TW201241148A - Fabricating method of organic electroluminescent device - Google Patents

Abstract

A fabricating method of an organic electroluminescent device is provided. The organic electroluminescent device includes an organic layer having a light emitting layer between an anode and a cathode. The fabricating method of an organic electroluminescent device includes coating a coating solution formed by dissolving or dispersing a light emitting material and a main material represented by at least one of formula (1) and formula (2) in a solvent, and heating the coating solution in a temperature higher than the glass transformation temperature of the main material and the boiling point of the solvent to form the light emitting layer.

Description

201241148 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing an organic electroluminescent device. [Prior Art] The organic electroluminescent device has the advantages of self-luminous, high-speed response, etc., and is expected to be applied to the flat panel display H, especially since the organic film (hole transport layer) having a layered hole transporting property and electron transport property are reported. Since a two-layer type (layer-type) organic electroluminescence element of an organic thin film (electron transport layer) has been attracting attention as a large-area light-emitting element that emits light at a low voltage of 10 V or less. The laminated (4) Qiandian (4) optical component is based on the positive electrode/electrical transmission layer/light-emitting layer/electron transport layer/negative electrode. In order to achieve homogenization of the film in the organic electroluminescence device of the next day, for example, a method of using a dicarbazole derivative (CBp) as a host material and using toluene as a solvent in the glass of the light-emitting layer is proposed. The heat transfer of the back φ heat transfer method is carried out at a temperature T of 30 C to +30 C and not exceeding the decomposition temperature of the organic compound constituting the light-emitting layer (refer to Patent Document 1); the light-emitting ship layer is heated to constitute a work during drying. The boiling point of the organic f agent of the New Ink is above the glass transition temperature (Tg). (Refer to Patent Document 2:... These methods can achieve homogenization of the film, but the organic electroluminescence light produced by these methods is used. There is a problem that the element has a large rate of change since the start of the driving (fourth degree). In addition, in order to achieve long life, for example, the following method is proposed: the composition of the light-emitting layer of the m-form compound, the doping compound, and the solvent is 5 6 201241148 The host compound has a higher surface transfer temperature and a higher temperature than the solvo boiling point (see Patent Document 3). However, 'the organic galvanic method produced by this method There is a problem that the optical element has a large rate of change in luminance attenuation from the start of driving. (4) This is a method of manufacturing an organic electroluminescence element that is required to rapidly develop a small rate of change from 7C degree attenuation immediately after the start of driving. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. 〇〇9_164〇33 SUMMARY OF INVENTION An object of the present invention is to provide a method for producing an organic electroluminescence device having a small rate of change in luminance attenuation from the start of driving. The method for solving the above problems is as follows. That is, the method for producing an organic electroluminescence device includes an organic layer including a light-emitting layer between the anode and the cathode, and the method for producing the organic electroluminescence device is characterized in that: A coating material obtained by dissolving or dispersing a luminescent material and a host material represented by at least one of the following general formula (1) and the following general formula (2) in a solvent Solution, and at a higher ratio than the above glass transition temperature of the material body> Buddha valley point at a temperature of the heating agent is more noble, the light emitting layer is formed '[Formula 1] 201 241 148

In the above formula (1), R represents any one of a third butyl group, a third pentyl group, a tridecyl decyl group, a triphenyl fluorenyl group, and a phenyl group, and Ri~R23 Any one of a hydrogen atom, a third butyl group, a third pentyl group, a trimethyl sulfonyl group, a triphenyl decyl group, a phenyl group, a cyano group, and an alkyl group having 1 to 5 carbon atoms, respectively. 2]

In the above formula (2), R represents an arbitrary substituent. <2> The method for producing an organic electroluminescence device according to the above <1>, wherein the molecular weight of the luminescent material is 1,500 or less, and the molecular weight of the main material of the main body 8 201241148 is 5% or less. The method for producing an organic electric excitation device according to any one of the above (1) to (2), wherein the main material structure (1) to the structural formula (6) and the structural formula (11) represented by the above formula (1) a compound represented by any of them, [Chemical 3]

[Chemical 4]

Structural formula (2) [Chemical 5]

Structural formula (3) 201241148 [Chem. 6]

Structural formula (4) [Chem. 7]

[化8]

Structural formula (6) [Chem. 9] 201241148

CN

Structural formula (11). The method for producing an organic electroluminescence device according to any one of the above-mentioned items (2), wherein the host material represented by the above formula (2) is the following structural formula C and structural formula E. a compound represented by any of them, [Chemical 10]

The method for producing an organic electroluminescent device according to any one of the above aspects, wherein the solvent is selected from the group consisting of 2-butanone, diphenylbenzene, toluene, and 2-methyltetrahydrofuran. And at least one of the methyl isobutyl ketones. And the organic electro-excited structural formula (8) according to any one of the above aspects, wherein the luminescent material is the following structural formula (7) ), compound of,. Construction (1)) [Chem. 11] 11 201241148

Structural formula (7) [Chem. 12]

Structural formula (8) [Chem. 13]

Structural formula (12) [Chem. 14] 5 12 201241148

The method for producing an organic electric excitation device according to any one of the above items (1) to (4), wherein the heating temperature is higher than a glass transition temperature of the host material by 1 (TC or more, and a specific solvent [Effects of the Invention] According to the present invention, the above-described objects can be solved by solving the above-mentioned problems, and it is possible to provide an organic electroluminescent device having a small rate of change in luminance attenuation from the start of driving. The above and other objects, features, and advantages of the present invention will become more apparent <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; (Method for Producing Element) The method for producing an organic electroluminescence device of the present invention includes at least a step of forming a light-emitting layer, and further includes another step which is appropriately selected as necessary. <Light-emitting layer forming step> The light-emitting layer forming step It is a step of applying a coating liquid obtained by dissolving or dispersing a luminescent material and a host material in a solvent, and heating to form a luminescent layer. 1241148 "Light-emitting material" The above-mentioned light-emitting material is not particularly limited, and a compound having a molecular weight of 1,500 or less is preferably selected depending on the purpose. When the above-mentioned light-emitting material is a mixture containing a plurality of compounds, the molecular weight of the above-mentioned light-emitting material It means the molecular weight of the compound having the largest molecular weight. The above-mentioned luminescent material usually includes a complex compound containing a transition metal atom or a lanthanoid atom. The above transition metal atom is preferably ruthenium, rhodium or ruthenium (rhodium). Palladium), tungsten (tungsten), rhenium, osmium, iridium, platinum, etc. Among the transition metal atoms, 'preferably ruthenium, rhodium, platinum, more preferably ruthenium, The above lanthanoid atoms include, for example, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, and terbium. , dysprosium, holmium, erbium, thulium, ytterbium, lutecium, etc. these steel atoms 'It is preferred to describe, shop, and. The complex of the complex is exemplified by G. Wilkinson et al., Comprehensive Coordination Chemistry, published by Pergamon Press, 1987, H. Yersin, and by Springer-Verlag Company, 1987. "Photochemistry and Photophysics of Coordination Compounds", which was released in the year, and 201241148, which is described in "Organic Metal Chemistry - Basics and Applications -" issued by Sangwa House Co., Ltd. in 1982. The specific ligand is preferably a halogen ligand (preferably a gas coordination ligand), an aromatic carbocyclic ligand (for example, a cyclopentadienyl anion, a benzene anion, or a naphthalene). a naphthyl anion, etc., a nitrogen-containing heterocyclic ligand (eg, phenyl pyridine, benzoquinoline, quinolinol, bipyridyl) ), or phenanthroline, etc., diketone ligand (such as aCetylacet〇ne, etc.), carboxylic acid (carb〇xylicadd) with carbon monoxide ligand, ligand More preferably, A is a - position, an isonitrile ligand, a cyan (cyan), and more preferably a nitrogen-containing heterocyclic ligand. The t-complex can have a side metal atom in the compound.

