TW200917893A - Organic electroluminescent device and fabricating method thereof - Google Patents

Abstract

The object of this invention is to provide an organic electroluminescence device which can be fabricated easily and the luminescence and life properties is excellent and fabricating method thereof. This invention provides the organic electroluminescence device and fabricating method thereof as follow. The organic electroluminescence device includes a anode, a light emitting layer, an cathode and a metal oxide layer disposed between the anode and the light emitting layer or between the cathode and the light emitting layer, and the metal oxide layer is formed by the following steps, (A) depositing metal oxide to the other layer of a forming device to obtain a untreated metal oxide layer, (B) exposing the untreated metal oxide layer in an oxygen-containing surroundings.

Description

200917893 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to an organic electroluminescence

Electroluminescence Devices (Orgamc and its manufacturing method. T is sometimes called organic anal element) [Prior Art] Compared with inorganic EL it, organic components can be driven at low voltage, high brightness, and can be accommodated. ^^The color of the illuminating, so in order to obtain higher performance components, so far = trial weaving all the suspect:, has been reported as ίί 'the use of metal oxide as an electron injection layer or hole injection layer . For example, JP-A No. 2,367,784 discloses that an inorganic oxide layer such as molybdenum oxide is provided on an electron-injecting electrode as a highly efficient electron injecting layer. At present, as a major issue in the development of organic EL elements, an element that can be driven for a long life even when illuminated with brightness is being developed. Further, an element having high luminous efficiency and high luminance at a low voltage has been developed. Therefore, various layers of constituent elements are still being explored to help solve the above problems. SUMMARY OF THE INVENTION An object of the present invention is to provide an organic EL device which can be easily produced and which has excellent light-emitting characteristics and lifetime characteristics, and a method for producing the same. The inventors of the present invention have conducted various studies in the above-mentioned circumstances. It is unexpectedly found that by performing a layer which is previously considered to reduce the layer of impurity energy, for example, exposing a layer of a metal oxide constituting the element to the inclusion = The present invention has been completed by the luminescent properties and lifetime characteristics of the organic EL device. That is, according to the present invention, the following items are provided: Π] an organic electroluminescence device having an anode, a cathode of a light-emitting layer, and disposed between the anode and the light-emitting layer or between the light-emitting layer and the cathode a metal oxide layer, wherein the metal oxide layer is a layer obtained by the following steps: (4) a step of depositing a metal oxide in another layer constituting the element to obtain a non-domain metal oxide layer; and (Β) The step of subjecting the above untreated metal oxide layer to an exposure treatment in an oxygen-containing atmosphere. [2] The organic electroluminescence device according to the above [1], wherein the metal oxide layer is a hole injecting layer or is directly in contact with the light emitting layer or the hole injecting layer. [3] The organic electroluminescence device according to [1] or [5], wherein the metal oxide layer has a visible light transmittance of 5 〇 0 / 〇 or more. [4] The organic electroluminescence device according to any one of the above [1], wherein the metal oxide is selected from the group consisting of molybdenum oxide, vanadium oxide, cerium oxide, group oxide, and the like In a group of oxides. [5] The organic electroluminescent element according to any one of [1] to [4] wherein the oxygen-containing atmosphere is controlled to have a humidity of 0.01% to 95% and an oxygen rolling degree of 0.01% to 3%. The method of producing the organic electroluminescent device according to any one of the above [1] to [5], wherein the temperature is in the range of 1 (rc to 6 〇t:). And comprising the steps of: depositing a metal oxide on the other layers of the device to obtain an untreated metal oxide layer; and exposing the unlocalized metal oxide layer to an oxygen-containing environment. Advantageous Effects of Invention The organic EL device of the present invention can be easily manufactured and has high power efficiency.

Since it emits light at a low voltage and has a long life, it can be suitably used as a planar light source for a backlight or a flat panel display. The above and other objects, features and advantages of the present invention will become more apparent <RTIgt; [Embodiment] The organic EL device of the invention has an anode, a light-emitting layer, and a cathode. The organic element of the ruthenium may further have another layer between the anode and the light-emitting layer, and the metal layer having the oxidation of the above-mentioned box may be better. The two T 鈒 oxides, oxides, sulphide and samarium oxides are preferably: oxygen: bis is especially good for indium oxide, which is pentoxide, and • the preferred material is pentoxide: that is good =二=200917893 The step (4) specified in the invention is applied to the case τ, and the rent ratio of yttrium and ytterbium in the metal oxide layer cannot be maintained. In this case, it can be preferably used in the present invention. . Further, the metal oxide may be one type or two or two types. The emulsion layer may contain the metal oxide or the like, and it is preferable that the metal layer is substantially more (4). In other words, the proportion of the gold-based layer/Γ/金:/:: the lower structure in the total amount of the constituent materials can be

