiation-absorbing layer is formed according to at least one embodiment of the organic component which has the corresponding properties described above.
  • the first UV-absorbing layer is produced in particular by means of atomic layer deposition, wherein very thin, transparent UV-radiation absorbing layers with a low surface roughness can be produced.
  • starting materials so-called precursors
  • precursors are cyclically added one after the other into a reaction chamber.
  • the chamber is usually flushed with an inert gas, for example nitrogen or argon.
  • the layer can be added to a monolayer ⁇ per cycle to.
  • the method of atomic layer deposition and suitable devices for this purpose are already known per se and are therefore not described explicitly here.
  • first precursors are used as starting material for the metal component of the metal oxide selected from a group comprising: metal chlorides, tetrakis (ethylmethylamino ) titanium, tetrakis (ethylmethylamino) zirconium, tetrakis (ethylmethylamino) hafnium, tetrakis (dimethylamino) titanium, tetrakis (dimethylamino) zirconium, tetrakis (dimethylamino) hafnium, diethylzinc, trimethylaluminum, and combinations thereof.
  • the metal oxide of the first UV-absorbing employed by atomic layer deposition second precursors as starting material for the oxide component of the metal oxide which are selected from a group comprising: water, ozone and combinations ⁇ of it.
  • These precursors may be optionally combined with Ammo ⁇ niak, hydrogen and / or hydrogen sulfide, which compounds may for example serve as a catalyst.
  • sputtering (sometimes also referred to as sputtering) is usually a solid, the target, bombarded with high-energy ions. At the same time, atoms are leached out of the solid which pass into the gas phase and can be deposited on another surface, for example a substrate.
  • the method of sputtering and suitable devices for this purpose are already known per se and are therefore not described explicitly here.
  • the first UV-radiation-absorbing layer is produced at a temperature of ⁇ 120 ° C. in method step B).
  • the first UV-absorbing layer can be produced at a temperature of ⁇ 100 ° C, for example at 90 ° C. Insbeson ⁇ particular by means of atomic layer deposition, this low temperatures to produce the first absorbent UV-radiation layer can be used.
  • the organic layer stack is not damaged, so that the first UV radiation absorbing layer may be applied in the presence of or ganic layers ⁇ stack.
  • the orga ⁇ African component can therefore be produced with little waste, whereby the production costs are reduced.
  • a protective layer is produced on the main surface of the first UV-radiation-absorbing layer facing away from the substrate.
  • Me ⁇ methods such as spin coating can be used.
  • the process step C) is carried out usually after the procedural rens Colour ⁇ B).
  • organic components can be produced in which the first UV-absorbing layer is arranged between the substrate and the first electrode.
  • execution ⁇ form must not necessarily have a protective layer.
  • the first UV radiation is absorbed in process step B)
  • the first UV rays ⁇ sorbent layer can be formed directly on the substrate.
  • a second UV-absorbing layer is produced on the second electrode at the same time in method step B). This can be done for example by means of atomic layer deposition, wherein the organic component can be coated from both sides.
  • first and second UV radiation absorbing layers can be formed with the same or very similar properties. This approach advantageously allows ⁇ enough, a very cost effective production of the organic component, since both UV radiation absorbing layers are produced in one step.
  • Figures 1 to 4 show schematic cross sections of organic ⁇ shear components of different application according to embodiments.
  • FIGS. 5a to 5b show absorption curves of UV-absorbing layers.
  • an organic component African 1 shows a schematic cross section through an organic component African 1 according to one according to the application execution ⁇ form is shown.
  • an organic component 1 an OLED is shown here, which is designed as a bottom emitter.
  • a transparent substrate 5 made of glass or plastic
  • a transparent first electrode 6 of, for example, ITO is arranged on a transparent substrate 5 made of glass or plastic.
  • the active layer is an organic electroluminescent layer which generates visible light during operation of the organic component 1. can.
  • a second, not transparent electrode 8 made of metal, for example made of aluminum, is arranged.
  • the stack of layers, to collectively ⁇ the first and second electrodes 6 and 8 and the or- ganic layer stack 7, can be referred to herein as optoe ⁇ lectronic layer stack. 9
  • the first UV-absorbing layer 10 may also include at ⁇ parts zinc oxide which is present, for example, in alternate ⁇ the layers with titanium oxide and / or zirconium oxide.
  • the beam path 20 is here representatively as arrow Darge ⁇ represents. However, the beam path 20 may also extend at an angle thereto and / or include reflections.
  • the first UV-absorbing layer 10 has a layer thickness between 15 nm and 150 nm, for example 50 nm, has a transparency of at least 80% in the visible region of the spectrum and is amorphous.
  • the first UV radiation absorbie ⁇ Rende layer 10 was formed by atomic layer deposition and thus has a small roughness on a RMS-value of ⁇ 0.5 nm.
  • the organic layers, particularly the active layer, ef fectively ⁇ , ge ⁇ protects against UV radiation that might come from the outside along the beam path in the organic component are 1.
  • the optically and aesthetically advantageous specular impression produced by the metallic second electrode 8 remains in the organic component 1 due to the transparent, amorphous UV radiation first absorbing layer 10.
  • a protective layer 15 is disposed of an epoxy resin.
  • FIG. 2 shows a schematic cross section of an organic component 1 according to a further embodiment according to the application.
  • the organic component 1 is here just ⁇ if designed as an OLED (bottom emitter).
  • the organic component 1 comprises a substrate 5, a transparent first electrode 6, an organic layer stack 7 and a second electrode 8, as described, for example, even for the or ganic ⁇ component 1 according to FIG. 1 Between the substrate 5 and the first electrode 6, a first UV radiation-absorbing layer 10 is produced here.
  • a protective layer as described above, may also be arranged between the first UV-absorbing layer 10 and the first electrode 6 (not shown here).
  • Protective layer can be the first ultraviolet radiation absorbing
  • Layer 10 during manufacture for example, when applying the first electrode 6, protect from damage.
  • organic component 1 are newly ⁇ if obtain the advantages described above.
  • FIG. 3 shows a schematic cross section of an organic component 1 according to a further embodiment.
  • the organic component 1 is here as fully transparent OLED, in which the beam path 20 extends through both the first and the second electrode 6 and 8.
  • the beam path 20 is again indicated by arrows.
  • the Organic component 1 here comprises a transparent substrate 5, a transparent first and a transparent second
  • a first UV-absorbing layer 10 is arranged according to at least one embodiment according to the application.
  • a second UV radiation absorbie ⁇ Rende layer is disposed on the side remote from the active layer side of the second electrode 8 .
  • a transparent protective layer is produced on one or both UV radiation-absorbing layers 10, 11 (not shown in FIG. 3), which protects the underlying UV radiation-absorbing layer 10, 11 from mechanical abrasion and / or harmful environmental influences , such as moisture, protects.
  • FIG. 4 shows a schematic cross section of an organic component 1 according to a further embodiment, which is likewise designed as a fully transparent OLED.
  • a first UV-absorbing layer 10 between the sub ⁇ strat 5 and the first electrode 6 is disposed here.
  • One or both UV radiation absorbing layers 10, 11 may optionally be provided with a protective layer (not shown).
  • FIGS. 5a to 5d show absorption curves of four different UV radiation-absorbing layers, as may be present in embodiments of organic components according to the present invention.
  • the corresponding layer produced from each of the specified material and in the respective specified layer thickness by means of atomic layer deposition on a 700 mm thick glass substrate.
  • the wavelength in nm is plotted on the x-axis and the absorption on the y-axis.
  • the value of 1.0 ⁇ ent speaks of a transmittance of 100%.
  • Fresnel losses which occur ⁇ upon entering and upon exiting from radiation in the UV radiation absorbing layer already contain (C ⁇ X "CCL 8" 6 Absorption). It was measured with an ellipsometer.
  • FIGS. 5a and 5b show measurement curves for UV radiation-absorbing layers of titanium oxide, which show a
  • FIGS. 5c and 5d show measured curves for UV radiation-absorbing layers of zirconium oxide, which show a

