TW201132229A - Organic electroluminescence device and fabricating method thereof, display device and lighting device - Google Patents

Abstract

An organic electroluminescence device and fabricating method thereof, with display device and lighting device having excellent lighting efficiency and durability, a low driving voltage, and which the fabricating cost can be reduced are provided. An organic electroluminescence device of this invention having a lighting layer and at least a layer adjoined to the lighting layer between a pair of electrodes, and at least the layer adjoined to the lighting layer is formed by spraying a liquid including two or more low molecular compounds of molecular weight of 1500 or less. An organic electroluminescence device, wherein at least the layer adjoined to the lighting layer is hole transport layer.

Description

201132229 VI. Description of the Invention: [Technical Field] The present invention relates to an organic electroluminescence device, a method of manufacturing an organic electroluminescence device, a display device, and a lighting device. [Prior Art] As a revolving device (four), a dipole = an excitation element (hereinafter also referred to as an organic EL element), a transistor using an organic conductor (a study of her et al. Several pieces are used as solid-state light-emitting large-area full-color display elements. The development of lighting applications for light sources. Under normal circumstances, two pieces of organic electric excitation are composed of an organic compound layer containing a light-emitting layer and two pairs of organic compounding forces are lost. For the electrode: if the organic electroluminescent device is injected into the organic compound layer and from the anode to the organic compound layer, the electron and the hole are re-entangled in the luminescent layer: η: conduction band When returning to the valence band, 'the energy is in the form of light: the illuminance is obtained by this. In the manufacture of the interpolar optical element, as for the method of forming the film attached to the 对 ί ,, it can be used as the evaporation method. The vacuum steaming is again, wet, the spin coating method of the method, the printing method, the ink method of the mouth, etc. / The method for forming a film on a substrate in a vacuum, such a machine: = electric excitation first element, also It is called a steaming type and has a light source. The display of the display such as Jie or TV, however, the step of the steaming and forging in the manufacture of the vapor-deposited organic EL element has a large energy cost for the equipment cost of the steaming mirror device or the evaporation material of the 4 201132229, and it is required to progress to reduce the organic electroluminescent light. The manufacturing cost of the component. The wet method can also use a polymer organic compound which is difficult to form a film in a dry process such as vapor deposition, and has the following advantages: a δ film forming method compared with a vapor deposition method or the like. It is simple, does not require a mask for coating, or a vacuum device, and is suitable for durability of flexing resistance or film strength when used in a flexible display or the like. In particular, it is suitable for large-area, high-definition, and suitable for future large-surface organic EL displays. An organic electroluminescent device (hereinafter, an organic EL device) which is a layer constituting the EL element is formed by a coating method, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. 7-42314. ). An organic layer 1 comprising at least one layer of an organic layer having two or more organic &; matter, formed by the / fool process (review pr〇cess). - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Further, an organic component which exhibits a high external emission enthalpy efficiency and a long luminescent lifetime which is formed by coating a dispersion liquid or a water-transfer coating liquid is disclosed. However, in the coated organic anal device, there is a difference in luminous efficiency and low yttrium. I think that the luminous efficiency is caused in the coated EL element or the polymer material of 201132229, although the film is formed by coating the bismuth fiber method. Low-molecular materials are usually formed by vapor deposition using a method that is more versatile. SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and achieve the object. r, that is, an object of the present invention is to provide an organic electroluminescence device which has low luminous efficiency and durability, low driving voltage, and reduced manufacturing cost. Further, an object of the present invention is to provide a method for producing an organic electroluminescence device which can produce an organic electric excitation which is excellent in luminous efficiency and durability and has a low driving voltage at a low manufacturing cost. Optical component. Further, an object of the present invention is to provide a display device and an illumination device. The display device and the illumination device have the organic electroluminescence element. That is, the means for solving the problem are as follows. [1] An organic electroluminescent device, which is an organic electroluminescent device having a light-emitting layer between a pair of electrodes and at least one layer adjacent to the light-emitting layer, wherein: the at least one layer is adjacent to the light-emitting layer The layer is formed by a spray method using a liquid containing two or more kinds of low molecular weight compounds having a molecular weight of 1,500 or less. [2] The organic electroluminescent device according to [1], wherein the at least one layer adjacent to the light-emitting layer is a hole transport layer. [3] The organic electroluminescent device according to [1], wherein the two or more low molecular compounds having a molecular weight of 15 Å or less are the first low molecular compound and the second low molecular compound. The compounding ratio of the two compounds is 20:80 to 80:20 by weight. [4] The organic electroluminescent device according to any one of [1], wherein the two or more low molecular compounds having a molecular weight of 15 Å or less are two or more types of hole transmission. material. [5] The organic electroluminescence device according to [4], wherein a difference in free potential between the two or more types of hole transport materials is 〇"eV or more and 〇6 eV or less. [6] The organic electroluminescent device according to [4], wherein the two or more types of hole transporting materials are arylamine derivatives or leaf/salt derivatives. [7] The organic electroluminescent device according to any one of [1], wherein the layer adjacent to the light-emitting layer of the at least one layer is an electron transport layer. [8] The organic electroluminescent device according to [7], wherein the electron transmission is 201132229

w. In particular, the A layer is formed by a liquid containing two or more kinds of electron transporting materials. [9] The organic electroluminescent device according to [8], wherein a difference in electron affinity between the two or more electron transporting materials is 〇 eV or more and 6 eV. [10] A method of producing an organic electroluminescence device, which is a method for producing an organic electroluminescence device having a light-emitting layer between a pair of electrodes and at least one layer adjacent to the light-emitting layer. The layer adjacent to the light-emitting layer of one layer is formed by a spray method by a liquid containing two or more kinds of low molecular weight compounds having a molecular weight of 1,500 or less. [11] The method for producing an organic electroluminescence device according to [10], wherein the light-emitting layer and each layer of the layer adjacent to the light-emitting layer are formed by the spraying method. [12] A display device of the present invention, wherein the organic electroluminescent device of any one of [1] to [9], or the organic device of any one of [10] or [1] An organic electroluminescent device obtained by a method of producing an excitation light element. [13] An illuminating device having the electroluminescent device of any one of [1] to [9], or the organic electro-excitation according to any one of [10] or [11] An organic electroluminescent device obtained by a method of manufacturing an optical element. 8 201132229 Effect of the Invention According to the present invention, the molecular weight of two or more types is _ _ _ _ _, (4) and the bribe layer is wrong, which provides thermal stability, excellent luminous efficiency and longevity, = low voltage, An organic electroluminescent device that can reduce manufacturing costs. ...moving 'Lingling gamma, can provide - U-method of the financial device Wei light element' Saki money electric excitation light element (four) making a stalk to manufacture the handle to create thermal stability, excellent rate of injection and subordination, low drive voltage Electromechanical excitation of optical components. According to the present invention, a display device and an illumination device having the above-described organic electro-optical member can be provided. For the above and other objects of the present invention, the advantages and advantages can be more obvious. The following is a preferred embodiment, which is described in the following drawings. The details are as follows. [Embodiment] The components are detailed below. Description of the organic EL of the embodiment. The organic EL device of the present invention is an organic electroluminescence device having a light-emitting layer between at a pair of electrodes and at least one layer adjacent to the light-emitting layer: the layer adjacent to the light-emitting layer may have two or more layers A liquid of a low molecular weight compound having a molecular weight of 1,500 or less is formed by spraying.屯,处, the low-molecular compound of the present day, which means that it will have an unsaturated sputum (5) gastric polymerizable monomer) 'use the initiator to make the unsaturated bond open 201132229 crack, so that the bond grows chain-like The obtained compound which is not a polymer or an oligomer, and which has a molecular weight distribution of a compound having a molecular weight of 1500 or less has a molecular weight distribution, and has a molecular weight of usually 100 or more. Thereby, the material forming the layer adjacent to the light-emitting layer does not contain impurities derived from the polymerization initiator, the polymerization terminal agent, and the chain transfer fresh compound used in the synthesis of the polymer or the oligomer. Thereby, it is possible to avoid such a phenomenon that the function of the layer is deteriorated, and thus an organic electroluminescence element having luminous efficiency and durability 俨 = can be obtained. The low molecular weight compound having a molecular weight of _ or less is more preferably a compound purified by a known purification method. Thereby, it is possible to more reliably avoid the phenomenon that the impurities deteriorate the function of each layer. Well-known purification methods include sublimation purification method, recrystallization purification method, column purification method, and the like. The polymer polymer 'is very difficult to purify such a polymer filament by purifying when the repeating unit has a structure other than the intended purpose of the reactant. Therefore, from this viewpoint, it is preferable that the molecular weight is 1,500 or less. Low molecular weight. . Two or more kinds of low molecular weight compounds having a molecular weight of 1,500 or less are two or four kinds, and more preferably two or three kinds, and more preferably two types. When the molecular weight is determined to be two kinds of low molecular compounds, the mixing ratio of the first low molecular compound to the second low molecular compound is preferably 20:80 to 80:20 by weight, more preferably In the organic EL device of the present invention having the above configuration, the driving voltage can be lowered. Further, by spraying a liquid which dissolves or disperses the material constituting the layer in a solvent, as described above, it is possible to reduce the manufacturing cost of the organic EL element without using a charging step.