Wt% is JL,), and more preferably 99 or more, and even more preferably 99.9 wt0/. . The illuminant layer is preferably provided by the hole injection layer ’ or directly in contact with the SC layer. More specifically, 〇) is provided in contact with the anode and the hole transport layer, and (·&quot;_) is placed in contact with the anode and the electron blocking layer, (..i) and the hole injection layer and The light-emitting layer is provided in contact with each other, (~) is placed in contact with the hole injection layer and the electron blocking layer, and (v) is placed in contact with the anode and the light-emitting layer, and any one of K is provided. The b〇ttom emission structure is more preferably 0·) or 〇), and the above metal oxide layer usually functions as a main in-layer. The top emission company = lower, more preferably (丨) or (iv), the above-mentioned metal oxygen k-hanging functions as a hole transport layer. The above metal oxide layer has a good visible light transmittance. It is greater than or equal to 200917893 50 /., less than or equal to ι 〇 0%. By having a visible light transmittance of 5% or more and 100 Å or less, it can be preferably used for illuminating through the above metal oxide layer. a form of organic a-component. The visible light transmittance is more preferably 70% or more and 1% or less. By having a visible light transmittance of 7〇% or more and 1GG% or less, the light self-luminous layer can be made. Further, the light emission efficiency of the organic EL element is improved by the internal emission, and the thickness of the metal oxide layer is not particularly limited, and is preferably 〇 nm to 50 nm.

The layer obtained by the following steps in the organic EL device of the invention: The upper metal oxide layer is a layer which is provided by g, and is provided by: (A) depositing a metal oxide on other layers constituting the element; The step of sitting on the treated metal oxide layer; and the other layer constituting the component of the upper silk domain (4) metal ruthenium oxide correction sheet can be formed by the phase m layer 'Kona' and the obtained organic Ε] The anode structure (four) is chosen. For example, it may be disposed on the substrate to obtain a direct connection with the electrode. Alternatively, after the electrode is disposed on the substrate, the electrical phase may be stunned +&quot; Layer, charge injection /: The charge-bearing layer is formed, and further deposited thereon, and the metal oxide layer in contact with the layer. The electroplating i product is carried out by vacuum evaporation, molecular beam evaporation, sputtering, or ion beam plating, coating, or the like. It is also possible to use an electropolymer-assisted vacuum vapor deposition method in which a plasma is introduced into a film chamber of 200917893 to improve reactivity or film formation. Examples of the evaporation source of the vacuum deposition method include resistance heating, electron beam heating, high frequency induction heating, and laser beam heating. A simpler method is better resistance heating, electron beam heating, high frequency induction heating. For splashing clocks (Sputtering Method), there are DC current sputtering method (Direct Current Sputter 'DC Sputter), RF Sputtering method (Radio Freqency Sputter, RF Sputter), electronic coupling resonance

Electrophoresis Method (Electron Coupling Resonance Sputter, ECR)