[15] A position (e.g., an acetic acid ligand, etc.), an alcoholate (acoholato) ligand (e.g., a phen〇jate ligand, etc.), 15 201241148

[化 16] 5 16 201241148 I \J^J v/^/xx

[Π化] 17 201241148

The luminescent material containing ruthenium is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a compound represented by the following structural formula. [化 18] 201241148

[Chem. 19] 19 201241148

- Host material - The host material is not particularly limited as long as it is represented by at least one of the following general formula (1) and the following general formula (2), but preferably has a molecular weight of 1,500 or less. Compound. [Chem. 20]

Rie

In the above formula (1), R represents any one of a third butyl group, a third pentyl group, a triterpene group, a triphenyl group, and a phenyl group, and each represents Any one of a hydrogen atom, a third butyl group, a third pentyl group, a tridecyl decyl group, a triphenyl fluorenyl group, a phenyl group, a cyano group, and an alkyl group having 1 to 5 carbon atoms. [Chem. 21]

In the above formula (2), R represents an arbitrary substituent. The above R and the second limitation are appropriately selected depending on the purpose, and examples thereof include a methyl group and a base group. Soil The above-mentioned bulk material is a mixture of a plurality of compounds, in an amount. The molecular weight of the molecule of the compound having the largest molecular weight is exemplified by the compound represented by any one of the following structural formulae (1) to (19).偁飞(9) [化22] 21 201241148

^ L

[Chem. 23]

Structural formula (2) [Chem. 24]

Structural formula (3) [Chem. 25]

Structural formula (4) 22 8 201241148 [Chem. 26]

[化27]

Structural formula (6) [Chem. 28] 23 201241148 ^ r w ^ λ

Structural formula (13) [Chem. 29] 24 201241148

Structural formula (18)

The compound represented by the above formula (2) is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a compound represented by any one of the following structural formula C and structural formula E. [化 30] 25 201241148

The glass transition temperature Tg of the host material refers to the temperature at which the supercooled liquid is transferred to the glass state, and can be measured in the following manner. <Method for Measuring Glass Transition Temperature Tg> The temperature of the endothermic peak can be measured as the glass transition temperature Tg by differential thermal analysis (DTA). In the case where the host material is a mixture containing a plurality of compounds, the glass transition temperature Tg of the host material means a glass transition temperature Tg of the compound having the highest glass transition temperature Tg. -Solvent_ The solvent is not particularly limited and may be appropriately selected according to the purpose. Examples of the ketone solvent include 2-butanone and methyl isobutylketone, and examples of the aromatic solvent include Examples of xylene, toluene, cumene, and trimethylbenzene 'ether solvents include tetrahydrofumn and 2-methyltetrahydrofuran (2_ shame%). 1 tetrahydrofuran) and so on. These solvents can be used alone! Two or more kinds may be used in combination. Among these solvents, diphenylbenzene, toluene, 2-butanone, and methyl isobutyl ketone 8 26 201241148 are preferable in terms of easiness of film formation. Solvent===:=;=Solution_condition, the above-mentioned materials === points (the above main _, the above-mentioned illuminating is 〇 _ 会 百 百 、, = can be appropriately selected according to the purpose, than 'ί Γ〇 c wt 〇/o) ^20 wt% 5 5wt/° is particularly preferably O.iwt%~10wt%. When the total solid content (tact time) is long and = G.G()1 Wt%, there is a case where the time during which the coating is applied to the ??Λ +0/ _ is longer, and if it is super. There is a case where a clogging of the nozzle ink or the ejection is generated. The content of the other gate = upper body component is in the above-mentioned particularly good range, which is advantageous in terms of the beat time and the maintenance of the apparatus. There is no particular limitation on the iitb rate of the material and the main material. It can be appropriately selected according to the purpose. Preferably, it is i: 99~3〇: 7〇佳 is 2: 98~20: 80, especially good is 4: 96~15 : 75. When the ratio of the luminescent material to the host material is less than 丨: if it exceeds 99, there is a case where electroluminescence (EL) luminescence cannot be performed. If it exceeds 30: less than 7 〇, EL luminescence efficiency is lowered due to concentration extinction. Case. On the other hand, if the ratio of the above-mentioned luminescent material to the host material is within the above-mentioned particularly preferable range, it is advantageous in that the luminous efficiency is high. <<Coating>> The coating method is not limited to a coating liquid obtained by dissolving or dispersing the above-mentioned luminescent material and the above-mentioned host material in the above solvent, and is not limited to the 201241148. Tu Wei and Jet 2: = Select 'for example, spin coating, spray "heating" turn 2 1 ==; = 2, the glass of the material is appropriate and 7, preferably more than the main: two: degrees. On the upper side, when the temperature of the domain is higher than 45t, the main glass degree is the transition temperature of the glass material of the above-mentioned main material, which becomes random in the continuous driving direction of the organic light-emitting element: In the case of the above-mentioned dissolution, if the organic layer is left in the organic solvent, the durability of the organic electroluminescence element and the el emission efficiency may be different. In a preferred range, it is advantageous in that the amplitude of the decrease in luminance at the initial stage of the continuous driving test is small. In addition, in the case where the host material is a mixture containing a plurality of compounds, the above heating temperature must be higher than the glass transition 2 of each compound in the mixture, that is, the above heating temperature must be the highest glass in the glass transition temperature of the compound in the mixture. The transfer temperature is higher. In addition, in the case where the solvent is a mixed solvent containing a plurality of solvents, the heating temperature must be higher than the boiling point of each solvent in the mixed solvent, that is, the heating temperature must be higher than the highest Buddha in the solvent of the mixed solvent. The point is higher. The heating time during the heating is not particularly limited, and may be appropriately selected according to the purpose of 5 28 201241148. Preferably, it is 1 minute to 5 hours, more preferably 5 minutes to 1 hour, and particularly preferably 5 minutes to 3 minutes. When the heating time is less than i minutes, there is a residual solution in the light-emitting layer, and the EL light-emitting efficiency and the durability of the organic electroluminescent device are lowered, and the alignment of the main body cannot be changed 'and the initial brightness of the continuous driving test is generated'. When it exceeds 5 hours, peeling of a film|membrane by oxidation, etc. may arise. On the other hand, when the heating time is within the above-mentioned specificity, since the solvent does not remain, the orientation of the organic electroluminescent device is improved in the initial direction of the host material, and the decrease in the shell degree at the initial stage of the continuous driving test is small. The aspect is favorable. The number of times of the above heating is not particularly limited, and may be appropriately selected one or more times depending on the purpose. Further, in the case where the number of times of heating is S, the heating temperature and the heating time may be the same in each of the additions (the hole injection layer forming step). The f-hole injection layer forming step is a step of forming the hole injection layer. The method for forming the hole injection layer is not particularly limited, and examples thereof include a steam film method, a dry film forming method such as a shovel method, and a maximum coating method. Cloth method, transfer method, printing method, ink jet method, and the like. <Curtain Transport Layer Formation Step> The above-described hole transport (four) age is a step of forming the above-mentioned material transport layer. The method for forming the hole transport layer is not particularly limited, 29 201241148 -----X-- 'For example, a dry film forming method such as a steaming method, a stalk cloth method, a transfer method, a print, an ink jet method, or the like can be given. <Other Steps> The other steps are not particularly limited, and may be appropriately selected according to the purpose, and may include an electron transport layer forming step, an electron injecting layer forming step blocking layer forming step, an electron blocking layer forming step, and the like. <Organic Electroluminescent Device> The organic electroluminescent device includes an organic layer between a pair of electrodes (anode and cathode), and may further include other layers which are appropriately selected as necessary. The organic layer includes at least a light-emitting layer, and further includes an electric/co-rotating layer, an electron transporting layer, a hole blocking layer, an electron blocking layer, a hole injecting layer, an electron injecting layer, and the like, as needed. <<Light-emitting layer>> The light-emitting layer is a layer containing the above-mentioned light-emitting material and the above-mentioned host material, and has a function of obtaining a hole from an anode, an electric injection layer, or a hole transport layer when an electric field is applied, and The electrons are taken from the cathode 'electron, the main layer, or the electron transport layer, and the place where the hole and the electron are recombined is provided to emit light. The thickness of the light-emitting layer is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 2 nm to 500 nm. From the viewpoint of external quantum efficiency: more preferably 3 nm to 200 nm, particularly preferably 10 nm to 2 Å. Nm. Further, the light-emitting layer may be one layer or two or more layers, or each layer may emit light in a different light-emitting color. "Polar injection layer, hole transmission layer" 201241148