Fig. 1 shows an example of the configuration of an organic EL device of the present invention. The organic electroluminescent device 10 of the present invention, which is not shown in Fig. J, is supported on the support substrate 2 with an organic layer interposed between the 11⁄4 pole 3 and the cathode 9. More specifically, the organic layer includes, for example, a hole injection layer 4 on the anode, a hole transport layer 5 on the hole injection layer 4, a light-emitting layer 6 on the hole transport layer 5, and the light-emitting layer 6. The hole blocking layer 7 on the upper hole blocks the electron transport layer 8 on the hole 357. The content of the solid matter is not particularly limited with respect to the total amount of the above liquid 'usually 0.0001 wt% to 1 〇 wt%'. If it is a spray method, it is preferably 0.0001 wt ° / 〇 〜 1 wt%. Moreover, it is preferred that at least one of the layers adjacent to the light-emitting layer is a hole transport layer. In particular, the light-emitting layer is directly disposed on the hole transport layer and the electron transport layer is directly disposed on the light-emitting layer, and the solvent of the (4) is the same as the organic solvent, thereby making the boundary between the layers © The bonding is further improved, and it is particularly easy to obtain an organic EL device excellent in luminous efficiency and durability. At least one of the + luminescent layer and the layer adjacent to the luminescent layer can be formed by applying the liquid by a spray method. Therefore, particularly in the case where the lower layer of the layer formed by the mist method is another organic layer, the liquid 11 201132229 organic/mixture can more reliably reduce the degree of dissolution of the other organic layer. Since the damage is caused by the like, an organic component which is more excellent in luminous efficiency, durability, and color reproducibility can be obtained. Further, compared with other coating methods, the spray method is easy to suppress the amount of the solvent used and is easy to dry, so that the manufacturing cost can be further reduced. Further, by the spray method, it is possible to form a film of a plurality of layers without damaging the layer under the layer # formed by the spray method. Further, the step of applying a liquid by a spray method, in other words, a step of spraying a gas (the carrier gas sheet is floated with a liquid particle of a liquid solvent (10), and is transferred to a predetermined surface by m (four). The form of the aerosol is not particularly limited, and the particle diameter of the liquid particles is usually 0.01 μm to ΙΟΟμιη: more preferably 〇〇1 μιη to 1 〇μιη. Examples of the gas include air, nitrogen, argon, and the like. The spray device can be arbitrarily used. The flow rate of the carrier gas of the known spray-air-filled gel is preferably 〇1 〜 L/miy - more preferably ai L/min 〜1 〇 [如化. The thickness of the desired layer of each layer is ～ΗΗ, 11, and (4) is the dry silk yarn. 疋1 12 201132229 I, in the illuminating layer, and the layer adjacent to the luminescent layer The coating method of the other layer is not particularly limited, and may be applied by spin coating, air knife coating, bar coating, knife coating, or slant coating. Cloth, curtain coating, spray method, method, method, ink method, etc. ^ For example, when a hole transport layer is directly disposed on the anode, the material of the anode is usually as follows: (10) organically dissolved, a material with high tolerance. Therefore, regarding the hole transport layer, Any of the previously exemplified liquid coating methods can be suitably used. However, in the above-mentioned advantages, for example, regarding the light-emitting layer and the electron transport layer, the spray method is also used for the transfer layer. : = can,: the coating method, so the result can reduce the manufacturing cost. Therefore, the shape of each layer of the layer which is formed by spraying the liquid by the spray method to form the light-emitting layer and the layer of η impurity is the best The composition of the layer of the organic layer is determined by the spray layer =, the body (four) into the hole transport layer, the money transfer, and the electron transport layer, and can be used according to the use of the organic EL device. The specific form of the A-shaped shape of the Meguro S can be exemplified as follows: 'But the % pole/electric' with the transport layer/light-emitting layer/electron transport layer/cathode 13 201132229 pole (2) anode/hole Transport layer / luminescent layer / barrier layer / electron transfer layer / negative (3) anode / electricity Transport layer / luminescent layer / barrier layer / electron transfer sub-injection layer / cathode θ electron transmission 2) /: hole injection layer / hole transmission layer coffee (5) anode / hole injection layer / hole transmission layer / luminescent layer /Resistor Transport Layer / Electron Injection Layer / Cathode e As described above, in the present invention, the layer adjacent to the light-emitting layer is opened by a liquid coated with a material which dissolves or disperses the constituent layer in the solvent towel. It is preferable to form a hole transport layer or an electron transport layer by a coating method, and it is more preferable to form a hole transport layer and an electron transport layer by a coating method. The light-emitting layer, the electric layer, and the electron transport layer are formed by a coating method. In the layers comprising a plurality of layers of the hole transport layer and the light-emitting layer and the electron-transport layer (where the plurality of layers are one of the organic layers; one or more layers) are more preferably Coating in a solvent or dispersing the (4) formation of each layer (4), or inserting another layer constituting the organic layer between the hole transport layer and the (4) layer n or the light-emitting layer and the electron transport layer (the above layer In the case of the configuration (2), the above-mentioned plurality of layers (the case where the layer configuration (7) is the case, the hole transmission f 'light-emitting layer, the _ layer, and the electron transport layer) and the arbitrary layer are formed by the test. In contrast, from the transition of a plurality of shapes to the end faces of the other end faces, the boundary between the layers is sharp, and θ has a tendency to obtain an organic EL element having excellent luminous efficiency and durability and capable of reducing the driving voltage. . The organic layer is not particularly limited. In addition to the light-emitting layer, it may have a hole 2 layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole blocking layer, a f-sub-ring, and an exciton. Reading materials. ^, these layers can also have other functions. The present invention also relates to a method for producing an organic electroluminescence device, which is characterized in that: a layer having an emission layer between electrodes and at least a layer adjacent to the light-emitting layer, and a method for producing an organic electroluminescence device, characterized in that: The layer adjacent to the light-emitting layer may be formed by a spray method by a liquid containing two or more kinds of two or more low molecular compounds of 1500 or less. The organic solvent can be exemplified by the organic solvent. Further, at least one layer adjacent to the light-emitting layer can be formed by a sputtering method. More preferably, each layer of the light-emitting layer and at least the layer adjacent to the layer of the layer is formed by a spray method. More preferably, the hole and the electron transport layer are formed by a spray method, and it is more preferable to form the hole transport layer and the electron transport layer by a tilting method. Preferably, the hole transport layer, the light-emitting layer, and the electron layer 1' are formed by spraying the body. More preferably, the liquid is coated by a spray method to form a hole transport layer and emit light. Layers and layers of the electron transport layer. The manufacturing method of the invention of the invention is described in a preferred aspect of the step of coating the liquid by the (four) method. The organic layer contained in the optical element (4) can be formed by any of the following methods. The reason is that the impurities (hydrocarbons, amines, particles) in the carrier gas (inert gas) or the particles/oil in the piping can be removed by forming the organic layer by spraying 201132229 ^ V-TL/AA. . In the production method of the present invention, it is preferred that the carrier gas composed of an inert gas and the coating liquid having an oxygen concentration of 1 〇〇 ppm or less and a water content of 100 ppm or less are mixed. The organic layer is laminated on the substrate. It is preferable to use an inert gas such as chlorine, gas or nitrogen for the inert gas, and argon or nitrogen is used. Further, in the organic layer formed by depositing the deposited layer on the substrate, it is preferable that the particles larger than 〇2411 are less than 1 in each of 4〇〇4111<1〇〇4111. One. Preferably, the oxygen concentration is 100 ppm or less and the dew point is ^. C is formed into a film under an inert gas atmosphere of 1. Further, it is preferable to dry or anneal the organic layer formed by the above method in an environment of an oxygen-producing #100 PPm or less and a dew point of _3 (in an inert gas of rc or less). The cloth liquid is preferably deposited on the insoluble organic layer to form an organic layer. The elements of the element are described in detail below for the description of the organic EL element constituting the present invention. (Substrate) The substrate used in the present invention is preferably. It is a substrate which does not scatter or reduce light emitted from the organic compound layer. Specific examples thereof include inorganic yttrium stabilized yttrium yttrium (YSZ), inorganic poly(ethylene terephthalate) such as glass, and polyethylene terephthalate. Polybutylene phthalate, polynaphthalene 201132229 :: vinegar and other polyester, polystyrene, polyaluminum polyethylenimine 'polycyclic hydrocarbon hydrocarbons, norbornene thin tree month W, money, etc. organic For the case of using a surface as a substrate, for example, when the surface is used as a substrate, it is preferable to reduce the ions eluted from the glass, and it is preferable that the glass is used for the case where the lime glass is used. Moreover, Shi Xi et al. Arrier e(10)) The lime test is the same as the material, the stability, the dimensional stability, the solvent resistance, and the electrical insulation and processability. El·!1, the shape, structure, size, etc. of the substrate can be selected according to the purpose and purpose of the light-emitting element. Usually, the base, the secret of the shape is better. The substrate is a laminated structure; and can be formed by a single component; more than one component. The straw can be made colorless or transparent, and it can be colored and transparent. It does not cause the light emitted by 3 to scatter or decay. (4) It is difficult to make a colorless layer on the substrate. (The material of the gas barrier layer I (the layer of the helium layer) may suitably be a nitride rock or an oxide stone. The moisture barrier layer (gas barrier layer) may be formed by, for example, a high-frequency money ore method. When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be provided as needed. (Anode) 201132229 The anode usually has a function as an electrode for supplying a hole to an organic compound layer, and regarding the shape thereof, The structure, the size, and the like are not particularly limited, and may be appropriately selected from known electrode materials depending on the use and purpose of the light-emitting element. The anode is usually a transparent anode. The material of the anode may be, for example, a metal, an alloy, a metal oxide, or a conductive material. The compound or a mixture thereof. Specific examples of the anode material include tin oxide (AT0, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (IT0). Conductive metal oxides such as zinc indium oxide (IZ0), metals such as gold, silver, chromium, and nickel, and mixtures or laminates of the metals and conductive metal oxides, and inorganic conductivity such as maleated copper and copper sulfide. a material, an organic conductive material such as polyaniline, polythiophene or polypyrrole, and a laminate of the same and the like, among which a conductive metal oxide is preferable, in particular, self-productivity, high conductivity, transparency, and the like. In view of the above, ITO is preferable. The anode can be, for example, a wet type such as a coating method in consideration of suitability for a material constituting the anode, and a physical method such as a vacuum evaporation method, a ruthenium plating method, an ion electricity method, or the like. A method, a chemical vapor deposition method, a chemical polymerization method, a chemical deposition method, or the like, which is suitably selected, is formed on the substrate. For example, when ITO is selected as the material of the anode, the anode is formed. The method can be carried out according to a direct current or high-frequency wave sputtering method, a vacuum evaporation method, or the like. In the organic EL element of the present invention, the position of the anode is formed and tanning, and the light-emitting element can be used according to the purpose and purpose of the light-emitting element. Preferably, a preferred crucible is formed on the substrate. In this case, the anode may be formed on the base 18 201132229 J «/-/! One of the materials, on the part of it. It can also be carried out by using Ray:== and by overlapping masks to carry out the real q material, physical _ engraving and doing the reading by the lifting method or the printing (4), or by l-=== It is suitable for the choice of materials. It can't be discussed as ~1〇2 hanging for 1〇nm~5〇_, preferably it is better to set it to 1G3 coffee, and better to set ί right=anode In the case of being transparent, it may be colorless and transparent (10). In order to emit light from the transparent electrode side, the transmittance is preferably 60% or more, more preferably 7 % by weight or more. In Sawada's Supervisor's "Expanding the New Year's Test" (detailed in the trouble, J = can be applied to the present invention. When a plastic substrate having low heat resistance is used, it is preferred to use iridium or IZO at 150. 〇: The following transparent anode formed at low temperature. (Cathode) The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and the shape, structure, size, and the like are not particularly limited, and the electrode material can be known from the use and purpose of the light-emitting element. Suitable for selection. Examples of the material constituting the cathode include a metal, an alloy, a metal oxide, a conductive compound, a mixture thereof, and the like. Specific examples thereof include an alkali metal (Example 19 201132229 such as Li, Na, K, Cs, etc.), an alkaline earth metal (for example, Mg, Ca, etc.), gold, silver, lead, aluminum, a sodium-potassium alloy, a lithium-salt alloy, and magnesium. - rare earth metals such as silver alloys, indium, and antimony. One of these may be used alone, but two or more kinds may be used in combination as appropriate from the viewpoint of both stability and electron injectability. Among these materials, in view of electron injectability, the material constituting the cathode is preferably an alkali metal or an alkaline earth metal, and the material constituting the cathode is preferably a material mainly composed of aluminum in terms of excellent storage stability. . The material referred to as the main material is aluminum alloy, aluminum and 0.01 wt% ~ 1 () wt% of an alkali metal or alkaline earth metal alloy or a mixture thereof (such as lithium · aluminum alloy, magnesium - aluminum alloy, etc.) . In addition, the material of the cathode is described in detail in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Λ The method for forming the cathode is not particularly limited, and may be carried out according to a known method: considering the composition method, the true shovel merging property, and the wet chemical vapor phase t such as a printing method or a coating method In the case of the chemical method such as the Lai method and the ion plating material, and the chemical method such as the H-plasma chemical vapor deposition method which is suitable for selection, it is possible to simultaneously select a metal or the like as a material of the cathode. When the ruthenium or the sputtering is carried out in accordance with the sputtering material, or when the cathode is formed, the vacuum can be performed by the stacking mask, and the chemistry of the photo-mineralization method can be used. Sexual silver: The physical etching of the film, etc., is carried out by plating or miscellaneous (four) lines, and the village corrects the method or the printing method of 201132229. (4) The date of formation of the cathode is not particularly limited, and all of the shapeable and conjugated layers may be formed on the portion thereof. The resultant is 0 1 η' between the cathode and the organic compound layer, and may also be inserted into the thick layer. It can also be regarded as an electron injection method, etc., and the shape i can be selected by vacuum test, frequency method, ion electricity, and the material of the pole, and it is impossible to select 5〇mn~1μιη. Hanging for 1〇譲~5〇's left and right' is better by: ΐ方明 can also be opaque. In addition, the transparent cathode can be thick, i-^. The material of the cathode is thinly formed into a layer of 1 (10)~0 or 1Z. A transparent conductive material. The organic layer of the piece is explained. The organic EL element of the present invention has an organic layer 电3 hole transport layer, a light-emitting layer, and an electron transport layer. Layer 1 layer, electricity =: etc.: r describes the blocking (light-emitting layer) θ. The illuminating difference has the following layer: the electric hole injection layer or the hole transmission layer receives the hole, from the cathode to the pole, and Or the electron transport layer accepts electrons, and provides the function of illuminating the electricity. It is a film containing an amorphous organic semiconductor. The material is formed of a material, preferably a mixed layer of a host material γ, referred to as a luminescent dopant. X-ray materials can be used as a light-emitting material. The shame (four) season and the bulk material are preferably charge transport materials. The main material may be a mixture of two or more kinds of main materials which can be transported by a host material such as electron transfer. Further, the light-emitting layer/middle may contain a material which does not have charge transport property and does not emit light. In order to enhance the color purity of the south or to broaden the wavelength range of the light emission, the light-emitting layer may contain two or more kinds of light-emitting materials. Moreover, the luminescent layer may be a layer or a layer of two or more layers, and the layers may also have different luminescent colors into the phosphorescent luminescent material. The photo luminescent material generally includes a transition metal atom or a steel ruthenium atom. Compound. For example, the transition metal atom is not particularly limited, and preferred examples thereof include ruthenium, 13⁄4, palladium, tungsten, rhenium, iron, silver, gold, silver, copper, and platinum, more preferably ruthenium, silver, and platinum. More preferred is 鈒, I white. Examples of the lanthanide atom include 镧, 饰, 铉, 铉, 钐, 铕, 礼, 钱, 销, 销, 录, 叙, and 销. Among the atoms in the shai class, it is preferred to converge, pin and ritual. The ligand of the complex compound can be exemplified by G· Wilkinson et al.