Sputter), conventi〇 sputtering, magnetron sputtering, ion beam sputtering (I〇n Beam Suppter), counter target sputtering, etc., can be used in any manner. . In order not to damage the lower layer, it is preferred to use a magnetron sputtering method, an ion beam sputtering method, or a counter target sputtering method. Further, at the time of film formation, it is also possible to introduce oxygen by introducing oxygen or a gas containing oxygen into the environment. Further, as the metal oxide, not only one, but also an oxide may be used, and a plurality of oxides or unoxidized metals may be used in combination. For example, the molybdenum oxide material is usually M〇〇3, but M〇 metal, or a mixture of these, or the like can also be used. The above step (B) can be carried out after obtaining the untreated metal halide layer in the above step (4) and before forming other layers on the layer. The specific body can be carried out by storing the substrate provided with the above-mentioned untreated metal oxide layer in an oxygen-containing atmosphere after the completion of the above step (A). In addition, the oxygen-containing environment is not particularly limited as long as it is an environment in which a gas containing oxygen flows. The oxygen concentration in the oxygen environment may be the range of the area where it is often, but is not limited thereto, and 11 200917893 is preferably set in the range of 0.01% to 30%, more preferably in the range of 〜30%. Inside. 0 The humidity in the oxygen-containing environment in the above step (B) is preferably set to 0.01% to 95%, more preferably 〇1% to 9〇%, and the s degree is preferably set to 1 (rc~6 (rc, more preferably set to 2〇50C. Further, it is preferable to control the humidity within ±5% of the prescribed value set within the above range during the entire exposure process) In the inside, the π degree is controlled within the hunger range of the predetermined value set in the above range. The period of the exposure process of the above step (8) can be appropriately adjusted according to the required j fruit, the manufacturing period, and the like. It can be set to! Day ~ 20 days 'Better is set to 2 days ~ 15 days. When you get paid for the above metal oxide layer, in addition to the above steps: ί i iB) Before or after the step, any other steps such as ozone (then 3) treatment, heat treatment, etc. may be carried out before or after the above step (8), and then the lamination step of the other layers may be further performed. The strong household treatment may be performed by lmWW~1〇 - The external line is 5 seconds to 3G minutes to perform the heat treatment at 5〇C~35〇C,! The composition of the organic &amp; element of the present invention is more specifically described. The organic EL element of the present invention must be right steep _μ ^ pole, and in addition, 1 having a % pole, a light-emitting layer, and a light-emitting μ pole and the above-mentioned light-emitting layer, and/or between the upper layer and the cathode have further layers. 12 200917893 Can be between the cathode and the light-emitting layer = 2 Layer: hole barrier layer, etc. In the case where it is provided, the layer close to the cathode becomes the electron injection layer, and the layer of the light-emitting layer becomes the electron transport layer. The electron injection layer is a layer having an electron charge to the cathode. The electron transport layer has the function of changing the electron transport from the cathode and the electrotransport layer to the light-emitting layer: the same-passing electron/electron injection layer, or the f-sub-transport layer has a blocking electric hole blocking layer. When the sub-transport layer also functions as a function of the same lightning and f-hole transmission, for example, it is possible to manufacture only the electric current== component, and it is surely set to the anode and the light-emitting layer according to the reduction amount of the current value of the hole current. For example, the layers between them can be enumerated as layers. a resistive layer, etc. In the case where both the hole hole k layer and the hole transport layer are provided, the layer close to the anode and the layer close to the light emitting layer become the hole transport layer. The wf hole injection layer has Replacing the hole injection efficiency from the anode, the so-called hole transport layer means that there is a hole transmission to the light-emitting layer from the anode, the electric or the near-anode of the anode; When the function of blocking the electron transmission is performed, for example, an element that flows only the electronic current of 13 200917893 can be produced, and the blocking effect is confirmed based on the amount of decrease in the current value of the electronic current. In the organic EL device of the present invention, the light-emitting layer is usually provided in one layer, but is not limited thereto, and two or more light-emitting layers may be provided. In this case, two or more light-emitting layers may be directly contacted to form a layer. The metal oxide layer or the like used in the present invention may be provided between the two or more layers. Further, the electron injecting layer and the hole injecting layer are collectively referred to as a charge injecting layer, and the electron transporting layer and the hole transporting layer are sometimes collectively referred to as a charge transporting layer. More specifically, the organic EL element of the present invention may have any one of the following drawers: θ a) anode/hole transport layer/light-emitting layer/cathode b) anode/light-emitting layer/electron transport layer/cathode Ο Anode/hole transport layer/light-emitting layer/electricity d) anode/riding ϋ e) anode/light-emitting layer/charge injection layer/cathode Ο, pole/charge injection layer/light-emitting layer/charge injection layer/cathode 5 anode/charge> Main layer/hole transport layer/light-emitting layer/cathode) anode/hole transport layer/light-emitting layer/charge injection layer/cathode cathode 0 anode/charge injection layer/hole transport layer/light-emitting layer/charge injection layer/2 = / charge injection layer / light-emitting layer / charge transport layer / cathode) drain / light-emitting layer / electron transport layer / charge injection layer / cathode 200917893 l) anode / charge injection layer / light-emitting layer / electron transport layer / charge injection layer / m) anode/charge injection layer/hole transport layer/light-emitting layer/charge transport layer cathode anode/hole transport layer/light-emitting layer/electron transport layer/charge injection layer/charge generation sub-transport layer/(where '/ Each layer is adjacent to each other and laminated. The same applies hereinafter.) In the respective examples of the group, *=layer 1 The organic EL element of the present invention may be provided in two layers or two layers to have two layers of luminescent phase organic EL elements. : Electrode i charge injection layer / hole transport layer / light-emitting layer / electron sound transmission / wheel layer transport layer / light-emitting layer, layer 4 of organic EL elements. Input = Note 8 layers as a repeating unit (to be called as = pass A)), which can be cited as: having a hard dry 7 〇 q) anode / charge injection layer / hole transport layer / luminescent layer / electron transfer layer / 15 200917893 Charge injection layer / repeating unit A / repeating unit Α ... / cathode contains two layers (9) layer to cut light unit EL · element. The organic layer structure is composed of the above-mentioned layer P and the layer structure q, and the layers other than the anode are omitted as needed. The haze emitting layer is referred to as a "so-called electrode" and refers to a layer of the applicator. Examples of the material constituting the electrode include, for example, Indium Tin Oxide, Molybdenum Oxide, and the like. Sheep vanadium and indium oxide Each of the above-mentioned layer constitution p and layer is provided as a charge injection layer and a hole transfer wheel. The organic EL element of the present invention can further have the above-mentioned layers. In the organic EL element of the present invention, each layer is opposite to the substrate - the side is two", and the substrate and the organic element composed of the layer are sandwiched on the substrate. For example, 目士甘』, e set a transparent layer. In the specific month, the substrate, the anode and the transmission layer can be arranged as a transparent layer, and the electric intrusion layer and the hole member can be made, or the bottom emission type of the electron can be transmitted to the bottom layer. The cathode and the sealing structure 16 200917893 are each provided as a transparent layer, and have a substrate/cathode/charge injection into the top-emitting type element. Further, the layer/charge injection layer/anode/sealing; in the case of the transmission of the two sub-holes, the organic EL element formed by the substrate and the cathode can be placed in a transparent layer to form a so-called: bottom; The layers are made into so-called pieces that are both permeable to visible = organic in the present invention; in the el element, in order to push the adhesion or improve the electrical step b of the self electrode and the placement of the electrodes, the injection layer or the device In order to improve the adhesion of the interface or prevent the mixing of the _ ' or the thin buffer at the interface of the luminescent layer ^ ', the order of the layers in the layer of the charge transport layer, the number, and the thickness of each layer or the lifetime of the device Use it properly. The material of each layer of the organic EL element which can be formed by the bristles, and the substrate of the organic EL element of the present invention are not changed as long as the electrode or the organic layer is formed. For example, glass or plastic can be used. A molecular film, a stone substrate, a substrate obtained by laminating these materials, and the like. Above 17

