JP5720253B2 - ORGANIC ELECTRONIC ELECTRONIC DEVICE, DISPLAY DEVICE AND LIGHTING DEVICE HAVING THE SAME - Google Patents

Description

  The present invention relates to an organic electronics element using a special organic electronics element material, a display device and an illumination device including the organic electronics element.

  More specifically, the present invention relates to an organic electronics element having a high luminous efficiency, a long luminous lifetime, a low driving voltage, and a small voltage change during low current driving, and a special organic electronics element material that can be realized.

  In recent years, there has been great interest in so-called organic electronics materials based on organic semiconductors, as well as organic electronics elements using them.

  Examples of the organic electronics element include an organic electroluminescence element (hereinafter also referred to as “organic EL element”), an organic thin film solar cell, and an organic transistor. In general, organic electronics elements are light, thin, and flexible. In addition to dry (vacuum) processes such as vapor deposition, which have been widely used in inorganic semiconductors, they can be applied to wet processes such as printing and coating film formation. Because of the good matching, there is an expectation for large area and low price. On the other hand, there is a problem in the stability of materials compared to inorganic semiconductors, and development of new materials is awaited.

  For example, an organic EL element that has been attracting attention in recent years has a configuration in which a light emitting layer containing a light emitting compound is sandwiched between a cathode and an anode, and by injecting electrons and holes into the light emitting layer and recombining them. It is an element that generates excitons (excitons) and emits light using light emission (fluorescence / phosphorescence) when the excitons are deactivated. Light emission is possible at a voltage of several volts to several tens of volts, and since it is a self-luminous type, it has a wide viewing angle, and since it is a thin-film type completely solid element, it is very interesting from the viewpoint of space saving and portability. Collecting.

  As for development of organic EL elements for practical use, Princeton University has reported organic EL elements that use phosphorescence emission from excited triplets (see, for example, Non-Patent Document 1). Research on the materials shown has been active (see, for example, Patent Document 1 and Non-Patent Document 2).

  In addition, recently discovered organic EL devices that use phosphorescence can realize a luminous efficiency that is approximately four times that of previous devices that use fluorescence. Research and development of light-emitting element layer configurations and electrodes are performed all over the world. For example, many compounds have been studied for synthesis centering on heavy metal complexes such as iridium complexes (see, for example, Non-Patent Document 3).

  Although this is a very high potential method, the organic EL device using phosphorescence emission is greatly different from the organic EL device using fluorescence emission, and the method for controlling the position of the emission center, particularly the emission layer, is particularly different. An important technical issue in capturing the efficiency and lifetime of the device is how to recombine inside to stably emit light.

  Therefore, in recent years, there has been a multilayer stack type element having a separation of functions, in particular, a hole transport layer located on the anode side of the light emitting layer and an electron transport layer located on the cathode side of the light emitting layer in a form adjacent to the light emitting layer. It has come to be used (for example, refer patent document 2).

  However, from the viewpoints of charge injection / transport properties, voltage change during low current driving, and the like, it is still not sufficient, and further improvements are required.

US Pat. No. 6,097,147 JP 2005-112765 A

M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) S. Lamansky et al. , J .; Am. Chem. Soc. 123, 4304 (2001)

  The present invention has been made in view of the above-described problems and situations, and the solution to the problem is an organic electronic device having high luminous efficiency, long luminous lifetime, low driving voltage, and small voltage change during low current driving. Is to provide. Moreover, it is providing the display apparatus and illuminating device with which the said organic electronics element was comprised.

  As a result of intensive studies to solve the above problems, the present inventors have found that the combination of the electron injection material containing an alkali metal and the partial structure of the adjacent layer material greatly contributes to the performance of the organic EL device. did. Furthermore, when an alkali metal such as potassium or cesium is used, an aromatic ring or aromatic heterocyclic ring is substituted as a substituent on the carbon at the N-position of the nitrogen (N) -containing aromatic heterocyclic ring as the adjacent layer material. By using the introduced one, it was found that the performance of the organic EL device was specifically improved, and the present invention was completed.

  That is, the said subject which concerns on this invention is solved by the following means.

1. An organic electronic device having an electron injection layer in contact with the cathode and a plurality of constituent layers including a light emitting layer between the anode and the cathode, wherein the constituent layer in contact with the electron injection layer is represented by the following general formula (1) A phosphorescent organometallic complex in the light emitting layer, a metal or metal compound of an element belonging to Group 1 of the periodic table in the electron injection layer, and the element The standard electrode potential of the metal ion (Mn ⁺ ) / metal (M) system of −3 Vvs. An organic electronic device characterized by being larger than SHE.

(Wherein, _{X 1} is Table to .X ₂ nitrogen atom (N) represents CR _2, the _{R 2} is a substituted or unsubstituted, .Y representing a phenyl group or a carbazolyl group, O, S, NR or Represents SiRR, R represents a hydrogen atom or a substituent, X ₃ , X ₄ , Z ₁ and Z ₂ each represent CR, and R represents a hydrogen atom or a substituent.)