Comprehensive Coordination Chemistry, Pergamon Press Public 22 201132229 Division issued in 1987; Η· Yersin's "Photochemistry and Photophysics of Coordination Compounds j Springer-Verlag △ Division 19 = annual release; Yamamoto Akira's "Organic Metal Chemistry _ Basics and Applications" The stall bases listed in the 1982 issue of the company. Specifically, the hexyl group is preferably a _ prime ligand (preferably a gas-coordinating earth) or an aromatic carbocyclic ligand (for example, preferably having a carbon number of 5 to 3 Å, more preferably a carbon number) 6 to 3 〇, more preferably, the carbon number is 6 to 2 (), particularly preferably, the carbon number is ^6 12, a cyclopentadienyl anion, a benzene anion, or a ketone anion, etc.), aza-containing a ring ligand (for example, preferably having a carbon number of 5 to 3 Å, more preferably a carbon number of 6 to 30, more preferably a carbon number of 6 to 2 G, particularly preferably a carbon number of 12, and a phenyl group). K, material, returning, screaming, or morphine, etc.), bis-coordination (such as acetamidine, etc.), carboxylic acid ligand (for example, preferably having a carbon number of 2 to 30, more preferably The carbon number is 2 to 20, more preferably 2 to 16 carbon atoms, an acetic acid ligand or the like, and an alkoxide ligand (for example, preferably 1 to 3 carbon atoms, more preferably carbon number i) ~2G, more preferred is a carbon number of 6 to 20', a salt ligand, etc.), a Wei oxygen ligand (for example, preferably a carbon number of 3 to 4 G, more preferably a carbon number of 3 to 3) 3G, further preferred is a carbon number of 3 to 20, such as a trimethyl decyloxy ligand, dimethyl-third a decane group, a triphenylpropoxy group, etc., an oxidizing group: a group, an isonitrile chain, a minus ligand group, a nucleus group (a carbon 3 to 40, more preferably a carbon) The number is 3 to 30, more preferably 3 to 2 carbon atoms, particularly preferably 6 to 2 carbon atoms, such as a triphenylphosphine ligand, etc., a thiolate ligand (preferably The carbon number is 1 to 30, more preferably the carbon number is 1 to 20, more preferably, the carbon number is 6 to 2, for example, a phenylthiolate ligand, etc., and the phosphine oxide is 23 201132229. a radical (preferably having a carbon number of from 3 to 30, more preferably a carbon number of from 8 to 30, still more preferably a carbon number of from 18 to 30, such as a triphenylphosphine oxide ligand, etc.), more preferably Nitrogen-containing heterocyclic ligand. The above complex compound may have one transition metal atom in the compound, and may also be a so-called multinuclear complex compound having two or more transition metal atoms. It can also contain different kinds of metal atoms. Among the compounds, specific examples of the luminescent material include, for example, US6303238B1, US6097147, WOOO/57676, WO00/70655, W001/08230, W〇01/39234A2, WO〇1/41512A1, W002/02714A2^WO02/15645A1 , WO02/44189A1 ^ WO〇5/19373A2, Japanese Patent Special Open 2 Xie Tear, Japanese Patent Special Open 2002-30267, Japanese Patent Special Open 2〇〇2_117978, Japanese Patent Special =: 074, 曰本专利专开 2 〇〇2_235076, 曰本专利特幵1,123982, Japanese Patent Special Open 2()()2_17.684,肥211257, 曰日开开2观26495,Japanese Patent Special Secret 2卿4,日ί秘247859 Japanese Patent Special Opener 0, Japanese f (4) 2]73674, Japanese Patent Special Open 2, 679, Japanese Patent Special Opener% Machine, Japanese Patent Special Open 2〇〇6_256999, 曰本专利特历历-_' Day:=,2007-19462, 敝 光 细 细 与 τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光 发光曰5, Rh complex, Ru for the character, shame, m for the plate, day 5, for the complex, 0s for the difference '9 &, Gd complex, Dy Complex and Ce 24 201132229 complex. Particularly preferred is an Ir complex, a pt complex or a Re complex, wherein at least one of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferred. Ir complex, pt complex or Re complex of the coordination pattern. Further, from the viewpoints of luminous efficiency, driving durability, chromaticity and the like, it is particularly preferable to include a multidentate ligand of 3 or more teeth, a Pt complex, or a Re complex. "fluorescent luminescent material" The fluorescent luminescent material generally includes benzoxazole, benzoimidazole, benzothiazole, styrylbenzene, diphenylbutadiene, tetraphenylbutadiene, naphthoquinone. Indole, coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadienyl, bisstyryl Quinacridone, pyrrolizin pyridine, thiadiazolidine pyridine, diene, styrene amine, aromatic secondary sulfhydryl compound, condensed polywangfang fragrant compound (蒽, morphine, 芘, 茈, red fluorene or pentacene, etc., 8-metal complex of the base material, strontium complex or rare earth complex, various metal complexes, organic stone, and Some derivatives and the like. The specific examples of the luminescent materials in the above-mentioned compounds include the specific compounds exemplified in paragraphs [0054] to [〇〇64] of JP-A-2009-16579, and the paragraphs of JP-A-2008-218972. The specific compound exemplified in [0068], and the X-ray material 1 and the like which are used in the examples described later are compounds which can be suitably selected, and therefore are not limited to these compounds. The luminescent material in the luminescent layer has a longness, an external quantum efficiency of wt=wt%~5〇wt%, and a self-resistance of 50wt%, more preferably than the weight of all the compounds in the luminescent layer that normally form the luminescent layer 25 201132229. It is a thickness of 2~, 'preferably containing 1 wt%~ luminescent layer. ~ 4 two Wt%. 500 nm, from the external quantum efficiency point = preferably 2 thin ~ ~ 2 〇Γ body screaming 5 then ^ is better ^ The main body used in the invention is good transmission hole body (four) excellent transmission "Curtain Transfer Subject" The present invention _ used the age of the hole to give the following materials. The specifics of the rumored rounds (4) can be listed, for example,: turn, ah, material, aza, aza, sit, sputum, sputum, sit, heart, °, aryl, burn, Each t, ° ratio (tetra) ketone, phenylenediamine, arylamine, amine-substituted 杳 酉 tong, stupid 蒽, _, 腙, $, Wei, _ compound, styrene amine compound , an aromatic di-diorganodecane, a carbon film, and derivatives thereof. A pre-chemical substance, preferably a derivative, a miso derivative, an aromatic compound, a thiophene derivative, and more preferably a human having an oxazolyl group, an electron transporting host σ as the present invention The electron-transporting body in the luminescent layer used in the process, 26 201132229 considers the 'electron affinity Ea 3·4 eV or less, = 3'5 eV from the viewpoint of durability, preferably 2.5 ev" In the following, it is more preferably 2 6 eV or more, and the self-improvement durability is preferably 2.8 eV or more and 3.3 eV or less. The ip is preferably 5.7 eV ^ drive voltage consideration, the free potential is below 7.0eV, above 7.5 eV, more preferably 5.8 eV. This electronic value is better than 5'9 eV or more 6.5 Below eV. material. Specifically, for example, the main body of the Buchi can be exemplified by the following materials: fixed, saliva, dioxin, _ ^, ♦ sitting " than saliva, three sputum,. Oxime, quinone diimide, cardamomethane, fluorenone, biphenyl fluorene, divalent aromatic compounds, tert-sinter, stilbene pyrazine, fluoride-derived derivatives, naphthoquinone, etc. a cyclic tetracarboxylic anhydride, a phthalocyanine, and a metal complex of the compound, "other rings form a condensed ring", a metal of 8-hydroxyquinoline derivative; each or awkward (d) electron-transporting host complex, etc. = 働 働, triazine derivatives, etc.), where == From the side of durability, (4) is a gold phase. Metal 错 (a) better 疋 has a wealth of at least η on the metal or A metal complex of a ligand of an oxygen atom or a sulfur atom. The metal complex has no particular limitation on the metal ion, and is more ion, _, hetero, miscellaneous, ionic, proton, = ion, ion filament More preferably, the ion, the ion, the gallium ion, the 27 201132229 zinc ion, the platinum ion or the ion, and more preferably the aluminum ion, the zinc ion or the ion. There are various well-known ligands in the base group', for example, "photochemistly and Photophysics of