Extreme side. The hole injection layer and the electric component or the different hole transport layer may be a single layer structure or may be a multilayer structure including a plurality of layers of the same composition. - Hole injection material, hole transport material _ The hole injection material used in the hole injection layer and the hole transport layer, or the hole transport material may be a low molecular compound or a high molecular compound. The hole injecting material or the hole transporting material is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a pyrrole derivative, a carbazole derivative, and a triazole. a derivative, an oxazole derivative, a oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline a derivative, pyrazolone, a phenylenediamine derivative, an arylamine derivative, an amine-substituted chalc〇ne derivative, Styryl anthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine a compound, a styrylamine compound, an aromatic dimethylidyne compound, a phthalocyanine compound, a porphyrin compound, a thiophene derivative, an organic decane (silane) Yan , Carbon and the like. These compounds may be used alone or in combination of two or more. 31 201241148 It is possible to contain a dopant in the hole injection layer and the hole transport layer. The electron-accepting dopant may be an inorganic compound or an organic compound as long as it is electron-accepting and has a property of oxidizing an organic compound. The inorganic compound is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a vaporized metal such as gasified iron, gasification, gallium chloride, gasification, and pentachlorination; Turn the metal oxide and so on. The organic compound is not particularly limited, and may be, for example, a compound having a substituent such as a nitro group, a dentate, a nitrogen group or a trimethyl group as a substituent, and a quinine (quingne) complex or an anthraquinone system. Compound, flillerene, and the like. These electron accepting dopants may be used alone or in combination of two or more. The amount of the above-mentioned electron-accepting dopant varies depending on the surface of the material, and is preferably 0.01 wt% to 50 Wt% 'more preferably 0.05 wt% with respect to the hole transport layer material or the hole injecting material. 2 〇 wt%, particularly preferably 0.1 wt% to 10 wt%. ‘ The thickness of the hole injection layer and the hole transmission layer is preferably 1 (10) to 5 〇〇 nm', more preferably 5 nm to 2 〇〇 nm, and particularly preferably 1 〇 nm to rigid leg. <<Electron Transport Layer, Electron Injection Layer>> The electron injection layer and the electron transport layer are layers having a function of acquiring electrons from the cathode or the cathode side and transporting them to the anode side. The electron injecting layer and the electron transporting layer preferably contain a reducing doping 5 32 201241148 • J / V ^ UL / ll. The reducing dopant is not particularly limited and may be appropriately selected according to the purpose, preferably selected. Self-test metal, soil test metal, rare earth metal, oxide of gold test, metallization of metallurgy, oxide of soil test metal, halide of soil test metal, oxide of rare earth metal, oxide of rare earth metal, At least one of an organic complex of a metal, an organic complex of a soil-measuring metal, and an organic complex of soil is examined. The amount of the above-mentioned reducing dopant used varies depending on the kind of the material, and is preferably from 01 wt% to 99 wt%, more preferably 〇·3 wt%, with respect to the electron transport layer material or the electron injecting material. 8G wt%, particularly preferably 〇5 (4) The above electron transport layer and electron injection layer can be formed according to a known method, for example, vapor deposition method, wet film formation method, (molecular beam epitaxy, MBE) method, and town ion beam can be used. (6) 咏-beam method, molecular layering method, laser beam (LB) method, printing method, transfer method, etc. are suitably formed. The thickness of the above electron transporting layer is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 1 nm to 2 Å, more preferably i nm to 1 〇〇 nm, and particularly preferably 1 nm to 50 nm. The thickness of the electron injecting layer is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 1 nm to 200 nm, more preferably i nm to 1 〇〇 nm, and particularly preferably 1 nm to 50 nm. "Break barrier layer, electron blocking layer" The above-mentioned hole barrier layer 疋 has a function of preventing the transmission from the anode side to the light-emitting layer 33. The layer of the 201241148 hole passing through the cathode side is generally disposed adjacent to the cathode side of the light-emitting layer. Organic compound layer. The above 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, and is usually provided as an organic compound layer adjacent to the anode side of the light emitting layer. Examples of the compound constituting the above-mentioned hole barrier layer include bis(2-methyl-8-pyridylquinoline)_4·(phenyl-phenolate)·Ming (bis-(2-methyl.8-quinolinolato) -4-(phenyl-phenolate)-alumi nium (III) 'BAlq), such as a complex, a tris-salt derivative, a succinyl _4,7-linked oxazolidine-g (2, 9-dimethyl.4,7-diphenyM, l〇-phenanthroline &gt; BCP) Μ 琳 琳 衍生物 derivative. The above-described example is not particularly limited as a known hole blocking layer, and it can be formed by a dry method such as a vapor method or a lining method by a film method or a wet type. Formula, transfer method, printing, inkjet; cut and suitable 200 η layer: the thickness of the electron blocking layer is preferably "m ~ outside, the hole barrier layer and two:: ^ 3 nm ~ 10 nm. The other two or more single-layer structures are also one-layer or multi-layered multilayer structures of the above materials. Dry 3-same-composition or different composition "electrode" 8 34 201241148 = The organic electroluminescent device comprises a pair of electrodes. In terms of the properties of the above-mentioned organic electroluminescent device, it is preferred that the electrode is electrically charged. Generally, the function of the electrode of the organic layer to supply the hole to the electrode of the organic compound layer may be mixed. The shape, the structure, the size, and the like of the root-thickness are not particularly limited, and the material of the electrode can be formed from a known electrode material for the purpose and purpose of the article. For example, a genus of cerium oxide or a conductive compound is preferably used. Or _ material mix: etc. -Anode - 〃 The material constituting the above-mentioned anode is, for example, "antimony tin 0xide (AT〇), fluorine doped oxidation, (Fluorine-doped Tin ,, doped with a recording or gas, etc.) FT0)), tin oxide, zinc oxide, indium oxide, indium tin oxide (Indium Tin), conductive metal oxides such as silver, chromium, nickel, etc.; these metals and conductive metal oxides Mixtures or laminates; inorganic conductive materials such as copper telluride and copper sulfide; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; or laminates of these materials with ITO. Among these materials, a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high electrical conductivity, transparency, and the like. • Cathode - The material constituting the cathode may, for example, be Li, Na, κ, Cs, etc. 35 201241148 Metallurgical metals such as 'Mg, Ca, etc., gold, silver, gold, lithium-aluminum alloy, magnesium-silver alloy, Rare earth metals such as indium and antimony. σ:: One type is used singly. However, it is preferable to use two or more types in combination with stability and electron injectability S point. In the case of 芘 蜣 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料Shao and