2 . 2. The organic electronic device according to item 1, wherein the compound represented by the general formula (1 ) is contained in an electron transport layer.

3 . 3. The organic electronic device according to item 1 or 2, wherein the element belonging to Group 1 of the periodic table is sodium, potassium, or cesium.

4 . The organic electronic device according to any one of Items 1 to 3, wherein the phosphorescent organometallic complex is an iridium (Ir) complex.

5 . The organic electronics element according to any one of items 1 to 4 , wherein the organic electronics element is an organic electroluminescence element that emits white light.

6 . A display device comprising the organic electronics element according to any one of items 1 to 5 above.

7 . 6. An illuminating device comprising the organic electronics element according to any one of items 1 to 5 .

  By the above means of the present invention, it is possible to provide an organic electronic device having a high light emission efficiency, a long light emission lifetime, a low drive voltage, and a small voltage change during low current drive. In addition, a display device and a lighting device including the organic electronic element can be provided.

  The manifestation mechanism of the effect of the present invention is not necessarily elucidated, but the background situation and background of the present invention related to the mechanism are as follows.

As the electron injection material, alkali metals and alkaline earth metals typified by lithium fluoride having a small work function are well known, and compounds represented by the general formulas (1) to (3) according to the present invention. As a result of a detailed examination of the combination with the above, the inventors of the present invention have found that the standard electrode potential of the Mn ⁺ / M system is −3 Vvs. By using together a metal or a metal compound (including a complex or a salt) of an element larger than SHE, the performance of the organic electronic device could be specifically improved.

  This is because an element large in comparison with an element having a small oxidation-reduction potential easily accepts electrons, and thus is easily reduced to a metal state. Such an element is represented by the general formulas (1) to (3) according to the present invention. This is probably due to a specific interaction with the compound.

  That is, a combination of a material in which an aromatic ring or an aromatic heterocyclic ring is introduced as a substituent into the N-position carbon of the N-containing aromatic heterocyclic ring as an adjacent layer material, and an alkali metal element having a large redox potential, It has been found that the performance of organic electronic devices, such as organic electroluminescent devices, is significantly improved, and the present invention has been achieved.

  By means of the present invention, there are provided an organic electronics element that exhibits high emission luminance, a long half-life, a low driving voltage, and a small voltage change during low current driving, and a display device and an illumination device using the element. It became possible.

Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of display part A It is a schematic diagram of a pixel. Schematic diagram of passive matrix type full color display device Schematic of lighting device The schematic diagram of an illuminating device. Schematic configuration diagram of organic EL full-color display device

The organic electronic element of the present invention is an organic electronic element having an electron injection layer in contact with the cathode and a plurality of constituent layers including a light emitting layer between the anode and the cathode, and the constituent layer in contact with the electron injection layer Containing a compound represented by the general formula (1), a phosphorescent organometallic complex in the light emitting layer, and a metal or metal of an element belonging to Group 1 of the periodic table in the electron injection layer And a standard electrode potential of the metal ion (Mn ⁺ ) / metal (M) system of the element is −3 Vvs. It is characterized by being larger than SHE. This feature is a technical feature common to the inventions according to claims 1 to 7 .

  As an embodiment of the present invention, it is preferable that the general formula (1) is an embodiment represented by the general formula (2) from the viewpoint of manifesting the effect of the present invention. Furthermore, the general formula (2) is preferably represented by the general formula (3).

  In this invention, it is preferable that the compound represented by the said General Formula (1)-(3) is contained in the electron carrying layer. The element belonging to Group 1 of the periodic table is preferably sodium, potassium, or cesium. Furthermore, the phosphorescent organometallic complex is preferably an iridium (Ir) complex.

  As an embodiment of the present invention, the organic electronics element is preferably an organic electroluminescence element that emits white light.

  The organic electronic element of the present invention can be suitably included in a display device and a lighting device.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

(Compounds represented by general formulas (1) to (3))
<Compound represented by formula (1)>
The organic electronics element of the present invention is characterized in that the constituent layer in contact with the electron injection layer contains a compound represented by the following general formula (1).

In the general formula (1), X _{1 to} X ₄ each represent CR or a nitrogen atom (N), and _one of X _{1 to} X ₄ is a nitrogen atom (N). R represents a hydrogen atom or a substituent.

Furthermore, when X ₁ = N, X ₂ = CR ₂ and R ₂ is a substituted or unsubstituted aryl group or heteroaryl group. When X ₂ = N, X ₁ = CR ₁ and X ₃ = CR ₃ and at least one of R ₁ and R ₃ is an unsubstituted aryl group or heteroaryl group.

When X ₃ = N, X ₂ = CR ₂ and X ₄ = CR ₄ and at least one of R ₂ and R ₄ is an unsubstituted aryl group or heteroarylene group. When X ₄ = N, X ₃ = CR ₃ and R ₃ is a substituted or unsubstituted aryl group or heteroaryl group.