Coordination Compounds, Springer-Verlag, H. Yersin, issued in 1987, "Organic Metals Chemistry_Basic and Application_", Sanghuafang Company, Yamamoto Akio, 1982 issue, etc. The ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having a carbon number of 1 to 3 Å, more preferably a carbon number of 2 to 2 Å, and particularly preferably a carbon number of 3 to 2). It may be a single-dentate ligand or a ligand of 2 or more teeth. It is preferably a ligand of 2 or more teeth below f teeth. Moreover, a ligand of 2 teeth or more and 6 teeth or less and a single tooth The mixed ligand is also preferred. The ligand may, for example, be a pyridazine ligand (for example, a pyridine complex, a ruthenium complex, a triplicate ligand #), or a phenyl-salt ligand (for example, Illustrative examples thereof include hydroxyphenylbenzimidazole with a base, a transphenyl group, and a lysine; := “i~2==^2 preferably has a carbon number of 1 to 30, more preferably a carbon one. The number of slaves is from 1 to 10, and examples thereof include a methoxy group, an ethyl group of 2-ethyl [oxy group], and a decyloxy group (preferably, for example, the carbon number is 6 to 20, particularly preferably The carbon number is 6 to 12, the oxy '4 · phenylene oxide, etc.) 1, the naphthyloxy group, the 2 -naphthyloxy group, the 2,4,6-trimethylbenzene: and the number of the anastomoses is 1 to 12 For example, a certain ratio of alkoxy groups, 28 201132229 pyridazinyloxy group, pyrimidinyloxy group, and quinolinyloxy group, alkylthio group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 丨~, particularly preferably a carbon number of J 12 to 12, for example, a methylthio group or an ethylthio group), and an arylthio group. (preferably having a carbon number of 6 to 30, more preferably a carbon number of 6 to 2 Å, particularly preferably a carbon number of 6 to 12, for example, a phenylthio group, etc.), or a heteroarylthio group (for example) Preferably, the carbon number is from 1 to 30, more preferably the carbon number is used, and particularly preferably the carbon number is, for example, a pyridylthio group, a 2-benzoimidazolium group, a 2-benzoquinazolylthio group, and 2 · ϋ sulfur scales), Wei oxygen filaments (preferably having a carbon number of 1 to 30, more preferably a carbon number of 3 to 25, and particularly preferably a carbon number of 6 to 2 Å, for example, triphenyl Wei An oxy group, a triethoxy methoxy group, and a triisopropyl valoxy hydride group _ sub-ligand (it is difficult to have a carbon number of 6 to 3 Å, more preferably a carbon number of 6 to 25). The carbon number is 6 to 2 Å, for example, benzophenone ion, naphthyl anion, and: anion anion, etc., aromatic=cyclic anion ligand (preferably, the carbon number is U, more preferably the carbon number is 2 to 25, particularly preferably, the carbon number is 2 to 2 〇, for example, an anion, an anion kiss can be cited. Anions, tri-salt anions, cesium salium anions, benzenes, νΪΪ anions, benzoquinones, sitting anions, ° phenanthrene, I, etc.), pseudo, (1) _ anion, alkoxy ligand, Aromatic-smoke anion ligand, - 乂方香知-Heterocyclic anion ligand. Earth-based chest enumeration, special opening 20 () 2 · 235 () 76, Japanese patent special opening 4 · 2 ΐ 4 ΐ 79, 曰 29 201132229 Open the secret test 62, the Japanese patent special open 2 buy 2 legs, the Japanese open brain -22 painting, the Japanese patent special open edit 13 and other compounds. The content of the host material in the present invention is not special. From the viewpoint of the definition, the ratio of the it and the driving voltage, it is preferably 15 wt% or more (four) or less with respect to the weight of the compound having the light-emitting layer. Point A The material used in this type is preferably glass transfer ‘,=5. 〇C is 15 or more (rc or less. More preferably, the glass transfer point is 6 or less and less than 50. If the glass transition point of the host material is less than 50, it is not good in terms of heat resistance of the component, if it exceeds In the case of the thief, the heat treatment after the film formation becomes difficult. In the case of the compound of the present invention, as a specific example of the main material in the present invention, Japanese Patent Laid-Open Publication No. Hei 20- 9-16579 Specific compounds exemplified in paragraphs [0〇79] to [0083], and host materials 1 and the like used in the examples described later, but are not limited to these compounds (hole injection layer, hole transport layer). The hole injection layer and the hole transport layer are layers having a function of receiving a hole from the anode or the anode side and transmitting to the cathode side. In the present invention, at least the layer adjacent to the light-emitting layer is preferably electrically. The hole transport layer 'two or more kinds of low molecular weight compounds having a molecular weight of i or less are preferably two or more kinds of hole transport materials. By mixing two or more kinds of compounds, hole injection property from the anode can be provided, and Excellent entry into the light-emitting layer The cloth type hole injection layer. Moreover, by mixing two kinds of 201132229 Γΐί low-yield compound ', the thermal stability such as crystallization can be greatly increased' and the thermal stability of the element can be improved. Two or more holes are transmitted. The difference between the free potential of the material is lev.lev or more. One or less 'better' is more than the above. The following is the coating type 7L towel, usually ❹PEDQT/PSS or arylamine polymer, starburst amine type. When the material is used as a hole injection layer, the free potential of these compounds is small. Therefore, the injection hole of the hole from the anode of IT0# is small, and the power to the hair layer is worried, which becomes the driving voltage rise. The main reason for the deterioration of the financial system is that a step layer can be provided between the electric energy layer and the light-emitting layer to promote the injection of holes, and the difference between the free potentials is two or more of G1 ev or more and 0.6 eV or less. The hole transporting material can reduce the number of layers and further reduce the cost. - Specifically, it is preferable to contain a derivative derivative, a salivary derivative, a triazole derivative, an oxazole derivative, and an oxadiazole derivative. , imidazole derivatives, polyaryl hydrocarbon derivatives, Side organisms, financial derivatives, benzene bribs, arylamine derivatization #, amine-substituted Chasaki organisms, styrylpurine derivatives, ketone derivatives, anthracene derivatives, anthracene derivatives, f nitrogen a burned derivative, an aromatic tertiary amine compound, a stupid ethylamine compound, an aromatic tertiary mono-human methyl compound, an anthracene polyphthalocyanine compound, a foreign compound, a thiophene derivative, an organic decane derivative, carbon, or the like In the present invention, it is preferred that two or more kinds of hole transporting materials contain an arylamine derivative or a material touch, and (4) a silk amine derivative and a ten-seat derivative. The hole transportability of these materials is large. 31 201132229 In the organic EL element of the present invention, a hole containing a Thunder can be included. The main entry layer or the hole transport layer is introduced into the hole injection layer or organic. Properties of Compound Oxidation 2:::: Organic compounds for electron acceptability. The compound of the domain can also be made of gallium: in terms of inorganic compounds, such as gasified iron or gasification, gasification, indium, five gasification, and the like, metal such as molybdenum, and the like. In the case of the reduction of the hunger and the emulsification of the organic compound, a compound having a county, a functional element, or an anhydride dioxime as a substituent, an anthraquinone compound, an acid anhydride compound, a fullerene or the like can be suitably used. In addition to this, it is possible to use Japanese Patent Special Kaiping (2) 53, j Lite Kaiping 1M11463, Japanese Patent Special Kaiping 11251〇67, j Lite Open 20.^4 (), Japanese Patent Special opening _286〇54, this patent special opening (four) 5, Japanese patent special opening 75, this patent special opening 200M60493, Japanese patent special opening 2〇〇2 252〇85, this patent special opening 2002-56985, Japanese Patent Laid-Open No. 2〇〇3_157981, Japanese Patent Laid-Open No. 2003-217862, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The compound described in JP-A-2005-166637, and the like. Preferred among these are hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, cyanogen, dimethyl carbonitrile, tetrafluorotetracyanoquinone, dimethyl ketone, and p-flu0ranil. Tetra-p-benzoquinone (p_chl〇ranii), tetrabromo-p-benzoquinone 32 201132229 (P-bn^nil), p-benzene, 2,6_di-p-benzoquinone, 2,5-dichlorobenzene, 1 , 2,4,5-tetracyanobenzene, [,4_dicyanotetrafluorobenzene, 2,3-dichloro-5,6-diaminobenzoquinone, p-dinitrobenzene, methylene Stupid, adjacent two-stone Schottky Benzene, M_Cai Brew, 2,3-D-Naphthalene Boat, Dinitronaphthalene, Dinitronaphthalene, 9 Nasal Onion, 1,3,6,8-Tetranitro (IV), 2, 4, 7_ three cranes (four), 2, 3, 5, 6_ four nitrogen based bites, or rich _ C6G, more preferably hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, Tetracyano-p-dioxane, tetrafluorotetracyano-p-dioxane, tetrafluoro-p-benzene, four-gas-to-benzene, four-diy, 2,6-di-p-benzoquinone, 25-di, benzene Stuffed, 2'3·dichloronaphthalene, • tetracyanobenzene, &amp; dichlorinated benzene, or 2,3,5,6-tetracyano, especially tetrafluorotetrazide Stir-fry. These electron accepting dopants may be used singly or in combination of two or more. The amount of the electron-accepting dopant used varies depending on the type of the material, and is preferably G Q1 wt% to 5 Qwt%, more preferably 0.05 wt% to 2 wt%, relative to the hole transport layer material. The most good one is 〇"wt%~1〇wt%. The thickness of the hole injection layer and the hole transport layer is preferably 500 nm or less from the viewpoint of lowering the driving voltage. The thickness of the hole transport layer is preferably from 1 nm to 500 nm, more preferably from 5 nm to 200 nm, and even more preferably from 1 〇 nm to 1 〇〇 nm. Moreover, the hole/main entrance layer is preferably 〇1 nm to 2 〇〇 nm, more preferably 〇5 nm 〜10 〇 nm, and more preferably 1 nm to 100 nm. Hole injection layer The hole transport layer may be a single layer structure composed of one or more of the above materials, or a multilayer structure composed of a plurality of layers of the same composition or different types. 