200917893 The substrate (4) substrate can be obtained, or the anode of the organic EL device of the present invention can be formed by using a transparent or semi-transparent electrode to form an element that emits light through the anode. The transparent electrode or the semi-finished electrode can make the film of metal oxide, metal sulfide or metal of _____ $, which is better to use the material with high transmittance, is used according to the local (4) organic layer (4). Specifically, for example, it is composed of cerium oxide, oxidized cerium, tin oxide, and a composite of these oxides, namely, indium tin oxide (V)-ITO (ITO) and indium zinc oxide (Indium Zinc 〇xide). Film (10) SA#) made of conductive glass, or gold, uranium, silver, copper, 1T. , indium oxide, tin oxide. The production method may, for example, be a /2 瘵 plating method, a sputtering method, an ion plating method, a plating method, or the like. Further, as the f, an organic transparent conductive film such as an amine ((10) qingling.) or a derivative thereof, a polythiophene or a derivative thereof may be used. θ for the anode ' can also utilize a material that reflects light, and the material preferably has a work function of 3. 〇 eV of metal, oxide, or metal sulfide. The film thickness of the anode may be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10, preferably melon, and 50 nm to 500 nm. &lt;Curtain injection layer&gt; The hole injection layer may be provided between the anode and the hole transport layer or between the anode and the light-emitting layer. In a particularly preferred aspect of the invention, the hole injection layer can be used in the above-mentioned metal oxide layer. In the case of the organic EL device of the present invention, in the case where the metal oxide layer is a layer other than the hole injection layer, a material for forming the hole injection layer may, for example, be a phenamine compound or a star-emitting type. Starburst) amine-phthalocyanine, oxides such as cerium oxide, oxidized knob, tungsten oxide, molybdenum oxide, cerium oxide, aluminum oxide, amorphous carbon (am〇rph〇us carbon), polyaniline, polythiophene Derivatives, etc. &lt;Core Transport Layer&gt; The above-mentioned metal oxide layer may be used in the hole transport layer. In other cases, the material constituting the hole transport layer may be exemplified by polyvinylcarbazole or a derivative, a polylithic or its derivative, a polyoxyalkylene derivative having an aromatic amine on a branched or main chain, a pyrazoline derivative, an arylamine derivative, an anthracene derivative ( Stilbene derivatives), triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polyarylamines or derivatives thereof, polypyrrole or derivatives thereof, poly(p-phenylacetylene) Cpoly(paraphenylenevinylene)) or a derivative thereof, or poly(2,5-thienylenevinylene) or a derivative thereof. Among these materials, the hole transporting material used in the hole transport layer is preferably polyvinyl carbazole or a derivative thereof, polydecane or a derivative thereof, or an aromatic amine compound group in a branched or main chain. a polyoxyalkylene derivative, polyaniline or a derivative thereof, polythiophene or a derivative thereof, a polyarylamine or a derivative thereof, poly(p-phenylacetylene) or a derivative thereof, or polyexepene ethylene or a derivative thereof Other polymer hole transport materials, more preferably polyvinyl carbazole or its derivatives, poly 200917893 Shi Xizhuan or its derivatives, the branch chain of the chain has a fragrant incense _ wei Weihe organism. In the case of a low-molecular-weight hole transporting material, the low-molecular-weight electric wheel material has a residual polymer adhesion, so that the film-forming method of the hole-transporting layer is not limited, and the low molecular-electrolytic transport material can be exemplified. : A method in which a mixed solution of a low molecular hole transport material and a polymer binder is used. Further, the polymer hole transporting wheel is not limited to a method of forming a film by using a solution.

The solvent used for film formation by the solution is not particularly limited as long as it dissolves the hole transporting material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane, and ether solvents such as tetrahydrofuran (tetrahydr〇furaj^, aromatic hydrocarbons such as toluene and xylene). A solvent, a ketone solvent such as acetone or methyl ethyl ketone, or an ester solvent such as ethyl acetate, butyl acetate or ethyl cellosolve acetate. The method of forming a film from a solution can be used, for example, by using a solution. Spin coating, casting, microgravure coating, gravure coating, bar coating ), roll coating (r〇U coating), wire-bar coating, dip coating, siit coating, capillary coating ( Coating methods such as capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing Printing ) Coating method such as offset printing, reverse printing, reprinting (reversal priming), inkjet printing (ink_jet printing), etc. In terms of easy formation of a pattern, gravure printing is preferred. Printing methods such as printing, screen printing, flexographic printing, plate printing, reverse printing, and inkjet printing.