Wt% of the metal or soil tester of the material. These materials are mixed (such as lithium aluminum alloy, magnesium-aluminum alloy, etc.). The method for forming the square electrode 3 is not particularly limited, 'a known vacuum can be used', a sputtering method, a wet method such as a printing method or a coating method, and a physical method such as a chemical method; Gas ^ * CVD) . cv;: In the case of the electrode material, it can be formed by using a method which is appropriately selected in consideration of the above-described electric λ, and can be formed by using the above-mentioned material as the anode. The case where the patterning is performed by the physical etching of * can be performed by using a laser or the like, or by using a laser or the like; It is disposed on the substrate, and the electrode may be disposed in direct contact with the substrate, or may be inserted in the form of an intermediate layer. The material of the above-mentioned substrate is not particularly limited, and may be appropriately selected depending on the purpose. For example, Yttrja stabilized Zirconia (YSZ), glass (alkali free glass, sodium soda glass, soda lime) Inorganic materials such as glass), polyethylene terephthalate, polybutylene phthalate, p〇lyethylene naphthalate, etc. Polyacetate; polystyrene, polycarbonate (polyether Sulf0ne), polyarylsulfonate, polyimide, polycyclic olefin (p〇lycycl〇〇lefm), An organic material such as norbornene (n〇rb〇mene) resin or poly(Chr〇r〇trifluoroethyiene). The above-mentioned base (tetra), structure, and size # are not limited, and may be appropriately selected depending on the use, purpose, and the like of the light-emitting element. Usually, the shape of the substrate is (4) plate shape. The base_negative scale structure, in addition, can be single-member (four) + then Η as a layer # ^ 幵 幵 成 into ' can also be more than two components ^. The substrate can be clearly defined, or it can be Dunming, in the case of _ _ # is colorless and transparent, and can also be colored and transparent. Brother, on the above substrate, barrier layer). A moisture-proof layer (a gas barrier layer (gas barrier layer) may be provided on the surface or the back surface thereof, for example, an inorganic material such as nitriding 37 201241148 矽 or cerium oxide. The moisture-proof layer (gas barrier layer) "Protective layer" The organic electroluminescent device is entirely protected by a protective layer. The material contained in the protective layer is not particularly limited as long as it has a function of inhibiting the deterioration of the component of the moisture-promoting element into the element. 'It can be appropriately selected according to the purpose, and examples thereof include: metals such as &amp;: Pb, Au, Cu, Ag, bismuth, Ti, Ni; MgO, Si〇, Si〇n2, A1203, GeO, NiO, CaO, Metal oxides such as Ba〇, Fe2〇3, γ2〇3, and Ti〇2, metal nitrides such as SiNx and SiNxOy; metal fluorides such as MgF2, LiF, A1F3, and CaFz; polyethylene, polypropylene, and polymethyl methacrylate a copolymer of dilute acid methyl ester, polyethylenimine, polyurea, polytetrafluoroethylene, polygas trifluoroethylene, polydifluoroethylene difluoroethylene, difluoroethylene difluoroethylene and diethylene difluoroethylene, a mixture of vinyl fluoride and a monomer comprising at least one comonomer a copolymer obtained by polymerization, a fluorinated 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 1% or less, etc. Formation of the above protective layer The method is not particularly limited and may be appropriately selected depending on the purpose. For example, a true method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, and an electric method may be mentioned. Slurry polymerization method (high-frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source cVD method, coating method, printing method, transfer method, etc. "Sealed container" 5 38 201241148 - / / opif The above-mentioned organic electroluminescent device can seal the entire device by using a sealed container. Further, a water absorbent or an inert liquid can be enclosed in the space between the above (10) H and the money-exciting optical element. It is not particularly limited, and may be appropriately selected depending on the purpose. For example, cerium oxide, sodium oxide, oxonium, oxidizing, sodium sulphate, sulfuric acid, magnesium sulfate, phosphorus pentoxide, chlorinated feed, gasification town, gas Copper Fluoride hammer, fluoridation, evolution, enthalpy, molecular sieve, zeolite, magnesia, etc. The above inert liquid is not particularly limited and may be appropriately selected according to the purpose 'for example, paraffin (paraffin) ) liquid paraffin; perfluorohydrogen (perflu〇r〇aikane), total ammonia (clear il-ne), whole _ (perflu_ther) and other gas-based solvents; gas system> cereals, oil-breaking (silicone oil), etc. "Resin sealing layer" The above organic electroluminescent device preferably suppresses deterioration of element properties caused by oxygen or moisture from the atmosphere by applying a two-sealing with a resin sealing layer. The resin material is not particularly limited, and examples thereof include an acrylic resin, a gas tree deer gas, a moon stagnation, a polyoxan resin, a rubber resin, and a vinegar resin. These 4 are particularly excellent in terms of the function of preventing the function. The above is preferably a thermosetting epoxy wax or a photocurable % oxygen resin. The method for producing the resin sealing layer is not particularly suitable, and may be appropriately selected according to the item No. 39 201241148, and examples thereof include a method of applying a resin solution, a method of pressure bonding, a thermocompression bonding resin, and a method of steaming. Method cage for carrying out polymerization such as mine or splashing. <<Sealing Adhesive>> The sealing adhesive used in the present invention has a function of preventing entry of moisture or oxygen from the end portion. The material of the above-mentioned sealing adhesive can be the same material as that used in the above-mentioned resin sealing layer. Among these materials, in terms of moisture prevention, an epoxy-based adhesive is preferred, and a photocurable adhesive or a thermosetting adhesive is also preferred. It is also preferred to add a filler to the above-mentioned sealing adhesive. . The filler is preferably made of, for example, Si〇2, Si0 (external oxidized Si(10) (nitrogen oxynitride), leg (nitrided sand), etc. by adding the filler, the viscosity of the sealing adhesive is increased, the processing suitability is improved, and the resistance is improved. The sealing agent may contain a desiccant. Examples of the desiccant include cerium oxide, calcium oxide, cerium oxide, etc. The amount of the desiccant added is preferably 0 01 wt% with respect to the sealing adhesive. %〜2〇wt%, more preferably 0.05 wt/G 15 wt%. If the above addition amount is less than 〇〇1 wt%, the effect of adding the dry agent becomes weak, and if it exceeds 2〇%, it is difficult to make The desiccant is uniformly dispersed in the sealing adhesive. In the present invention, any amount of the above-mentioned desiccant-filled sealing adhesive may be applied by a dispenser or the like, and the second substrate may be overlapped after coating. Fig. 1 shows an example of a layer structure of the organic electroluminescence device of the present invention. The semiconductor element (201241148) has an anode 2 (for example, a ΙΤ0 electrode) formed on the glass substrate 1 in this order. Hole injection layer 3, transport layer 4 The light emitting layer 5, an electron transport layer 61 sub-injection layer 7 (e.g., _ of the fluorine-containing layer), a cathode 8 (e.g. A1_Li electrode) formed layer. Further, the anode 2 (for example, the IT0 electrode) and the cathode δ (for example, the ai_u electrode are connected to each other via a power source. - Driving _ The above organic electroluminescent device can apply a direct current to the anode and the cathode (including an alternating current component as needed) The voltage (usually 2 volts to volts volts) or direct current is used to obtain light. The organic electroluminescent device can be applied to an active matrix by a thin film transistor (TFT). The layer can be applied to amorphous silic〇n, high temperature polycrystalline germanium (P〇lysiliC〇n), low temperature polycrystalline litmus, microcrystalline germanium (oxide semiconductor, organic semiconductor, carb〇n nanotube) For example, the above-mentioned organic electroluminescent device can be applied, for example, to a thin film transistor described in the pamphlet of International Publication No. 2005/088726, Japanese Patent Laid-Open No. Hei. No. 2006-165529, and the specification of the Japanese Patent Application Publication No. 2008/0237598 A1. The element is not particularly limited, and various known methods can be used to improve the light extraction efficiency, for example, by processing the surface shape of the substrate (for example, Forming a fine concavo-convex pattern), controlling the refractive index of the substrate, the IT0 layer, and the organic layer, controlling the thickness of the substrate, the ΙΤ0 layer, and the organic layer, thereby improving the light extraction efficiency of 201241148 and improving the external quantum efficiency. The light-receiving method may be a top-emitting (1Cm) method or a bottom emission method. The organic electroluminescent device may have a resonator structure, for example, overlapping on a transparent substrate and having a refractive index. A multilayer film mirror m semi-transparent electrode, a light-emitting layer, and a metal electrode having a plurality of laminated films having different rates. The light generated in the light-emitting layer is reflected by the multilayer mirror surface and the metal electrode as a reflector, and is resonated and resonated. Further, in a preferred embodiment, the transparent or semi-transparent electrode and the metal electrode function as a reflecting plate, and the light generated in the light-emitting layer is reflected and resonated in the reverse direction. To form a resonant structure, two blocks are formed. The effective refractive index of the reflector, the reflector, the fold of each layer, and the thickness of the silk of the mosquito are optimal for the desired The value of the oscillating wavelength is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Use - The use of the above organic electroluminescent device is not particularly limited and may be appropriately selected according to the purpose, and may be suitably used for display elements, displays, backlights, electronic photographs, illumination sources, recording light sources, exposure light sources, reading light sources, Marking, kanban, interior material, optical communication, etc. The display using the above organic electroluminescent element forms a full color display 42 8 201241148: Know the following methods: such as "Monthly Display" 2 colors - 5 colors (The baskets are described on pages f3 and 7). The two primary colors corresponding to the color (blue (B), green (6), and red organic EL elements are placed on the substrate, and the three-color light-emitting method is used. The white luminescence obtained by the excitation element is divided into three white colors by '(C〇1〇r filte〇); the blue luminescence obtained by using the organic electroluminescence 7G piece by the blue hair 1 Fluorescent dye layer is converted into red (R) and green color shift ⑹ like. Further, a plurality of organic electroluminescent elements having different luminescent colors obtained by the above method are used, and a flat-light source of a desired illuminating color is used. For example, it is possible to combine two kinds of colors: a self-color light having a blue and yellow light-emitting element, a white light source having a blue, green, and red light-emitting element. [Examples] Hereinafter, examples of the invention will be described, but the invention is not limited by the examples. 1 (Example 1) - Fabrication of Organic Electroluminescent Device _ A 0.7 mm thick, 25 mm square glass substrate was placed in a cleaning container, ultrasonically cleaned in 2-propanol, and UVV was performed for 3 minutes. Iet, UV) _ ozone treatment. Then, the following layers were formed on the glass substrate. Further, the vapor deposition rate in the following examples and comparative examples was 〇 2 nm/sec unless otherwise specified. The vapor deposition rate was measured using a crystal oscillator. In addition, the thickness of each layer below was measured using a stylus type wheel (XP-200' AMBiOS Technplogy, Inc.). 43