33 201132229 (Electron injection layer, electron transport layer) The two-input layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transmitting them to the anode side. Preferably, at least one of the layers adjacent to the luminescent layer is a sub-transport layer. Further, it is preferable to form an electron transport layer by a liquid containing two or more kinds of electron transport materials. By mixing two or more kinds of compounds, it is possible to provide a coating type electron injecting layer which is excellent in electron injectability from a cathode and excellent in electron injectability into a light emitting layer. The difference in electron affinity between the two or more types of electron transport (4) is preferably 〇.1~above 6.6^乂', and more preferably 〇2~above〇5~5. Specifically, a layer containing a compound such as a pyridine derivative, a ruthenium derivative, a caffeine derivative, a bisazine derivative, a diazaxan derivative, a phenanthroline derivative, a triazine derivative, or the like is preferable. a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a ketone derivative, a quinodimethane derivative, an anthrone derivative, a biphenyl hydrazine derivative, a thiofuran derivative, a metal complex of a carbodiimide derivative, a decylene methane derivative, a stilbene pyrazine derivative, a naphthyl, anthracene, etc., an aromatic ring of a tetramine acid, a phthalocyanine derivative, and a hydroxyquinoline derivative Or an organic decane derivative represented by a metal complex represented by a metal phthalocyanine, a metal complex represented by benzoxazole or benzothiazole, and a silole, etc. The electron injecting layer or the electron transporting layer of the organic EL element may contain an electron-donating dopant. As an electron-donating dopant introduced into the electron-injecting layer, the electron-donating dopant may have an electron-donating organic compound. The nature of the reduction can be 'suitable Using a metal such as Li, 34 201132229 —, —, —, ν_ΤΜΑΧ g # alkaline earth metal, a transition metal containing a rare earth metal, a reducing organic compound, etc. As the metal, particularly suitable (4) a metal having a work function of 4 2 ev or less 'Specifically, Li, Na, K, Be, Mg, Ca, =, 丫, (, (: 5 七, ^, (} (1 and %, etc.), and examples of the reducing organic compound include Ut compound, sulfur-containing compound, compound-containing compound, etc. In addition, Japanese Patent Laid-Open No. Hei 6-212153, Japanese Patent Laid-Open No. 2000-196140, Japanese Patent Laid-Open No. Hei No. Hei. The materials described in Japanese Patent Laid-Open No. Hei 2-342614, etc. The electron-donating dopants may be used singly or in combination of two or more. The amount of electron-donating dopants used is due to materials. Depending on the type of material, it is preferably from 1 wt% to 99 wt%, more preferably from 1.0 wt% to 80 wt%, particularly preferably from 2 〇 wt% to 7 〇%%. From the viewpoint of lowering the driving voltage, it is preferred that the electron injection layer, electron transfer The thickness of the layer is respectively below 500 nm. The thickness of the electron transport layer is preferably 1 nm to lake nm, more preferably 200 nm, and even more preferably 1 〇 nm to 1 〇〇. The thickness is preferably 0.1 nm to 200 nm, more preferably 0.2 to 100 nm, and even more preferably 0.5 to 50 nm. The V human layer and the electron transport layer may be one or two of the above materials. The single-layer structure formed by the treatment may also be a layer structure composed of a plurality of layers composed of the same composition or different species. (Break barrier layer) The electric/coherent barrier layer has a function of preventing transmission from the anode side to the light emission. Layer hole 35 201132229 Layer through the function of the cathode side. In the present invention, a hole blocking layer may be provided as an organic compound layer adjacent to the light-emitting layer on the cathode side. Examples of the compound constituting the hole-blocking layer include bis(2-fluorenyl) phenyl group (seeking salt) chain-specific complex, tris-salt derivative, 2,9-dimethyl--4 a phenanthroline derivative such as 7-diphenyl-l,l-morphine or the like. The thickness of the hole resistance layer is preferably 1 nm to 500 nm, more preferably 5 to 200 legs, and more preferably 1 to 11111 to 1 gland. The hole blocking layer may be a single layer structure composed of one or more of the above materials, or a multilayer structure composed of a plurality of layers of the same composition or different types. (Electron barrier layer) The electron blocking layer is a layer having a function of preventing electrons transmitted from the cathode side to the light-emitting layer from passing through the anode side. In the present invention, an electron-resistant layer may be provided as an organic compound layer adjacent to the light-emitting layer. As an example of the compound constituting the electron blocking layer, for example, the compounds exemplified above as the hole transporting material can be applied. The thickness of the electron blocking layer is preferably from 1 nm to 500 nm, more preferably m 2 〇〇 nm, still more preferably from 10 〜 nm to l 〇〇 nm. The barrier layer may be composed of one or more of the above materials: 曰, , . The structure ' can also be a multilayer structure composed of the same or different groups. (Purification of the material) The material of the organic layer of the pure organic light-emitting element is preferably a material used. More preferably, at least one of the above-mentioned materials is made by a zone melting method. If the material of the membrane method is purified, there is a case where the performance of the element is lowered.曰 by sublimation for the present use: the combination of the purification method and the wet film forming method of the domain slewing method, the combination of the effect and the effect can be achieved, and the durability = H is at least one m material is achieved by the band An organic electroluminescent device produced by wet film deposition/fabrication. , the soil is sprayed) layered; the material can be formed by the domain melting method purification purification temperature compared to the material = in the band process temperature is usually closer to the band melting lower. The material which is well coated and purified by the zone melting method is used. If the film is equipped with mm, the luminous efficiency of the organic electroluminescent device is improved, and the material: = 2 is preferably in the range of 1 〇〇 t to 400 ° c. Further, the host material, the charge transporting material, the host material, and the j material are more preferably a π-caloric derivative, an arylamine derivative or a metal complex. (Protective layer) # 3!!: People can also protect the entire organic EL element by a protective layer. The material contained in the protective layer may be a material having a function of preventing substances such as moisture or oxygen from deteriorating into the element. Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, and Ti, Ni, such as MgO, Si0, Si〇2, Ai2〇3, Ge0, Ni〇, Ca〇, BaO, and Fe2〇3. Metal oxides such as y2〇3, Ti02, metal nitrides such as SiNx and siNx〇y, metal fluorides such as MgFz, LiF, AIF3, and CaF2, polyethylene, polypropylene, polymethyl methacrylate, and poly Amine, polyurea, polytetrafluoroethylene, polygas trifluoroethylene, polydifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and a single comprising at least one comonomer A copolymer obtained by copolymerizing a bulk mixture, a fluorine-containing copolymer having a cyclic structure in a copolymerization main chain, a water-absorbent substance having a water absorption ratio of 1% or more, a moisture-proof substance having a water absorption ratio of 0.1% or less, or the like. The method for forming a protective layer is not particularly limited, and examples thereof include a vacuum smear method, a weaving method, a reactive bismuth ore method, an MBE (molecular beam smear), a 3 = beam method, an ion plating method, and a money polymerization method. (High-frequency wave excitation-off plasma chemical vapor deposition method, laser chemical vapor deposition method, j-phase phase deposition method, gas chemical vapor deposition method, coating method, transfer method. (Sealing) Element S: ί ί ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ Phlegm, fluorination, chlorination, magnesium chloride, chloranil/smelly dance, desertification mites, molecular sieves, buddha, 38 201132229 i oxygen (four) and scaly mosquitoes, examples of enumerated money liquid heart sarcophagus Class, perfluorodecyl or chlorine-based solvents and polymers from (silleQne=/_4l_, 1 2 and free of use and use: by using cerium oxide, cerium oxide, cerium lanthanum, cerium oxyhydroxide, oxidizing button Hope + hi... 7 Resin, epoxy resin, 1 machine (4) or use acrylic resin to touch (4) ride the dense method.糸 (in, sealing agent) 八 f: The sealing adhesive used in the Ming has a function of preventing moisture or milk from infiltrating from the end. &lt;Material&gt; The material of the sealing adhesive can be used with the resin The same material as the sealing layer. Among them, a preferred 疋% oxygen-based adhesive is preferred from the viewpoint of moisture prevention, and among them, a photo-curing type thermosetting adhesive is preferred. It is also preferable to add a filler. The filler to be added to the sealant is preferably an inorganic material such as Si〇2, SiO (Oxidized Oxide), SiON (Nitrox Oxide) or siN (Nitrix). The viscosity of the sealant can be increased, the processing suitability can be improved, and the moisture resistance can be improved. <Formulation of Sealing Adhesive> - The polymer composition and the concentration sealing adhesive are not particularly limited, and the above can be used. Said adhesive. 39 201132229