The polymer binder to be mixed preferably does not greatly inhibit charge transport, and a polymer binder which does not strongly absorb visible light can be preferably used. Examples of the polymer binder include polycarbonate, polyacrylic acid acrylate, polymethyl acrylate, polymethyl methacrylate (methacrylate), and polystyrene (p). 〇lystyrene ), polyvinyl chloride, polyoxane, etc. - The optimum value of the film thickness of the electric/transfer layer varies depending on the materials used. 'As long as the chest-effect cake and the luminous efficiency are appropriate values, 'but at least pinholes must not be produced (pinhc&gt;le) If the thickness of the hole transmission layer is too thick, the driving dust of the element becomes high and the thickness of the hole transport layer (10) is, for example, 1 coffee to 1 qing, preferably 2 nm to 500 nm', more preferably 5 nm to 20 〇 nm. . &lt;Light-emitting layer&gt; In the present invention, the organic light-emitting layer is preferably a main layer of moxibustion, and is usually mainly used for re-lighting time (low molecular compound and macromolecular compound: it may be more complicated (4). Examples of the material that can be used include the following luminescent material dye-based material dye-based materials, for example, cyclopentylamine (eye-) 21 200917893 or a derivative thereof, tetraphenylbutadiene or a derivative thereof, triphenyl group Amine or a derivative thereof, oxadiazole or a derivative thereof, pyrazoloquinoline or a derivative thereof, distyrylbenzen or a derivative thereof, distyryl arene (distyrylarylene) or a derivative thereof, pyrrole (pyrr〇ie) or a derivative thereof, a porphin ring compound, a η ratio β-ring compound, b-peri-ruthene or a derivative thereof, perylene or a derivative thereof, oligothiophene or a derivative thereof, an oxadiazole dimer, a pyrazoline dimer, a quinacridone or a derivative thereof, coumarin or Derivative, rubrene or its derivative, squalene oxime (sq) Ualilium) or a derivative thereof, porphyrin (P0rphyrin) or its organism, the present ethylene dye, tetracene or a derivative thereof, pyrazolone or a derivative thereof, decacyclomethene (decacyclene), phenoxazone, etc. Metal complex compound material The metal complex compound material may, for example, be a metal having a luminescence excited by a doublet state, such as a ruthenium complex or a platinum complex. Complex, alumi-quinolinol compiex, beryllium-benzoquinolinol complex, benzoquinone-zinc-zinc complex, benzothiazole zinc complex a compound, an azomethyl zinc complex, a zinc porphyrin complex, a ruthenium complex, etc., and a central metal having a rare earth metal such as A1, Zn: Be荨 or Tb, _Eu, Dy, etc. The base has a metal complex such as hydrazine, thiadiazole, phenylpyridine, phenylbenzimidazole, or quinoline structure. 'σ 22 200917893 The polymer material is, for example, a poly pair. Phenylene block or its derivative, 3, Hebi, polyparaphen Ethylene or its derivative, polyglybdenum or its derivatives, polyethylidene or its derivatives, poly (poy) or its derivatives, polyethylene or its derivatives, the above pigments or metals The complex compound (4) is a sub-material obtained by polymerizing a material. The material of the above-mentioned hair-emitting material, which emits blue light, may be exemplified by diphenyl ethoxylate: k or a derivative thereof. Ethylene 2 or a derivative thereof and a polymer of the compound, a polyethylene material, a touch thereof, a polyparaphenylene or a derivative thereof, a polydip or a mellow thereof. The towel is preferably a polyethylene 2 seat of a polymer material or a derivative thereof, a polyparaphenylene or a derivative thereof or a poly or a derivative thereof. The material which emits green light may be exemplified by quinacridone or a derivative thereof, coumarin or a derivative thereof, and a polymer of the compound, polyparaphenylene acetylene or a derivative thereof, polydipeptide or a derivative thereof. Wait. Among them, preferred are polymer materials poly-p-phenylacetylene or a derivative thereof, polyfluorene or a derivative thereof. Further, examples of the material that emits red light include coumarin or a derivative thereof, a compound of the phenophene ring and a polymer of the compound, polyparaphenylene acetylene or a derivative thereof, polythiophene or a derivative thereof, polyfluorene or Derivatives, etc. Among them, a polymer material polyparaphenylene acetylene or a derivative thereof, polythiophene or a derivative thereof, polyfluorene or a derivative thereof, and the like are preferable. In order to improve the luminous efficiency or change the emission wavelength, the doping material may be used in the light-emitting layer 23 200917893. The doping material may be, for example, an anthracene derivative, a rust derivative, or a lazy organism J::阙: The thickness of the /cornerene light layer is usually equal to the side. Further, such a method of forming a film of a light-emitting layer, a method of forming a light-emitting phase containing an organic substance, can be used by applying a solution of a material to a substrate or a solvent used for film formation. = transport material; the same solvent as the liquid forms the hole transport layer when the dissolution hole transfer method solution is applied to the substrate or above the substrate = for example: spin coating, lying, micro embossing roller Paint

C ^ method = plate coating method, bar coating method, roll coating method, wire bar coating =, (10) coating method, slit coating method, capillary coating method, nozzle spray coating ', nozzle A coating method such as a coating method such as a coating method, a gravure printing method, a screen printing method, a printing method such as a lithography method, a reverse printing method, or an inkjet printing method. From the viewpoint of easily forming a pattern or easily distinguishing a plurality of colors, a printing method such as a gravure printing method, a printing method, a flexographic printing method, a stencil printing method, a reverse printing method, or an inkjet printing method is preferable. In the case where the material is a sublimable low molecular compound, a vacuum method can be used. Further, it is also possible to use a method of forming a light-emitting layer only at a desired position by transfer or thermal transfer using a laser. μ 24 200917893 &lt;Electron transport layer&gt; The above-mentioned metal oxide layer may be used as the electron transport layer. In other cases, a material which constitutes the electron transport layer may be a known material, and it is exemplified by: a derivative, anthraquinodimethane or a derivative thereof, benz〇quin〇ne or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, Tetracyano anthraquinodimethane or a derivative thereof, fluorenone derivatives, diphenyldicyano ethylene or a derivative thereof, a biphenyl hydrazine derivative, or 8- A metal complex of quinolinol or a derivative thereof, polyfluorene or a derivative thereof, polyquinoxaline or a derivative thereof, polydipeptide or a derivative thereof, and the like. Among these materials, preferred are oxadiazole derivatives, benzoquinone or derivatives thereof, hydrazine or a derivative thereof, or a metal complex of 8-hydroxyquinoline or a derivative thereof. It is better to use 2_(4_biphenyl)_5_(4_t-butylbenzene electron transport layer shouting __ , rash electronic transmission: so that Lai shouted to the plating method, or to make a solution or in the process of smashing = _ method, polymer electron transport material can be exemplified: in the 2: = melt! When using the solution ϋΐί domain, the polymer adhesive layer can also be used. The method of forming the cold electron transport layer can be exemplified by the same film forming method as the method of forming the hole transport layer by using the solution 25 200917893 liquid. The optimum value of the film thickness of the transport layer varies depending on the materials used. 'As long as the voltage and the rate of the bribes are appropriate values, the thickness of the pinholes is not generated at least for a certain period of time. If the electron transport layer is too thick, Therefore, the driving voltage of the element may become high and is not preferable. Therefore, the film thickness of the electron transporting layer is, for example, Inm 〜1, preferably 2 nm to 5 〇〇 nm, more preferably 5 nm to 200 nm. Electron injection layer &gt;