201241148 O/OJOpU In addition, the glass transition temperature Tg of each substance was measured by the following measurement method. <Method for Measuring Slope Transition Temperature Tg> Using a thermogravimetric differential measurement device (exstar TG/DTA6000, manufactured by Seiko Instruments Co., Ltd.), the glass transition temperature Tg was measured from the endothermic change. First, on the glass substrate, ITO (Indium Tin Oxide) was sputtered and evaporated to a thickness of 15 〇 nm as an anode. The resulting transparent support substrate is then etched and cleaned. Then, on the anode (ITO), spin coating to make the arylamine derivative (trade name: PTPDES-2, manufactured by Chemipro Kasei, Ding § = 205. (:) 2 parts by weight dissolved or dispersed in the electronics industry A coating liquid of 98 parts by weight of a ketone (manufactured by Kanto Chemical Co., Ltd.) was then dried for 30 minutes, and then annealed at i6 〇〇c for 1 minute to form a cavity injection having a thickness of about 40 nm. Next, a compound represented by the following structural formula (9) which is an arylamine derivative (Mw=8,000) is further used, and the above weight average molecular weight is a gel permeation chromatograph (GPC). 19 parts by weight of the compound represented by the following structural formula (1〇) is dissolved or dispersed in xylene (manufactured by Kanto Chemical Co., Ltd.) 2, 〇〇〇 weight, calculated in terms of standard polystyrene. The mixture was stirred for 1 hour to prepare a hole-transfer coating solution, and then the hole transport layer coating liquid was spin-coated on the hole injection layer, and then dried at 12 (TC for 30 minutes, then at 150). Annealing at °C for 1 minute A hole transport layer having a thickness of about 15 nm and a glass transition of 8 44 201241148 (Tg) = 160 ° C or more is formed. Further, the weight average molecular weight of the bell (9) is measured in the following manner, the main layer of the hole, The spin coating of the hole transport layer was carried out in a glove box (dew point oxygen concentration of 8 ppm).

η represents an arbitrary integer [化32]

Structural Formula (1 〇) Next, in the hole transfer potential, the following light-emitting layer coating liquid was spin-coated in a glove box, and dried at 125 ° C for 30 minutes to form a light-emitting layer having a thickness of 3 〇 nm. The light-emitting layer coating liquid is 9 parts by weight of a compound (Tg=ii5°c) represented by the following structural formula (1) as a host material, and a compound represented by the following structural formula (7) as a phosphorescent material. : (product 45 201241148: Ir(ppy) 3, manufactured by Chemipro Kasei Co., Ltd.) 1 part by weight, dissolved or dispersed in 990 parts by weight of 2-butanone (boiling point 79.5 ° C, manufactured by Kanto Chemical Co., Ltd.) for the electronics industry, and then A molecular sieve (trade name: molecular sieve 5A 1/16, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and it was prepared by filtering using a syringe filter having a pore size of 0.22 μm in a glove box. [化33]

Structural formula (1) [Chem. 34]

Structural Formula (7) Next, BAlq (bis-(2-methyl-8-quinolinolato)-4-(phenyl-phenolate)-alumi nium-(III)) is deposited on the light-emitting layer by vacuum evaporation to form An electron transport layer having a thickness of 40 nm. Next, lithium fluoride (LiF) was deposited on the electron transport layer to form an electron injecting layer having a thickness of 1 nm. Then, metal aluminum was vapor-deposited on the electron injecting layer to form a cathode having a thickness of 70 nm 8 46 201241148 〒f. The produced laminate was placed in an argon-substituted glove box, and sealed with a stainless steel sealed can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Further, the synthesis scheme of the compound represented by the above structural formula (1) is as follows. <Synthesis flow of the compound represented by the structural formula (1)> [Chem. 35]

(Comparative Example 1A) In Example 1, a light-emitting layer coating liquid was spin-coated in a glove box, and dried at 85 ° C for 30 minutes to form a light-emitting layer instead of spin coating a light-emitting layer in a glove box. The cloth liquid was dried at 125 for 3 minutes to form a light-emitting layer, and in addition, the electro-optical element was excited in the same manner as in Example 掣.乂 (Comparative Example 1B) 201241148 In Example 1, the luminescent layer coating liquid was spin-coated in a glove box at 100 C for 30 minutes to form a luminescent layer instead of spin coating the luminescent layer in a glove box. An organic electroluminescent device was produced in the same manner as in Example 1 except that the coating liquid was dried at 125 ° C for 30 minutes to form a light-emitting layer. (Example 2) In the example 1, when the light-emitting layer was formed, the compound represented by the following structural formula (8) was used as a photoluminescent material, and the electron industry was used as a light-emitting material (boiling point: 144 ° C, manufactured by Kanto Chemical Co., Ltd.). And a mixed solvent of dehydration (boiling point ll 〇 ° C, manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, dried at 125 ° C for 3 ' minutes and further annealed at 15 ° C ° 1 Instead of using the compound represented by the following structural formula (7) as a calender luminescent material, a 2-butanone for the electronics industry was used as a solvent at 125 minutes. (The organic electroluminescent device was produced in the same manner as in Example 1 except that the drying was carried out for 30 minutes. [Chem. 36]

Structural Formula (8) (Comparative Example 2) In the example 2, when the light-emitting layer was formed, the organic 201241148 electroluminescence light was produced in the same manner as the actual crucible 2 except that the annealing treatment was performed at 150 C for 1 minute. yuan#. (Example 3) In Example 1, when a light-emitting layer was formed, a compound represented by the above formula (2) (glass transition temperature (Tg) == l〇2t) was used as a main body == (1) the compound represented, in addition, w is made in the same way as the organic; "outside, with the example [Chem. 37]

Structural Formula (2) <Structural Formula (2) [Chemical Formula 38] Synthesis Process of Compounds Illustrated > 49 201241148

[化39]