For example, a photocurable epoxy-based adhesive can be exemplified by Nagase chemteX.

XNR5516 manufactured by Corporation. • Thickness The coating thickness of the sealing adhesive is preferably 丨μηη or more 丨mm to 1. If it is thinner, it becomes impossible to apply the sealing adhesive uniformly. Further, if it is thicker, the passage through which moisture penetrates becomes wider and is less preferable. &lt;Sealing Method&gt; In the present invention, any amount of the above-mentioned sealing adhesive can be applied by a dispenser or the like, and the second substrate is laminated and hardened after coating. And get the functional components. (Drive) The organic EL device of the present invention can emit light by applying a DC (which may optionally contain an alternating current component) voltage (usually 2 volts to b volts) or a direct current between the anode and the cathode. The driving method of the organic EL element of the present invention can be applied to Japanese Patent Laid-Open No. Hei 2-148687, Japanese Patent Laid-Open No. Hei. Japanese Patent Laid-Open No. 5_29, Japanese Patent Unexamined Patent No. 8-234685, Japanese Patent Laid-Open No. 8-241-47, Japanese Patent No. 278, US Patent No. 5828429, USA The driving method is described in each specification of the patent No. 6〇233〇8. The light-emitting element of the present invention can improve the light-emitting efficiency by various well-known ideas. In the case of f, it is possible to control the refractive index of the substrate, the IT layer and the organic layer by controlling the surface shape of the substrate (for example, forming a fine concavo-convex pattern), and control the emission efficiency of the light and the emission of the light on the anode side by controlling 201132229. The thickness of the top substrate, the ITO layer, and the organic layer increases the external quantum efficiency. The light-emitting element of the present invention may also be a self-luminous light source. The organic m in the present invention has a resonator structure by being superposed on a transparent substrate. For example, a multi-layered mirror surface, (10) a plurality of laminated films having different enthalpy ratios, two=two poles, and a _ plate, which are reflected in a shape thereof, and a mirror surface and a metal are reflected on other buildings on the plate. The turned or semi-transparent electrode and the metal electrode are respectively used as a reflecting plate (four) to suppress the (four) row of reflected material vibration. In order to form a resonant structure, the length of the optical path determined by the refraction of the core and the reflection (4) of the refractive index and thickness of each layer is calculated as the optimum value of the resonance wavelength of the chick. The formula is described in, for example, Japanese Laid-Open Patent Publication No. Hei 9-180883. The calculation formula in the case of the second aspect is described in, for example, Japanese Laid-Open Patent Publication No. 2004-127795. As a method of making the organic EL display a full-color type, for example, as described in "Monitoring Monthly", September 2000, pages 33 to 37, it is known that the primary colors of the colors are respectively emitted ( A three-color luminescence method in which an organic EL element of light corresponding to blue (B), green (G), and red (R) is disposed on a substrate; and white luminescence of an organic EL element for white luminescence is passed through a color filter The white method of the three primary colors; the blue light emission of the organic EL element for blue light is converted into red (R) 41 201132229 and the color conversion method of green (G) by the fluorescent pigment layer. Further, a plurality of organic EL elements of different luminescent colors obtained by the above method are used in combination, whereby a desired light source can be obtained. For example, a white light-emitting source in which blue and yellow light-emitting elements are combined, and a white light-emitting source in which blue, green, and red light-emitting elements are combined. (Application) The EL element and the manufacturing method of the present invention can be included in the display of a digital still camera, a mobile phone display, a personal digital assistant (PDA), a fine display device, an information display of a car, a television monitor (τν momtor) ) or in a wide range of general lighting areas. (Display device) Next, a display of an embodiment of the present invention will be described with reference to Fig. 2 . Fig. 2 is a cross-sectional view schematically showing an example of a display device according to an embodiment of the present invention. In the display of the present invention, the display of the present invention includes a transparent substrate (support substrate), an organic EL element 1 , an organic EL element 10 such as a sealing device 16 , and a sequential electrode on the substrate 2 , organic The layer u and the cathode (second electrode) 9 are replaced by a sealed container 16. Further, one of the electrodes 省略 is omitted, a separator, an insulating layer, and the like. Preferably, the layer 42 201132229 is composed of a brix adhesive. The display device 20 displays the light from the organic EL element 10 as a display surface on the side opposite to the anode 3 of the substrate 2. A illuminating device according to an embodiment of the present invention will be described with reference to Fig. 3. Fig. 3 is a cross-sectional view schematically showing an example of illumination according to an embodiment of the present invention. '&amp; illuminating device according to an embodiment of the present invention 40, as shown in Fig. 3, the organic EL element 1 and the light-scattering member 3A are included. More specifically, the substrate 2 of the organic EL τ 10 and the light-scattering member 3 〇 constitute the illuminating device 40. ^ 'Guangzheng If the firing element 30 can scatter light, there is no special The limitation is as shown in Fig. 3, which is a component of the microparticles 32. The transparent substrate 31 may, for example, be a glass substrate. The microparticles 32 may suitably be a transparent resin micro, a sub-glass substrate, and a transparent resin microparticle. A known glass substrate and transparent resin fine particles can be used. When the illumination device 4Q causes the light emitted from the organic EL element 1 to enter the light incident surface 3A of the light-scattering member, the light-scattering member 3 can be used. The incident light is scattered, and the scattered light is emitted as illumination light from the light exit surface 3〇B. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. The n-touch, the amount of material f and its ratio, operation are shown in the following examples. The present invention can be suitably modified as long as it does not deviate from the gist of the present invention. Therefore, the present invention is not limited to the following specific examples. (Modulation of coating liquid) 20 wt% of pre-decompression drying is added (2分子°cxl hour, ο ι atmospheric pressure) molecular sieve 4A/8x, placed for 1 hour. In a nitrogen-substituted glove box (with a dew point of _68 degrees, oxygen concentration of 10 ppm), nitrogen foaming was utilized. The deoxidation treatment is carried out by a filter (pore size: 0.2 μm, ρΤΙΈ membrane filter) to prepare a coating liquid. (Mapping machine) Nitrogen (purity of 99.9%, dew point of _4 (rc or less) as a supply source) It is connected to a sprayer installed in a glove box (with a dew point of _45. 〇, oxygen concentration 刈ppm) via a gas filter: SFB100-02 (product name of SMC Co., Ltd.) [Example 1] A glass substrate (manufactured by Geomatec Co., Ltd., surface resistance of 1 〇 mouth: size: 0.5 mm thick, 2.5 cm square) having a vaporized layer of indium tin oxide (abbreviated as ITO) was placed in a cleaning vessel in propanol After performing ultrasonic cleaning in the 'after 30 minutes of uv_ ozone treatment. On the transparent anode, the following layers were sequentially placed by a spray method. In addition, &lt;in the formation of the long layer, the carrier gas of the gas-melting victory is gamified as ^, and the carrier gas volume is set to 1 L/min. Moreover, the particle size of the Wei shot body is set to 1 μιη. (1) Hole transport layer (5Gnm): One of the following hole transport material 1 and hole transport material 2 (weight ratio · 5 〇 / 5 〇) by the 対 method _ 曱 溶液 solution (solid concentration: Lwt%), the obtained hole 201132229 was thick and became 50 rnn. After being applied to a transparent anode, it was vacuum dried at 7 Torr for 1 hour. Further, the material of the hole transporting material 1 and the hole transporting material 2 can be purified by sublimation purification. The difference between the free potential of the hole transporting material 1 and the hole transporting material 2

eV ° P (2) Luminescent layer (40 nm): by spraying, the ratio of %: 5 is 1 to contain the main material 1: CDBP and luminescent material 丨: Compound A in diphenylbenzene solution (solid concentration: 0.6 wt%), the thickness of the obtained light-emitting layer was 40 nm, and after coating on the hole transport layer, vacuum drying was performed at 100 C for 1 hour. Further, the host material and the luminescent material 1 were each purified by sublimation purification. (3) Electron transport layer (30 nm): The substrate was mounted in a vacuum evaporation apparatus without being exposed to the atmosphere. Further, BAlq was placed in a molybdenum electric resistance heating boat, installed in a vacuum unit, and the vacuum chamber was depressurized to 4 x 1 G.4 Pa. Thereafter, the boat was heated by electric current, and BAlq was vapor-deposited on the light-emitting layer at a vapor deposition rate of 0.2 nm/sec to form an electron transport layer having a film thickness of 30 nm. J4) Electron injection layer (1 nm): LiF was deposited on the electron transport layer by a vacuum deposition method so that the thickness of the obtained electron injecting layer became 1 nm. ^5) Cathode (100 nm): Aluminum (A1) was deposited on the electron injecting layer by a vacuum evaporation method so that the thickness of the obtained cathode became 1 〇〇 nm. The produced laminate was placed in a glove box replaced with argon gas, and 45 201132229 was sealed with a stainless steel sealed can and an ultraviolet curing adhesive (XNR 5516 manufactured by Nagase ChemteX Corporation), thereby producing Example 1 Organic EL element. [Example 2, Example 3, and Comparative Example 1 to Comparative Example 2] In Example 1, 'the weight ratio of the hole transporting material 1 and the hole transporting material 2 of the hole transporting layer was changed to the ratio described in Table 1, except The procedure similar to that of Example 1 was carried out, whereby the organic EL elements of Example 2, Example 3, and Comparative Example 1 to Comparative Example 2 were formed. [Comparative Example 3] The same procedure as in Example 1 was carried out except that the hole transport layer was replaced with the following hole transport layer in Example 1, whereby the organic EL device of Comparative Example 3 was formed. (1) Hole transport layer (50 rnn): The substrate was mounted in a vacuum evaporation apparatus without being exposed to the atmosphere. Further, in the molybdenum resistance heating wafer boat, the hole transporting material 1 and the hole transporting material 2 are placed. After depressurizing the vacuum chamber to 4×10 5 pa, the wafer boat is energized and heated, and the crucible plating speed is adjusted so that the weight ratio of the hole transporting material 1 to the hole transporting material 2 becomes 50:50, and vapor deposition is performed. On the substrate, a hole transport layer having a film thickness of 5 〇 nm was formed. [Comparative Example 4] The same procedure as in Example 进行 was carried out except that the hole transport layer was replaced with the following hole transport layer in Example 1, whereby the organic EL device of Comparative Example 4 was formed. (1) Hole transport layer (50 nm): by spin coating, the following electricity 46 201132229 --- hole transport material 1 and hole transport material 2 (weight ratio: 50/50) dioxane The solution (solid content concentration: 1 wt%) was applied to a transparent anode in such a manner that the thickness of the obtained hole transport layer became 50 nm, followed by vacuum drying at 70 ° C for 1 hour. Further, the hole transporting material 1 and the hole transporting material 2 are materials which have been purified by sublimation purification. [Chemical 1]

Q

〇

δ hole transport material 2 (I ρ = 5. 8 Θ V) hole transport material 1 (I p = 5. 4 β V) f\ BAIq

CDBP

Compound A (Evaluation of Organic EL Element) The obtained organic EL element of the examples and the comparative examples were evaluated by the following evaluation criteria. The evaluation results are shown in Table 1. 47 201132229 ---- &lt;Luminous efficiency&gt; The organic EL element produced by the source is made of a 24 〇〇 type manufactured by KEITHLEY, and a DC voltage is applied to the light-emitting element so that it is 1 υυυ cd/in2 by the SR3 , , ^ illuminate with redundancy. Using the brightness meter manufactured by TOPCON, the emission spectrum and amount of light are determined, and the external 4 sub-efficiency is calculated based on the emission spectrum, the amount of light, and the current measured. &lt;Drive voltage&gt; Feng Dan pair = fabricated organic EL device, using the electric H test sheet &amp; 2_type manufactured by KEITHLEY to apply a DC voltage to the S element, and evaluate the voltage of the illuminating IGOOed/m2 as the driving voltage . &lt;Durability&gt;, /§ θ For the produced organic EL device, a DC voltage was applied to the light-emitting device using the manufactured electric=measurement unit 24G0 type, and the initial light was turned on, and, I000&gt;cd/m The continuous driving test was carried out under the conditions. The luminance is halved = time (the time when the luminance becomes 5GG ed/m2) is obtained as the endurance time. The value of the comparative example 1 is referred to as W, and the relative value is described. 48 201132229 [Table i] Table 1 Hole transport material 1 Concentration (wt%) Hole transport material 2 Concentration (wt%) External quantum efficiency (%) Drive voltage (V) Luminance halving time Example 1 50 50 15.3 7.3 1.6 Example 2 30 70 Spray 14.8 8.0 1.4 Example 3 70 30 13.1 8.1 1.5 Comparative Example 1 100 0 Spray ^S' 5.7 9.6 1.0 Comparative Example 2 0 100 Spray ^S 9.8 9.5 0.67 Comparative Example 3 50 50 a 10.2 8.8 1.1 Comparative Example 4 50 50 You - stolon 10.2 9.5 1.0 [Example 4 to Example 6 and Comparative Example s ~ Comparative Example 6] In Example 1, the hole transport material was replaced with the hole transport material 3 described in Table 2 and The hole transporting material 4 was converted to the ratio of Table 2, except that the same steps as in Example 进行 were carried out, thereby forming Examples 4 to 6 with phase = minute === half time, and the value of Comparative Example 5 was set. w [Comparative Example 7] In Comparative Example 3, the hole transporting material was replaced with the hole transporting material 3 and the hole transporting material 4, and the same procedure as in Example 3 of Example 3 was carried out, thereby forming Comparative Example 7. ^Bu conduct and compare <organic EL elements. 49 201132229 [Comparative Example 8] The same procedure as in Comparative Example 4 was carried out except that the material of the hole was replaced with the material TM and the hole transporting material 4, thereby forming the organic EL of Comparative Example 8. element. [Chemical 2]