The electron injecting layer is disposed between the electron transporting layer and the cathode or between the cathode and the cathode. In the case of the electron injection layer, the above metal oxide may be used. In other cases, depending on the type of the light-emitting layer, the electron injection/曰 may be exemplified by metal or soil test, or one or The alloy I is an oxide of the above metal, a toothed material, and a mixture of the above materials of the plate 2. Examples of metals and their oxides and substances can be exemplified by lithium, sodium, potassium, rubidium, planer, sodium oxide, sodium fluoride, potassium oxide, fluorination, oxygen and potted bismuth, and fluorinated hammer. , carbonic acid. Further, examples of soil test & & quot 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Electric 26 200917893 &lt;cathode material&gt; is the material of the cathode used in the two-piece material, the material with high yield, the material of == electron injection, and the metal of the metal, the metal of the test, and the transition metal Lithium, sodium, potassium, strontium, planer, strontium, magnesium, levy: metals such as: zinc, gram, 锢, 钸r #, 钡, 钡, aluminum, 铳, vanadium, medium- 钸a metal such as ruthenium or the like, or a metal of one of the above metals and alloys, such as titanium, Si, Lu, He, and - in the above-mentioned metals and alloys - "叮 ° ° gold" or graphite or graphite inter-layer compounds, etc. The examples of human gold can be exemplified by: magnesium-silver alloy, gold of gold, lithium-button, Λ», paste 1, magnesium-aluminum alloy, indium-silver, gold, lithium-magnesium alloy, lithium For the indium alloy and the transparent conductive electrode, for example, a conductive indium or the like can be used. Specifically, the conductive metal oxide can be made of indium tin nTm f: tin oxide, and an oxide-depleting compound, that is, oxygen (10). ), the conductive organic substance can be used as an organic transparent conductive material such as a membrane, a singularity, a polystimene or a derivative thereof. The cathode has a laminated structure of two or more layers. Further, the electron injecting layer is sometimes used as a cathode. The film thickness of the cathode can be appropriately selected in consideration of electrical conductivity and durability, and = 1 〇 mn 10 (four)' It is preferably 2 〇 〜 ~ ... more preferably 50 nm ~ 500 nm. The method of making the cathode can be used for the operation of the air, the sputtering method, and the lamination method for bonding the metal film. 27 200917893 &lt;Insulating layer&gt; The insulating layer having a film thickness of 2 nm or less which can be arbitrarily possessed by the organic EL element of the present invention has a function of facilitating charge injection. (IV) The above-mentioned insulating material can be exemplified by metal fluoride. a compound, a metal oxide, an organic insulating material, etc. An organic EL element provided with an insulating layer having a film thickness of 2 nm or less can be exemplified by an organic layer having a film thickness of 2 nm or less adjacent to the cathode. An EL element and an organic EL element provided with an insulating layer having a film thickness of 2 nm or less adjacent to the anode. [The organic EL device of the present invention can be used as a planar light source, a segment display device, and a dot shape. Matrix display device (d〇t In order to obtain planar light emission by using the organic EL element of the present invention, it is only necessary to arrange a planar anode and a cathode so as to overlap each other. A method of providing a mask having a pattern-like window on a surface of the planar light-emitting device, a method of forming an organic layer of the non-light-emitting portion to be extremely thick, and substantially not emitting light, or causing ablation in an anode or a cathode A method of forming any one or both of the electrodes into a pattern. By using any of these methods to form a pattern and arranging a plurality of electrodes in a manner of being independently turnable on/off (0N/0FF), A segment type display element capable of displaying numbers, characters, or simple symbols. Further, in order to form the matrix element, the anode and the cathode may be formed in a strip shape and arranged in an orthogonal I form. Partial color display and colorful display can be realized by a method of separately applying a plurality of kinds of light-emitting materials having different light-emitting colors or a method of using a color filter or a color conversion filter. The dot matrix element 28 200917893 can be driven by passive or combined with a thin film transistor (Thin_Film Transistor ’TFT). The display elements can be used as display devices for brains, televisions, mobile terminals, mobile phones, car navigation, viewfinders of video cameras, and the like. Further, the above-mentioned planar light-emitting element is of a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar light source for illumination. Further, when a flexible substrate is used, it can also be used as a curved light source or display device. EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples and Comparative Examples. &lt;Example 1&gt; (1 - 1: Preparation of electron blocking layer material) In a separable flask equipped with a stirring blade, a baffle, a length-adjustable nitrogen introduction tube, a cold/coil tube, and a thermometer, 2 was added. , 7-bis(1,3,2-dioxaborolanyl)-9,9-dioctylfluorene 158.29 parts by weight, bis-(4-disindolyl)-4-(1-mercaptopropylidene) 136.11 parts by weight of aniline, 27 parts by weight of trioctylguanidinium chloride (Aliquat 336 manufactured by HENKEL Co., Ltd.) and 1800 parts by weight of toluene. On the one hand, nitrogen gas flows from the nitrogen introduction tube, and the temperature is raised to the surface under scramble. 90 ° C. After adding 0.066 parts by weight of acetic acid and 0.45 parts by weight of tris(o-tolyl)phosphine, 573 parts by weight of a 17.5% aqueous sodium carbonate solution was added dropwise over 1 hour. After the completion of the dropwise addition, the nitrogen introduction tube was lifted from the liquid surface to be kept under reflux for 7 hours, and then 3.6 parts by weight of phenylboric acid was added, and 29 200917893 was kept under reflux for 14 hours, and then the mixture was cooled to room temperature. After removing the aqueous layer of the reaction liquid, the reaction liquid layer was diluted with toluene, and then washed with 3% acetic acid aqueous solution and ion parent water. After adding 13 parts by weight of N,N-diethyldithiocarbamate-methyl trihydrate to the liquid-separated oil layer and dissolving for 4 hours, the liquid-reactive oxygen is passed through the mixing column of the oxidized Weigel. Then, in the &amp; column, the toaster was cleaned by toluene (four). The filtrate and the washing liquid were mixed and added dropwise to a decyl alcohol towel to record the polymer. The polymer obtained by the separation of the sediment: After washing with methanol, the polymer was dried by vacuum drying to obtain 192 parts by weight of the polymer. The obtained polymer is referred to as polymer compound 1. The weight average molecular weight and the number average molecular weight of the polymer compound 1 were determined by the following gel permeation chromatography (GPC) analysis method, and the weight average molecular weight of the polymer compound 1 was 3 7 χι. 〇5, the number average molecular weight is 8.9 x l 〇 4. (GPC analysis method) The weight average molecular weight and the number average molecular weight in terms of polystyrene were determined by GPC. Standard polystyrene manufactured by POLYMER LABORATORIES was used to make a calibration curve for GPC. The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0,02 wt%, and the solution 10 /zL was injected into a GPC apparatus. The GPC device is a LC-10ADvp manufactured by Shimadzu Corporation. The column is a PLgel 10 μ m MIXED-B column (300 mm x 7.5 mm) manufactured by two POLYMER LABORATORIES companies in series, and the mobile phase is flowed at a flow rate of LO mL/min at 25 ° C in the column. Of the four 30 200917893 hydrogen furan. The detector used a uv detector and measured absorbance at 228 nm. (1-2: Production of Organic EL Element: m〇〇3 Layer) A glass substrate having an IOK film patterned on its surface was used as a substrate on the ITO film, and the film was vapor-deposited by vacuum evaporation in the following order. M0O3 layer with a thickness of 10 nm. The light transmittance of the M〇〇3 layer at this time is about 80% at a light wavelength of 440 nm, which is about 7 〇0/〇 at a light wavelength of 5 〇〇 nm and about 82% at a light wavelength of 620 nm. The surface of the glass substrate partially covering the side of the IT film was deposited using a vapor deposition mask. The glass substrate was mounted in the vapor deposition chamber using a substrate holder. Μο〇3 powder (purity of 99.99% manufactured by ALDRICH) was loaded into a tungsten boat for box type sublimation materials, and covered with a perforated crucible so that the material did not fly, and then placed In the evaporation chamber. ...