/ + 0 Br

B(OR)2

0Lb(〇R)2 Βώ

IN (Comparative Example 3) In Example 3, when the light-emitting layer was formed, it was dried at 85 ° C for 30 minutes, 50 8 201241148 instead of 12G\: under dry 3G minutes, except that it was produced in the same manner as in Example 3. Organic electroluminescent elements. (Example 4) In Example 1, when a light-emitting layer was formed, a compound represented by the following structural formula (3) (glass transition temperature (Tg) 222 was used. 〇 was used as a host material instead of using the above structural formula 〇) The compound represented is used as the main component, and 'in addition' to the example 1 towel, when the light-emitting layer is formed, it is at 130. Under the armpit, dry for 30 minutes instead of 125. (: An organic electroluminescent device was produced in the same manner as in Example 1 except that drying was performed for 30 minutes. [Chem. 40]

Structural Formula (3) Further, the synthesis scheme of the compound represented by the above structural formula (3) is as follows. <Synthesis flow of the compound represented by the structural formula (3)> [Chem. 41] 201241148 o\jil

(Comparative Example 4) In Example 4, when the light-emitting layer was formed, 'drying at 85 ° C for 30 minutes' was used instead of 130. (The organic electroluminescent device was produced in the same manner as in Example 4 except that the drying was carried out for 30 minutes. (Example 5) In the case of "Forming the light-emitting layer" in Example 1, the following structural formula (4) was used. The compound (glass transition temperature (Tg) = 105 〇 C) was used as the main bone = material instead of using the compound represented by the above structural formula (1) as a 3 fluorene material, and in Example i, a light-emitting layer was formed. When the money of the (10) component is stored at 125t: Nisaki 3G minutes _ ' 'In the same way as Example 1, the organic electric excitation is made 3 [42] 2012 52148

Structural Formula (4) <Synthesis Scheme of Compounds Represented by Structural Formula (4)> [Chem. 43]

Br ΝΗ2

[化 44] 53 201241148

(Comparative Example 5) In Example 5, when the light-emitting layer was formed, it was dried at 85 ° for 3 minutes instead of drying at 120 C for 30 minutes, except that organic electroluminescence was produced in the same manner as in Example 5. element. ~ (Example 6) - Fabrication of Organic Electroluminescent Device - A 0.7 mm thick, 25 mm square glass substrate was placed in a cleaning container, ultrasonically cleaned in 2-propanol, and subjected to a minute uv-odor treatment. The following layers were then formed on the glass substrate. Further, in the case of no particular explanation, the vaporization rate in the following examples and comparative examples was 〇 2 nm/sec. The vapor deposition rate was measured using a crystal oscillator. In addition, the thickness of each layer below was measured using a stylus profiler (XP-200, manufactured by AMBiOS Technplogy. Inc.). First, on the glass substrate, ITO (Indium Tin Oxide) was deposited by vapor deposition to have a thickness of 150 nm as an anode. The resulting transparent support substrate is then engraved and cleaned. Next, on the anode, spin coating was carried out by mixing 90 parts by weight of a hole injecting material 8 54 201241148 (trade name: CLEVIOS P AI4083, manufactured by HC Sterck, Tg = 190 ° C) and 10 parts by weight of ethanol. After the coating liquid, it was dried at 100 C for 1 minute and then at 16 Torr. The crucible was vacuum dried for 120 minutes to form a hole injection layer having a thickness of 4 〇 nm. Next, on the hole injection layer, a light-emitting layer coating liquid described below was spin-coated in a glove box to dry at 160 ° C for 30 minutes to form a light-emitting layer having a thickness of 3 〇 nm, and the light-emitting layer coating liquid was 9 parts by weight of a compound (Tg=i24° C.) represented by the following structural formula (5) as a host material, and a compound represented by the above structural formula (7) as a phosphorescent material (trade name: Ir (ppy) 3 parts by weight of Chemipro Kasei Co., Ltd., dissolved or dispersed in 990 parts by weight of 2-mercaptotetrahydrofuran (boiling point 78〇c, manufactured by Tokyo Chemical Industry Co., Ltd.) for the electronics industry, and then added molecular sieve (trade name: molecular sieve 5A 1) /16, manufactured by Wako Pure Chemical Industries, Ltd.), prepared by filtering in a glove box using a syringe filter with a pore size of 22 μm. [化45]

Structural Formula (5) Next, vapor deposition of BAlq (bis-(2-methyl-8-quinolinolato)-4-(phenyl-phenolate)-alumi 55 201241148 nium-(III)) on the light-emitting layer Forming an electron transport layer with a thickness of 40 nm. Next, lithium fluoride (LiF) was deposited on the electron transport layer to form an electron injecting layer having a thickness of 1 nm. Then, metal aluminum is vapor-deposited on the electron injecting layer to form a cathode having a twist of nm. The produced laminate was placed in an argon-substituted glove case, and sealed with a stainless steel sealed can and an ultraviolet curing adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Further, the synthesis scheme of the compound represented by the above structural formula (5) is as follows. <Synthesis scheme of the compound represented by the structural formula (5)> [Chem. 46]

(Comparative Example 6) When the light-emitting layer was formed in Example 6, it was at 80. (An organic electroluminescent device was produced in the same manner as in Example 6 except that drying was carried out for 30 minutes, 8 56 201241148 instead of drying at 160 C for 30 minutes. (Example 7) In Example 6, on the anode , spin coating of a compound represented by the above structural formula (9) as an arylamine derivative (weight average molecular weight (Mw) = 8,000 'glass transition temperature 14 (rc, further, the above weight average molecular weight is GPC (condensed) 2 pieces by weight of a mixed solvent dissolved or dispersed in dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and dehydrated benzene (manufactured by Kanto Chemical Co., Ltd.) (mixing ratio 7:3) After 98 parts by weight of the coating liquid, it was dried at 120 C for 30 minutes, and then annealed at i3 ° C for 1 minute to form a hole injection layer having a thickness of about 40 nm instead of the anode. , spin coating, a hole injection material (trade name: CLEVIOSPAI4083, manufactured by HCSterck, glass transition temperature (Tg) = 19 〇. 〇 9 〇 parts by weight, and 10 parts by weight of ethanol mixed to prepare a coating liquid Drying at 1 °c for 10 minutes, and then vacuum drying at 160 ° C for 12 minutes to form a hole injection layer having a thickness of about 40 nm; in addition, in Example 6, on the hole injection layer, Spray coating is a compound represented by the following structural formula (6) as a host material (glass transition temperature (Tg) = 112. 〇) 45 parts by weight, and represented by the above structural formula (7) as a phosphorescent material. 0.5 parts by weight of the luminescent layer coating liquid prepared by dissolving or dispersing in 995 parts by weight of methyl isobutyl ketone (boiling point 116. 〇, manufactured by Kanto Chemical Co., Ltd.), and dried at 125 C for 30 minutes to form a thickness of 3 The 发光nm luminescent layer is replaced by the electric/same slab layer, and the spin coating in the glove box is used as the main body 57 201241148 ----- Γ - the compound represented by the above structural formula (5) The luminescent layer coating liquid prepared by dissolving or dispersing a part by weight of the compound represented by the above structural formula (7) as a wall photoluminescent material in a weight fraction of 2 - fluorenyl tetrahydrogen for use in the electronic industry (10) Dry under the armpit for 3 () minutes to form a thickness of 30 legs Emitting layer 'except in the same manner as in Example 6 to fabricate an organic luminescent device. [Formula 47] ⑤

Further, the synthesis scheme of the compound represented by the above structural formula (4) is as follows. <Synthesis flow of the compound represented by the structural formula (6)> [Chem. 48]