Hole transmission material 3 (lp=5.4eV)

Hole transport material 4 〇P=5. 7eV) [Table 2] Table 2 Cavity transport material 3 Concentration (wt%) Hole transport material 4 Concentration (wt%) Film-forming method External quantum efficiency (°/〇) Drive Voltage (V) Luminance halving time Example 4 50 50 Spraying 13.2 6.8 2.3 Example 5 30 70 Spraying 12.9 7.2 2.2 Example 6 70 30 Spraying 12.7 7.3 2.1 Comparative Example 5 100 0 Spraying 6.3 8.8 1.0 Comparative Example 6 0 100 Spraying 8.7 9.0 0.9 Comparative Example 7 50 50 Evaporation 9.8 7.0 1.7 Comparative Example 8 50 50 Spin coating 9.5 9.4 1.2 [Example 7] In Example 1, the hole transport material 1 and the hole transport material 2 were replaced with the following The hole transporting material 1 and the hole transporting material 5 were subjected to the same steps as in the example 1 in 201132229, whereby the organic EL element of Example 7 was formed. The difference between the free potential of the hole transporting material 1 and the hole transporting material 5: ΛΙρ is 0.2 eV. [Chemical 3]

Hole transport material 1 (lp = 5.4 eV) Hole transport material 5 (lp = 5.6 eV) [Example 8] In Example 1, the hole transport material 1 and the hole transport material 2 were replaced with the following holes The same procedure as in Example 1 was carried out except that the material 1 and the hole transporting material 6 were transported, whereby the organic EL element of Example 8 was formed. The difference between the free potential of the hole transporting material 1 and the hole transporting material 6 is ΛΙρ is 0.1 eV. [Chemical 4]

Hole transport material 1 (lp = 5. 4 eV) Hole transport material 6 (lp = 5. 5 eV) 51 201132229 [Example 9] In Example 1, the hole transport material 1 and the hole transport material 2 were replaced with the next The hole transporting material 1 and the hole transporting material 7 were described, except that the same procedure as in Example 1 was carried out, whereby the organic EL element of Example 9 was formed. The free potential of the hole transporting material 1 and the hole transporting material 7 was 0.6 eV. Further, regarding the luminance halving time (Example 7 to Example 9), the value of Comparative Example 1 was set to 1.0, and the relative values were separately described. [Chemical 5]

Hole transmission material 1 (lp=5.4eV)

Hole transport material 7 dp=6. OeV) [Table 3] Table 3 — Real 丨7 Hole Transfer # Feed 1 Concentration (Wt%) cr» Material 5~7 Degree of Acceptance (wt%) Film Formation Rate ( %) (V) Luminance halving time jU 50-- --- 50 Spray 122 8.2 1.4 ----- JU Spray 6.8 ' 9.0 1 〇 Spray _ 7.0 IZ ΰ [Comparative Example 9] 52 201132229 In the first embodiment, the hole transporting material 1 and the hole transporting material 2 of the hole transporting layer are replaced by the following hole transporting material 1 and the hole transporting material 8 (PTPDES2: manufactured by CHEMIPRO KASEI KAISHA, LTD., weight average molecular weight: 15,000) In the same manner as in Example 1, except that the organic EL device of Comparative Example 9 was formed. The difference between the free potential of the hole transporting material 1 and the hole transporting material 8 is: Αίρ is 〇丨ev. Further, regarding the luminance halving time, the value of Comparative Example 1 is set to 1·〇 ’, and the relative values are described separately. [Chemical 6]

Hole transmission material 1 (lp=5.4eV) Electric wheel material {, P=5.3eV) 8 [Table 4] Table 4 Hole transport material 1 Concentration (wt%) Hole transport material 8 Concentration (wt0/〇) Membrane method efficiency (%) Driving voltage (V) Time comparison example 9 50 1 50 Spraying --- 8.8 0.9 —---- [Comparative Example 10] 53 201132229 In Example 1, 'the hole in the hole transport layer The transport material 1 and the hole transport material 2 are replaced by the following hole transport material 2 and hole transport material 8 (PTPDES2: manufactured by CHEMIPRO KASEI KAISHA, LTD., weight average molecular weight: 15, 〇〇〇), in addition to The same procedure as in Example 1 was carried out, whereby the organic EL device of Comparative Example 1 was formed. The difference between the free potential of the hole transporting material 2 and the hole transporting material 8 is Αίρ of 0.5 eV. Further, regarding the luminance halving time, the value of Comparative Example 1 was set to 1.0, and the relative values were separately described. [Chemistry 7]

Hole transport material 2 (lp=5.8eV) Hole transport material 8 (lp=5.3eV) [Table 5] Table 5 Hole transport material 2 Concentration (wt°/〇) '50 Hole transfer swallow ip 0 system Membrane external quantum driving voltage brightness reduction concentration (wt%) 50-~ efficiency (%) (V) half time ^2 8.5 0.6 [example ίο] 54 201132229 In the example 1, the hole transmission layer, the luminescent layer And the electronic transmission sound is replaced by the following hole transport layer, light-emitting layer and electron transport layer, and the same steps as in the example i are performed, thereby forming an organic one of the examples. The electron affinity ΔEa of the electron transporting material 1 and the electron transporting material 2 was 0.4 eV. "The difference between the forces. (1) Hole transport layer (50 nm): pED〇Tpss solution by spray method ((polyethylene dioxybenzophene poly(p-phenylene ether) acid doping company μ·, y liquid (solid content concentration: 1 wt%) of weight average molecular weight 4 100 000)) was applied to a transparent anode in an amount of 50 run of the obtained hole transport layer, and then at 15 Torr = 5 hours Vacuum drying (2) Light-emitting layer (40 nm): by the spray method, the weight ratio of the following body 2 and the luminescent material 2 (solid concentration: lwt%) The thickness of the obtained light-emitting layer was applied to the hole transport layer in an amount of 4 〇 nm, and dried at 10 (TC) for 1 hour. Further, the body 2 and the luminescent material 2 were respectively used by sublimation. =^ The purified material was obtained. (3) Electron transport layer (3 〇 nm): Toluene solution containing electron transport material 1 and electron transport material 2 in a weight ratio of 5 〇:5 藉 by a spray method (solid content concentration: 1 wt%) was applied to the light-emitting layer by the thickness of the obtained electron-transporting layer being 30 nm, and then carried out at 1 〇〇t Vacuum drying was performed for 1 hour. Further, the electron transporting material 丨 and the electron transporting material 2 were respectively purified by sublimation purification. [Example 11, Example 12, and Comparative Example 11 to Comparative Example 12] 55 201132229 In Example 10, the weight ratio of the electron transporting material 1 and the electron transporting material 2 of the electron transporting layer was replaced with the ratio described in Table 6, except that the same steps as in Example 10 were carried out, thereby forming Example 11 and Example 12. And the organic EL device of Comparative Example 11 to Comparative Example 12. [Comparative Example 13] In Example 10, the electron transport layer was replaced with the following electron transport layer, and the same procedure as in Example 10 was carried out, thereby forming The organic EL device of Comparative Example 13. (3) Electron transport layer (30 nm): The substrate was mounted in a vacuum evaporation apparatus without being exposed to the atmosphere, and electron transport was separately provided in a molybdenum resistance heating boat. The material 1 and the electron transporting material 2. After the vacuum chamber is depressurized to 4x1 〇·5 pa, the wafer boat is energized and heated, and the vapor deposition rate is adjusted so that the weight ratio of the electron transporting material 1 to the electron transporting material 2 becomes 50:50, vapor-deposited on the substrate to form an electron transport layer having a film thickness of 3 Å. [Comparative Example 14] In Example 10, the electron transport layer was replaced with the following electron transport layer, and The same procedure as in Example 10 was carried out, thereby forming an organic EL element of ratio j 14. (3) Electron transport layer (50 nm): Transfer material 1 and electron transport material 2 by spin coating (weight ratio = 5 〇 / 5〇) A = (solid content concentration: 1 wt%), applied to the luminescence with the obtained hole transport layer, = 30 nm, and dried under vacuum at 1 Torr. In addition, the electron transporting material and the sub-wheel material 2 are used to purify the material by sublimation purification. Further, regarding the luminance halving time, the relative comparison was performed based on the value of Comparative Example 11. [化8]

57 201132229 [Table 6] Table 6 Electron transport material 1 Concentration (Wt%) Electron transport material 2 Concentration (wt%) Film-forming method External quantum efficiency (%) Driving voltage (v) Luminance halving time Example 10 50 50 Spraying 13.8 5.4 1.7 Example 11 30 70 Spraying 13.6 5.7 1.6 Example 12 70 30 Spraying 13.2 5.4 1.5 Comparative Example 11 100 0 Spraying 11.0 6.0 1.0 Comparative Example 12 0 100 Spraying 10.4 5.7 0.54 Comparative Example 13 50 50 Evaporating 12.7 6.1 1.3 Comparative Example 14 50 50 Spin coating 8.4 10.7 0.43 [Example 13] In Example 10, the electron transporting material 1 and the electron transporting material 2 of the electron transporting layer were replaced with the electron transporting material 2 and the electron transporting material of the electron transporting layer described below. 3. The same procedure as in Example 10 was carried out, except that the organic EL element of Example 13 was formed. The difference in electron affinity between the electron transporting material 2 and the electron transporting material 3: AEa is 0.2 eV. [Chemistry 9]

Electron transport material 2 (Ea=2.9 nV) Electron transport material 3 (Ea=3.1eV) 58 201132229 &quot;'' 'r-- [Example 14] In Example 10, the electron transport layer of the electron transport layer 2 Replace with the electron-transporting material 3 of the electron transport layer described below, and perform the same method as the example 1G to form the instance 14 &amp; /:fe±A, 乂 ' '精精»»^ . The difference between the electron transfer material 1 and the electron #, Dou's electron affinity: AEa is 0.6 eV. Wheel [10]

Electron transport material ί (Ea=2.5eV) Electron transport material 3 (Ea=3.1eV) LX Example 15] Transfer material 2 replaced with ==: electronic transfer material 1 and electron transport material 4, € transfer material 3 and The electronic material 4 of the electronic pro-guangguang: pieces. The difference between the electron transport material 3 and the electron transport 卞 gauge and force: AEa is 0.1 ev. Further, regarding [Example 13 to Example Comparative Example 11 is a standard, a relative comparison is made. - minus + time" to [Chem. 11] 59 201132229