The degree of vacuum in the ruthenium plating chamber was set to 3 x 10 Å to 5 Pa, and M0O 3 was gradually heated by a resistance heating method, and degassing was sufficiently performed, followed by evaporation. The degree of vacuum in the evaporation process is made less than or equal to 9 x 1 〇 -5 Pa. The film thickness is always monitored by a crystal oscillator (crystal 〇scillat〇r). When the vapor deposition rate of Mo〇3 reaches about 28 nm/s, the main shutter is turned on to start film formation on the substrate. The evaporation process ^ rotates the substrate to make the film thickness uniform. The film formation was carried out for about 36 seconds by controlling the vapor deposition rate to the above speed, and a substrate provided with a vapor film having a film thickness of about 1 〇 nm was obtained. ...X The obtained substrate was taken out to the atmosphere and stored in a clean room. 2 31 200917893 = Pre-exposure treatment. After the treatment, the clean room towel is ventilated, and the humidity is adjusted within the range of 50% ± 1% humidity and 2 rc ± rc. (1 - 3 · Production of organic EL element: production and sealing of other layers), and secondly, obtained in the above-mentioned (Η) by the spin coating method on the obtained M〇〇3 layer of the exposed treatment The electron blocking layer material is formed into a film, and the electron blocking layer having a film thickness of 2 Gmn is taken out, and the electrode portion and the sealing region are taken out, and the formed electron blocking layer is removed, and is thinned by a heating plate. B. Bake for 20 minutes. Then, on the electron blocking layer, a polymer light-emitting organic material (RP158 SUMAT) was formed by a spin coating method to form a light-emitting layer having a film thickness of 90 rnn. The light-emitting layer formed in the electrode portion and the sealing region was taken out. Thereafter, the process up to the sealing is carried out in a vacuum towel so that the components in the process are not exposed to the atmosphere. The substrate was heated in a vacuum heating chamber at a substrate temperature of about 10 (rc) for 60 minutes. Thereafter, the substrate was transferred to a steaming house towel to form a cathode on the light-emitting portion and the extraction electrode portion, and on the light-emitting layer. a quasi-a (aHgnmef) cathode mask. Further, on the one hand, the mask and the substrate are rotated in terms of a clock cathode. As a cathode, the metal Ba is heated by a resistance heating method and plated at a vaporization rate of about ο nm / s. The film formation thickness was 5 nm. Then, A1 was vapor-deposited to a film thickness of 150 nm on the metal Ba by a electron beam evaporation method at a temperature of about 2 Å/s on the metal Ba. Thereafter, the substrate and the prepared periphery were prepared. Coated with 1; ¥ hardened resin 32 200917893 Qiao Mi:: the glass is bonded, the silk is applied to the vacuum towel, and then under the atmospheric pressure, the hunting is fixed by the irradiation of UV to make the light-emitting area 2 mmx2 mm = machine el The obtained organic EL device has a layer structure of a glass substrate / Μ〇〇 3 layer / 电子 3 layer / electron blocking layer / luminescent layer / Ba layer / Α 1 layer / sealing glass. (1 - 4: evaluation of organic components) Powering on the fabricated components, the light is illuminated to 1 〇cd/m2. Light emission start voltage and, so that brightness is energized outline.