</ br> Instead of 125 Τ: drying the light-emitting element, 'organic galvanic was produced in the same manner as in Example 7 (Comparative Example 7). In Example 7, when the luminescent layer was formed, (10) was used instead of the lower drying and the gossip. (3) The organic electroluminescent device was fabricated in the same manner as in Example 7. (Comparative Example 8) Material: In the case of I, on the hole injection layer, spray coating was performed 4 = 5 parts by weight of the main derivative = (CBp), and 5 parts by weight of the compound of the above formula (7) which is used as a light-emitting octene solution or dissolved in xylene (Buddha's point 144 〇) C, manufactured by Kanto Chemical Co., Ltd.), a luminescent layer coating liquid prepared in 995 parts by weight, dried at 155 tT for 3 () minutes to form a light-emitting layer having a thickness of 30 nm instead of the hole injection layer, in the glove The spin coating in the box is used as the main material, and the chemical composition represented by the above structural formula (5) is 9 parts by weight, and as a scale light. The light-emitting layer coating liquid prepared by dissolving or dispersing 1 part by weight of the compound represented by the above structural formula (7) of the optical material in 990 parts by weight of 2, mercapto tetrahydrofuran for the electronic industry, was dried at 160 ° C for 30 minutes. An organic electroluminescent device was produced in the same manner as in Example 6 except that a light-emitting layer having a thickness of 30 nm was formed. As a result, the light-emitting layer was cloudy. It was considered that the white turbidity of the light-emitting layer was derived from heating by dioxazole. The compound (CBP) is crystallized. 59 201241148, (Example 9) In Example 1, when the precursor layer is formed, the compound represented by the formula (11) (the glass transition temperature (TS) is used as the main body) The material is used, and the compound represented by the structural formula (U) is used as the phosphorescent material instead of the chemical cooperation represented by the above structural formula (1), and the above structural formula (7) is used. Indicated: For the light-emitting luminescent material, in addition, in Example i, the underside is dried for 3 minutes, and when the first layer is _123, the drying of the clock is performed, in addition to the actual implementation. Divide the excitation element. As organic [Formula 49]

Structural formula (1

Structural Formula (12) (Comparative Example 9) 201241148 In Example 9, when the light-emitting layer was formed, it was dried at 85 ° C for 3 minutes instead of drying at 140 ° C for 30 minutes, in addition to 9$ the same way to make organic electroluminescent components. (Comparative Example 10) In Example 1, when a light-emitting layer was formed, a compound represented by the above structural formula was used as a phosphorescent material at 115. (: Drying was performed for 3 minutes, and in addition, the light-emitting element was fabricated in the same manner as in Example €. After the element was energized, red EL light was observed. (Example 10) - Organic electroluminescence Preparation of the device A glass substrate of 0.7 mm thick and 25 mm square was placed in a cleaning container, ultrasonically cleaned in 2-propanol, and subjected to ozone treatment for 3 minutes. The layers were formed on the woven glass substrate. It is measured using a crystal oscillator. ',,, 疋 First, the IT 〇 (Indium Tin 〇 xide) is sprayed on the glass substrate to a thickness of ISO nm as an anode. The resulting transparent support substrate is then etched and cleaned. Then, on the anode (ITO), 5 parts by weight of the compound of the following structural formula A was dissolved or dispersed in 995 parts by weight of an electron #关己胴 (manufactured by Kanto Chemicals Co., Ltd.) by spin coating. After the human layer coating liquid, it is dried in the layer (: drying for 30 minutes to form a hole injection having a thickness of 5 (10).

Rb 51] 201241148

In the formula A, 10 parts by weight of the compound of the following structural formula B was dissolved in 990 parts by weight of toluene (dehydrated) (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a hole transport layer coating liquid. The hole transport layer coating liquid was spin-coated on the cavity injection layer, and dried at 20 (TC for 30 minutes) to form a hole transport layer having a thickness of 丨 8. [Chem. 52]

Structural Formula B Next, on the hole transport layer, the following light-emitting layer coating liquid was spin-coated in a glove box, and dried at 15 (TC for 30 minutes to form a light-emitting layer having a thickness of 3 〇 nm, and the above-mentioned light-emitting layer was coated. The cloth liquid is a compound represented by the following structural formula c (exemplified compound 22 described in JP-A-2001-335776) as a host material (glass transition temperature (Tg) = 14 rc), 9 parts by weight, 8 62 201241148. And 1 part by weight of the compound represented by the following structural formula D as a phosphorescent luminescent material is dissolved or dispersed in 990 parts by weight of 2-butanone (boiling point 88 〇C, manufactured by Kanto Chemical Co., Ltd.) for the electronic industry, and then molecular sieve is added ( Product Name: Molecular Sieve 3A &quot;16, manufactured by Wako Pure Chemical Industries Co., Ltd.), prepared by using a syringe filter with a pore size of 0.22 μm in a glove box to prepare 0 [Chem. 53]

Structural formula c

Structural formula b Next, on the light-emitting layer, BAlq (bis-(2-methyl-8-quinolinolato)-4-(phenyl-phenolate)-alumi nium-(III))' is deposited by vacuum evaporation to form a thickness of 40 nm. Electronic transport layer. Next, lithium fluoride (Uf) was deposited on the electron transport layer to form an electron injecting layer having a thickness of 1 nm. Then, metal aluminum was vapor-deposited on the electron injecting layer to form a cathode having a thickness of 70 nm. The produced laminate was placed in an argon-substituted glove box, and sealed with a non-ferrous steel sealed can and an ultraviolet curing adhesive (XNR5516HV 'Nagase Ciba Co., Ltd.). (Comparative Example 11) 63 201241148, J t V^OUll In Example 10, an organic electroluminescent element was produced in the same manner as in Example 10 except that the drying temperature was from 15 Torr: (Example 11) In Example W In place of the above structural formula, a compound (glass transition temperature (Tg) = 136 ° c) represented by the following structural formula E (Japanese Patent Laid-Open Publication No. 2001 335776-A. An organic electroluminescent device was produced in the same manner as in Example 10 except that the compound (glass transition temperature (Tg) 141C) was represented by C and the drying temperature was changed from i5 〇 °C to 145 °C. [化54]

Structural Formula E (Comparative Example 12) In Example 11, the drying temperature was changed from 145 ° C to 12 (TC, except that 'an organic electroluminescent device was produced in the same manner as in Example 11. (Example 12) In the case of 10, the compound represented by the above structural formula (11) (glass transition temperature (Tg) = 125 ° C) is used as a host material instead of using the compound represented by the above structural formula C (glass transition temperature (Tg) 5 64 An organic electroluminescent device was produced in the same manner as in Example 10 except that the drying temperature was changed from 150 ° C to 14 ° C. (Comparative Example 13) In Example 12 The drying temperature was changed from i4 〇 °c to 120. (:, other than this, an organic electroluminescent device was produced in the same manner as in Example 12. Next, 'Completed Example 1 to Example 12 and Comparative Example 1 were compared In the organic electroluminescence device of Example 13, the external neutron efficiency and the rate of change in luminance attenuation (20% decay time) in each layer were measured as follows. <Measurement of External Quantum Efficiency> Sources manufactured by Toyo Technica Co., Ltd. Measurement unit 2400, A direct current voltage was applied to each element at room temperature, and the light was continuously driven to emit light. The emission spectrum and the brightness were measured using a spectrum analyzer SR-3 manufactured by T〇pc〇n Co., Ltd., based on these values, using luminance conversion. The external quantum efficiency at a current of 10 mA/cm 2 was calculated by the method. The results are shown in Tables 1 to 11. <Change rate of luminance attenuation (20% decay time)> Measured according to the spectrum analyzer sr_3 manufactured by Topcxm. The brightness data 'as shown in Fig. 2, when the time is just turned on (10) c-, the brain, the brightness is attenuated by 20% = ^ time as an indicator of the rate of change of brightness decay. The result is == °·', 11 of Table 1 to Table Table 1 is based on Comparative Example 1B, Table) Comparative Example 6 is based on the basis, Table 3 is based on Comparative Example 3, Table 4 is based on Comparative Example 2, and Table 5 is based on Comparative Example 5 is a reference. In Table 6, X Comparative Example 4 is 65 201241148, Table 7 is based on Comparative Example 7, Table 8 is based on Comparative Example 9, and Table 9 is based on Comparative Example 11 10 is based on Comparative Example 12, and Table 11 is based on Comparative Example 13. Outside the above criteria In the example and the comparative example, the external quantum efficiency and the rate of change of the luminance attenuation (20% decay time) in the comparative example as the above reference are set to 1 and the relative values thereof are shown. [Table 1] Changes in luminance decay of the external quantum efficiency Rate (20% decay time) Example 1 1.0 1.3 Comparative Example 1A 1.0 1.0 Comparative Example 1B 1.0 1.0 [Table 2] Rate of change of external quantum efficiency luminance decay (20% decay time) Example 2 1.2 1.2 Comparative Example 2 1.0 1.0 [Table 3] Rate of change of external quantum efficiency luminance attenuation (20% decay time) Example 3 1.0 1.4 Comparative Example 3 1.0 1.0 [Table 4] 5 66 201241148 Change rate of external quantum efficiency luminance attenuation (20% decay time) Example 4 1.0 1.3 Comparative Example 4 1.0 1.0 [Table 5] Rate of change of external quantum efficiency luminance decay (20% decay time) Example 5 1.0 1.1 Comparative Example 5 1.0 1.0 [Table 6] Rate of change of external quantum efficiency luminance attenuation (20% decay time) Example 6 1.0 1.3 Comparative Example 6 1.0 1.0 [Table 7] Rate of change of external quantum efficiency luminance decay (20% decay time) Example 7 1.0 1.3 Example 8 1.2 1.1 Comparative Example 7 1.0 1.0 [Table 8] External amount Rate of change of efficiency luminance decay (20% decay time) Example 9 1.0 1.2 Comparative Example 9 1.0 1.0 67 [Table 9] Change rate of luminance decay Example 10 ~----- (20% decay time) Comparative example ΪΤ ~~~-- 1.3 1.0 201241148 [Table 10] External Zou quantum efficiency