Abstract

Un mode de réalisation de l'invention décrit un composant optoélectronique organique (1) comprenant un substrat (5), une première électrode (6) qui est disposée sur le substrat (5), une deuxième électrode (8), un empilement de couches organiques (7) qui comprend au moins une couche organique active et est disposé entre la première et la deuxième électrode (6, 8), et une première couche (10) qui est disposée au moins dans le trajet de rayonnement (20) du composant et absorbe le rayonnement UV et qui comprend un oxyde métallique et est transparente à la lumière visible.
PCT/EP2012/061847 2011-07-13 2012-06-20 Composant optoélectronique organique et procédé de son fabrication WO2013007488A1 (fr)

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DE102011079101A DE102011079101A1 (de) 2011-07-13 2011-07-13 Organisches optoelektronisches bauteil und verfahren zu dessen herstellung
DE102011079101.9 2011-07-13

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DE102012220586A1 (de) 2012-11-12 2014-05-15 Osram Opto Semiconductors Gmbh Element zur Stabilisierung eines optoelektronischen Bauelements, Verfahren zur Herstellung eines Elements und optoelektronisches Bauelement
US10826016B2 (en) 2018-04-20 2020-11-03 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Organic light-emitting diode package, display panel and method for manufacturing the same

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WO2009126115A1 (fr) * 2008-04-09 2009-10-15 Agency For Science, Technology And Research Film multicouche pour encapsuler des appareils électroniques sensibles à l'oxygène et/ou à l'humidité

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WO2019200650A1 (fr) * 2018-04-20 2019-10-24 武汉华星光电半导体显示技术有限公司 Structure d'encapsulation de diode électroluminescente et son procédé de préparation

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