Electronic transfer material 3 (Ea=3.1eV)

(Ea=3.2eV) [Table 7] Table 7

[Comparative Example 15] In the case of N.0, the electron transporting material 1 and the electron=transporting material 2 of the electron transporting layer were replaced with the electron transporting material 3 of only the above electron transporting layer, except for the organic EL device of the step of the outer and the (4) 1G. [Comparative Example 16] In Example 10, the electron transporting material i and the electron transporting material 2 of the electron transporting layer were replaced with the electron transporting material 4 of only the above electron transporting layer, and the same procedure as in the example 1Q was carried out. Thus, the organic EL device of Comparative Example 16 was woven. In the case of the lapse of half the time, the comparison was made with respect to (Comparative Example 15 to 16) and Example 11 as the standard. [Table 8] Table 8 Electron concentration (wt%, film-forming method external quantum efficiency (0/0) driving voltage (v) brightness halving time comparison example 15 100 ~~~ Comparative Example 16 100 &quot; Spraying 9.7 7.2 0.89 One ----1 Spraying 9.5 7.5 0-92 [Example 16] (Thermal stability test) About the organic EL elements of Example 1, Example 2, and Example 3, and the organic EL elements of Comparative Example 2, respectively, in U ( The heat treatment for μ hours under rc was carried out, and the luminous efficiency of the δ flat mussel before and after it was driven and the electric house was driven. The gentleman's fruit is shown in Table 9. [Table 9] Table 9 Concentration of the hole transport material 1 (Wt°/〇 ) Hole transport material 2 Concentration (wt%) Film heat treatment External heat efficiency (%) Drive voltage (ν) Example 1 50 50 Spray no 15.3 7.3 14.8 ~~~ 7.5 Example 2 30 70 Spray no 14^8 '~~ 8.0 14.3 8.2 Example 3 70 30 Spraying no '. ------ 13.1 8.1 Ipo '~~~ 8.4 Comparative example 1 100 0 *Coating 5.7 9.6 23~~~ 14.7 Comparative example 2 0 100 Spraying k 9^8 9.5 ϋ8 '~~~ 13.8 61 201132229 For the 歹I~ Example 3 2EL 混合 混合 mixed with a hole transmission material thick 1 such as hole transmission material 2, because Even in iurCT = the material 枓 1 and the electric efficiency and the driving voltage are less changed. The other ~ ..., the processing. The components of the quantum example 2 are separately used for the hole transfer case 1. Compare 2 'by Some of the higher temperatures of Tg are: = the quantum efficiency of the transfer material and the driving voltage are greatly degraded. (Ts &amp; processing, so that the external ^, Tg (hole transport material 2): 9 ^) (the hole transmission material is small [Example 201] (purification by the zone melting method) = Pyrex (registered trademark) compound 2 GM having a diameter of 10 mm, finely rotated ^ _ empty sealed |

Then, the purification was carried out by a descending band stimuli method with a shift of 1 cm/min and a melting band of 4 em. The obtained compound was taken up in an inert atmosphere and stored under light-shielding and heterogeneous environments. Compound 2〇12 was purified by band melting in the same manner. 62 201132229 χ-- [Chem. 13]

Compound 20 1-2 : |p=5.5 eV (Preparation of hole transport layer coating liquid 201) 5 parts by weight of Compound 2 (^4, 5 parts by weight of Compound 2〇12) was dissolved in 990 parts by weight of the electronics industry Using dioxin (manufactured by Kanto Chemical Co., Ltd.) to modulate the hole transport layer coating liquid 2〇1 (manufactured by organic EL element 201), it will be steamed at a thickness of 15 〇 nm on a glass substrate of 25 mm x 25 mm x 0.7 mm. The ITO was coated with a film as a transparent support substrate. The transparent support substrate was pasted and cleaned. The ITO glass substrate was spin-coated on 98 parts by weight of cyclohexanone to dissolve 2 parts by weight of PTPDES-2. The coating liquid (manufactured by CHEMIPRO KASEI KAISHA, LTD.) was dried to form a film injection layer (having a film thickness of about 40 nm). On the above, 'the hole transport layer coating liquid 2 〇 1 was used. A hole transport layer (film thickness of about 20 nm) was prepared from the sprayed film. The film was dried under vacuum at 120 ° C for 1 hour. Secondly, CBP was used as a vacuum evaporation method. The host material, Ir(ppy)3 is used as the luminescent material, and the weight ratio thereof is 95:5 and 63 201132229 film-forming luminescent layer. On the other hand, BAlq was evaporated to 40 nm by vacuum evaporation as an electron injecting layer, and then lithium was irradiated with i nm, and 70 nm of metal aluminum was further vapor-deposited as a cathode. The produced laminate was placed in a glove box which was replaced with argon gas, and sealed with a stainless steel sealed can and an ultraviolet curable adhesive (XNR 5516 HV, manufactured by Nagase-CIBA Ltd.).

, r (ppy) 3 [Comparative Example 201-1] (Preparation of hole transport layer coating liquid 201-1) 10 parts by weight of compound 201-1 and 990 parts by weight of terpene benzene for electronic industry (Kanto Chemical Co., Ltd.) Manufacturing) mixing, dissolving, and modulating the hole transporting liquid coating liquid 201-1. 64 201132229 (Production of Comparative Organic EL Element 201-1) The organic EL element 201-1 was produced in the same manner as in Example 201 except that the hole transport layer coating liquid was changed to 201-1. [Comparative Example 201-2] (Preparation of the hole transport layer coating liquid 201-2) 10 parts by weight of the compound 201-2 and 990 parts by weight of an industrial chemical terpene benzene (manufactured by Kanto Chemical Co., Ltd.) were mixed and dissolved. The hole transport layer coating liquid 201-2 is modulated. (Production of Comparative Organic EL Element 201-2) An organic EL element 201-2 was produced in the same manner as in Example 201 except that the hole transport layer coating liquid was changed to 201-2. [Component evaluation] For the obtained element, external quantum efficiency and component longevity (brightness halving time) were evaluated by the above evaluation criteria. Further, the evaluation results are shown in the following Table 10 as relative values when the value of Comparative Example 201-2 is 1.0. [Table 10] Table 10 &quot;-----. 眚You 1 201 -------- External quantum efficiency components fortune ~~ Comparative Example 201-1 ~~-- 1.5 1.5 uL&gt; ^ / χ,ϊ ΟΛ1 Λ ---- 08 ~ 1.2 Compared with the flat parent case ZUK 1.0 1.0, 4 by using the compound purified by the zone melting method, using two kinds of this hole-transport layer can improve the external Quantum efficiency and components 65 201132229 Durability. [Industrial Applicability] According to the present invention, a low molecular compound having two or more molecular weights of 15 Å or less is used, and a layer adjacent to the luminescent layer is formed by the method of the ruthenium, thereby providing thermal stability. An organic electroluminescent device that is excellent in luminous efficiency and durability, has a low driving voltage, and can reduce manufacturing costs. Further, by the present invention, a method for producing an organic electroluminescence device can be provided. The method for producing an organic f-excited device can be manufactured with low thermal efficiency, excellent luminous efficiency and durability, and low driving voltage at a low manufacturing cost. The organic electroluminescent device. Further, according to the present invention, a display device and an illumination device having the above-described organic electroluminescent device can be provided. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the sigh is subject to the definition of the scope of the patent application attached. This application was filed with the Intellectual Property Office of Japan on September 1, 2009: Benli Application No. 2009-202091 and application to Sakamoto Intellectual Property Office on the 29th of January, 2001. Japan's special office please (4) the priority of ^667, the content disclosed in the patent application is in the complete company manual. , mouth, one [simplified description]

Fig. 1 is a schematic view showing a layer of an organic EL device of the present invention. 4 J 66 201132229 Fig. 2 is a schematic view showing an example of a display device of the present invention. Fig. 3 is a schematic view showing an example of a lighting device of the present invention. [Main component symbol description] 2: Substrate 3: Anode 4: Hole injection layer 5: Hole transport layer 6: Light-emitting layer 7: Hole barrier layer 8: Electron transport layer 9: Cathode 10: Organic electroluminescence element ( Organic EL element 11 : Organic layer 12 : Protective layer 14 : Next layer 16 : Sealed container 20 : Light-emitting device 30 : Light-scattering member 30A : Light-incident surface 30B : Light-emitting surface 31 : Transparent substrate 32 : Fine particles 40 : Illuminating device 67

Claims (1)

201132229 VII. Patent application scope: 1. An organic electroluminescence device, which is a surface electroluminescent device with a light-emitting layer and at least a layer of a layer mixed with a light-emitting layer, characterized in that: The layer adjacent to the light-emitting layer of one layer is formed by a spray method using a liquid containing two or more kinds of low molecular weight compounds having a molecular weight of 1,500 or less. 2. The organic electroluminescent device according to claim 1, wherein the at least one layer adjacent to the light-emitting layer is a hole transport layer. 3. The organic light-emitting device according to the above-mentioned item, wherein the two or more low molecular compounds having a molecular weight of 1,500 or less are the first low molecular compound and the second low molecular compound. The compounding ratio of the two compounds is 20:80 to 8:2 重量 in a weight ratio. 4. The organic electroluminescent device according to the first or second aspect of the invention, wherein the two or more low molecular compounds having a molecular weight of 15 Å or less are two or more types of hole transporting materials. 5. The organic electroluminescent device according to claim 4, wherein a difference in free potential between the two or more types of hole transport materials is ο"eV or more and 0.6 eV or less. 6. The organic electroluminescent device according to claim 4, wherein the two or more hole transporting materials are aryl derivatives. Earth Milk 4: Optical element: For example, the layer adjacent to the light-emitting layer of the organic electro-active layer of the first or second aspect of the patent is an electron transport layer. 8. The organic electroluminescent device according to claim 7, wherein the sub-transport layer is formed by a liquid containing two or more kinds of electron transporting materials. 9. The organic electroluminescent device according to claim 8, wherein the difference in electron affinity between the two or more electron transporting materials is 0.1 eV or more and 0.6 eV or less. 10. A method of producing an organic electroluminescence device, which is a method for producing an organic electroluminescence device having a light-emitting phase and at least a layer adjacent to a light-emitting layer between a pair of electrodes, wherein: the at least one layer The layer adjacent to the light-emitting layer is formed by a spray method using a liquid containing two or more kinds of low molecular weight compounds having a molecular weight of 1,500 or less. The method of producing an organic electroluminescence device according to the first aspect of the invention, wherein the light-emitting layer and each layer of the layer adjacent to the light-emitting layer are formed by the spraying method. 69 201132229 12. A display device comprising the organic electroluminescent device according to claim 1 or 2. 13. A lighting device having an organic electroluminescent device as described in claim 1 or 2. 70