[Table 11] Rate of change of luminance attenuation (20% decay time) ΰ '~~ 1.0 ~~~ External quantum efficiency

As is clear from Table 1, the external quantum efficiencies of Example 1 and Comparative Example 1 比较 and Comparative Example 1 相等 were equal', and the rate of change in luminance attenuation was smaller than that of Comparative Example 1 Α and Comparative Example 1 ( (20% decay time was long). Further, as is clear from Table 2, the external quantum efficiency of Example 2 was higher than that of Comparative Example 2, and the rate of change in luminance attenuation was smaller than that of Comparative Example 2 (2%% decay time was long). Further, as is clear from Table 3, the external quantum efficiency of Example 3 and Comparative Example 3 was equal' and the rate of change in luminance attenuation was smaller than that of Comparative Example 3 (2%% decay 8 68 201241148 minus time length). Further, as can be seen from Table 4, the external quantum efficiency of Example 4 and Comparative Example 4 was equal' and the rate of change of luminance decay was higher than that of Comparative Example 4 (2%% decay time was long). &lt; Further, as is clear from Table 5, the external quantum efficiency of Example 5 and Comparative Example 5 was equal' and the rate of change in luminance attenuation was smaller than that of Comparative Example 5 (2%% decay time was long). Further, as is clear from Table 6, the external quantum efficiency of Example 6 and Comparative Example 6 was equal, and the rate of change in luminance attenuation was smaller than that of Comparative Example 6 (2%% decay time was long). Further, from Table 7, the external quantum efficiency of Example 7 and Comparative Example 7 was equal, and the rate of change in luminance attenuation was smaller than that of Comparative Example 7 (2%% decay time was long). &lt; Further, as is clear from Table 7, Example 8 has a higher external quantum efficiency than Comparative Example 7, and the rate of change in luminance attenuation is smaller than that of Comparative Example 7 (2%% decay time is long). &lt; Example 7 of the glass transition temperature is higher than the mixing of the surface of the sample. Therefore, the external amount is large (2 〇. In addition, as shown in Table 7, the glass transition temperature (14 〇 C) or higher of the hole injection layer is heated. Example 8 and the glass that was not heated to the hole injection layer produced a hole injection layer and

69 201241148 Further, as can be seen from Table 9, the external quantum efficiency of Example 10 and Comparative Example 11 was equal, and the rate of change in luminance attenuation was smaller than that of Comparative Example U (2 〇〇 /. The decay time was long). Further, from Table 10, the external quantum efficiency of Example 11 and Comparative Example 12 was equal, and the rate of change of luminance decay was longer than that of Comparative Example 12. Further, from Table 11, the external quantum efficiency of Example 12 and Comparative Example 13 was equal, and the rate of change in luminance attenuation was smaller than that of Comparative Example 13 (2%% decay time was long). ° [Industrial Applicability] The organic electroluminescence device manufactured by the method of the present invention can be suitably used for, for example, a display element, a display, a backlight, an electronic photograph, and an illumination source because it can achieve excellent luminous efficiency and luminous lifetime. Recording light source, exposure light source, light source, logo, kanban, interior materials, optical communication, etc. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a layer configuration of an organic electroluminescence device of the present invention. Fig. 2 is a graph showing an example of a change in luminance attenuation of the organic electroluminescence device produced by the method of manufacturing the organic electroluminescence device of the present invention from the start of driving. 201241148 [Description of main component symbols] 1 : Substrate 2 : Anode 3 : Hole injection layer 4 : Hole transmission layer 5 : Light-emitting layer 6 : Electron transport layer 7 : Electron injection layer 8 : Cathode 10 : Organic electroluminescence element 71

Claims (1)

201241148 VII. Patent application scope: A method for manufacturing an organic electroluminescence element, wherein the organic electroluminescence light 7L includes an organic layer including a light-emitting layer between the anode and the cathode; and the manufacturing method of the organic electroluminescence element In the coating liquid obtained by dispersing or dispersing a light-emitting material and a host material of at least one of the following general formula (1) and the following general formula (2) in a solvent, Heating to form the above-mentioned light-emitting layer at a temperature higher than the glass transition temperature of the above-mentioned host material and at a temperature greater than that of the upper/troughing agent/folk point, [Chemical Formula 1] In the above formula (1), R represents any one of a third butyl group, a third pentyl group, a trimethyl decyl group, a triphenyl fluorenyl group, and a phenyl group, and R1 to R2. Any one of a hydrogen atom, a third butyl group, a third pentyl group, a trimethyl decyl group, a diphenylmethane group, a phenyl group, a cyano group, and a carbon number of 1 to 5; [Chemical 2] 72 201241148 In the above formula (2), R represents an arbitrary substituent. 2. The method for producing an organic electroluminescence device according to claim 1, wherein the luminescent material has a molecular weight of 1,500 or less, and the host material has a molecular weight of 1,500 or less. 3. The method for producing an organic electroluminescence device according to claim 1, wherein the host material represented by the above formula (1) is the following structural formula (1) to structural formula (6) and structure. a compound represented by any one of the formula (11): [Chemical 3] [4] 73 201241148 Structural formula (2) [Chemical 5] Structural formula (3) [Chemical 6] Structural formula (4) [Chem. 7] 201241148 [化8] Structural formula (5) Structural formula (6) [Chemical 9] Structural formula (11). 4. The method for producing an organic electroluminescence device according to the above aspect, wherein the host material represented by the above formula (2) is any one of the following structural formula C and structural formula E. Compounds indicated: [Chem. 10] 75 201241148 5. The method of producing an organic electroluminescent device according to claim 1, wherein the solvent is selected from the group consisting of 2-butanone, diphenylbenzene, toluene, 2-methyltetrahydrofuran, and mercaptoisobutyl ketone. At least one of them. 6. The method of producing an organic electroluminescent device according to claim 1, wherein the luminescent material is in the following structural formula (7), structural formula (8), structural formula (12), and structural formula D. Compound represented by either one··Hb 11] /3 . Structural formula (7 ) [Chem. 12] 8 76 201241148 Structural formula (8) [Chem. 13] Structural formula (12) [Chem. 14] Irr°j 0=&lt;Structure D. 7. The method of producing an organic electroluminescent device according to claim 1, wherein the heating temperature is higher than a glass transition temperature of the host material by more than 10 ° C and is 45 ° higher than a boiling point of the solvent. Above C. 77