Cd/m \ measures luminous efficiency and brightness halving life. The results are shown in Table 1. As compared with Comparative Example 1 described later, the light-emitting efficiency of Example 1 was high, the light-emission starting voltage was low, and the luminance halving life was remarkably prolonged. &lt;Example 2&gt; An organic EL was produced in the same manner as (1 - 1) to (I - 4) of Example 1 except that the exposure period was set to 9 days in the step (1-2). Components are evaluated. The results are shown in Table 1. It can be observed that the light-emitting efficiency of the second embodiment is higher than that of the comparative example 1 described later, the light-emission starting voltage is low, and the luminance half-life is remarkably prolonged. &lt;Example 3 &gt; In the same manner as (1-1) to (1-4) of Example 1, except that the exposure period was set to 2 days in the step (1-2) , Organic EL elements were produced and evaluated. The results are shown in Table 1. It is observed that the luminous efficiency of the third embodiment is higher than that of the comparative example 1 described later, the light-emission starting voltage is low, and the luminance half-life is prolonged. Same as 33 200917893 &lt;Comparative Example 1&gt; In the step (丨-2), the exposure period is not set, but the step (1) is immediately performed after the vapor deposition film is obtained, and otherwise the same operation as in the embodiment 1 is performed. An organic EL element was produced and evaluated. The results are shown in Table 1. [Table 1] Flow-voltage characteristics and characteristics of exposure Open-air number maximum power efficiency (lm/W) Luminescence start voltage (V; at 10 cd/m2) Luminance halving life (hr; at 2000 cd/m2) Example 1 2 Day 0.57 4.05 324 Example 2 9 days 0.67 3.94 394 Example 3 20 days 0.84 r 3.76 234 Comparative Example 1 No 0.52 429 209 Scope The scope of the appended claims is disclosed as the preferred embodiment of the present invention. It is not intended to limit the invention, and any person skilled in the art will be able to modify and modify the invention without departing from the spirit of the invention.

A brief description of the schema] is defined as the standard. Benefit [Main component symbol description] None 34

Claims (1)

200917893 X. Patent Application Range: 1. An organic electroluminescent device having an anode, a light-emitting layer, a cathode, and a metal oxide layer disposed between the anode and the light-emitting layer or between the light-emitting layer and the cathode And the above metal oxide layer is a layer obtained by the following steps: (A) a step of depositing a metal oxide on other layers constituting the element to obtain an untreated metal oxide layer; and (B) The step of subjecting the above untreated metal oxide layer to an exposure treatment in an oxygen atmosphere. 2. The organic electroluminescent element according to claim 1, wherein the metal oxide layer is a hole injection layer, or the crucible or the hole injection layer is directly in contact with each other. The organic electroluminescence device according to claim 1, wherein the metal oxide layer has a visible light transmittance of 50% or more. 4. The organic electroluminescence according to claim 1, wherein the metal oxide is selected from the group consisting of oxides, vanadium oxides, hegan oxides, group oxides, and ages of the derivative. Ethnic group. 5. For example, apply for organic electroluminescence as described in (4). The above oxygen-containing environment is controlled by a humidity of 〇1%~95% and an oxygen of 0.0P/. ~30%, the temperature is in the range of 1〇t~6〇t. /35 200917893 6. A method of manufacturing, which is a method of producing an organic electroluminescence device according to the invention of claim 1, comprising the steps of: depositing a metal oxide on other layers constituting the element to obtain a step of treating the metal oxide layer; and exposing the above untreated metal oxide layer to an oxygen-containing environment. 36 200917893 VII. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None