Y represents O, S, NR, C RR , or Si RR . Z ₁ and Z ₂ each represent CR. R represents a hydrogen atom or a substituent.

  Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group). Groups, etc.), alkyl groups (eg, cyclopentyl groups, cyclohexyl groups, etc.), alkenyl groups (eg, vinyl groups, allyl groups, etc.), alkynyl groups (eg, ethynyl groups, argyl groups, etc.), aromatic carbonization Hydrogen group (also referred to as aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-alkoxy phenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, Azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl ), Aromatic heterocyclic groups (for example, pyridyl group, pyrimidinyl group, furyl group, piparyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole-1) -Yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzo Furyl group, benzothienyl group, dibenzothienyl group, indolyl group, force rubazolyl group, force rubolinyl group, diaza force rubazolyl group (one in which one of the carbon atoms constituting the force rubolin ring of the force rubolinyl group is replaced by a nitrogen atom) Quinoxalinyl group, biridazinyl group, triazinyl group, quina Linyl group, phthalazinyl group, etc.), heterocyclic group (eg, pipridyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyl) Oxy group, octyloxy group, dodecyloxy group, etc.), cyclyl alkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, A methylthio group, an ethylthio group, a propylthio group, a pentylthio group, a hexylthio group, an octylthio group, a dodecylthio group, etc.), a cycloalkylthio group (for example, a cyclopentylthio group, a cyclohexylthio group, etc.), an arylthio group (for example, a phenylthio group, a naphthylthio group) Etc.), alkoxycarbonyl groups (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group etc.), aryloxycarbonyl groups (eg phenyloxycarbonyl group, naphthyloxy) Carbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenyl) Aminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethyl group sulfonyl group, propyl) Sulfonyl group, pentyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, dodecyl group, phenyl group, naphthyl group, naphthyl group, pyridyl group, etc.), acyloxy group ( For example, acetyloxy group, ethyl group carbonyloxy group, butyl group sulfonyloxy group, octyl group sulfonyloxy group, dodecyl group carbonyloxy group, phenyl group carbonyloxy group, etc.), amide group (for example, methyl group carbonylamino group, ethyl group) Force carbonyl amino group, dimethyl force sulfonyl amino group, propyl force sulfonyl amino group, pentyl force sulfonyl amino group, cyclohexyl force carbonyl amino group, 2-ethylhexyl force carbonyl amino group, octyl force sulfonyl amino group, dodecyl force carbonyl amino group Group, phenyl group sulfonylamino group, naphthyl group carbonylamino group, etc.), group rubamoyl group (for example, amino group carbonyl group, methylamino group carbonyl group, dimethylamino group carbonyl group, propylamino group carbonyl group, pentylamino group carbonyl group) Group, cyclohexylamino group, octylamino group, 2-ethylhexylamino group, dodecylamino group, phenylamino group, naphthylamino group, 2-pyridylamino group, ureido Groups (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), sulfinyl Group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-bilidylsulfinyl group), alkyl A sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl) Group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethyl) Hexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, Trifluoromethyl group, pentafluorine ethyl group, pentafluorine phenyl group, etc.), cyano group, nitro group, hydroxy group, mercatopto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyl) A diethylsilyl group and the like) and a phosphono group.

  In addition, these substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

  Examples of the aryl group include the aromatic hydrocarbon groups represented by the above substituents.

  Examples of the heteroaryl group include aromatic heterocyclic groups represented by the above substituents.

  In the following general formulas (2) and (3), the same substituents, aryl groups, and heteroaryl groups may be mentioned, but in general formulas (1) to (3), they are listed here. These are representative examples and are not limited to these.

<Compound represented by formula (2)>
In the present invention, the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).

In the general formula (2), X ₁ and X ₂ each represent CR. Ar represents a substituted or unsubstituted aryl group or heteroaryl group. Y represents O, S, NR, CRR ′, or SiRR ′. Z ₁ and Z ₂ each represent CR. R and R ′ each represents a hydrogen atom or a substituent.

<Compound represented by formula (3)>
In the present invention, the compound represented by the general formula (2) is preferably a compound represented by the following general formula (3).

In General Formula (3), X _{1 to} X ₂ and X _{5 to} X ₈ each represent CR. Ar represents a substituted or unsubstituted aryl group or heteroaryl group. Y represents O, S, NR, CRR ′, or SiRR ′. R and R ′ each represents a hydrogen atom or a substituent.

  The compounds represented by the general formulas (1) to (3) are preferably contained in a buffer layer between the light emitting layer and the electron injection layer, and particularly preferably contained in the electron transport layer.

  The electron injection layer contains a metal or metal compound of an element belonging to Group 1 of the periodic table, and the standard electrode potential of the metal ion (Mn +) / metal (M) system of the element is −3 Vvs. It is preferably larger than SHE, and examples of the element belonging to Group 1 of the periodic table include sodium, potassium, cesium and the like, and more preferably potassium and calcium.

  Hereinafter, although the specific example of a compound represented by General formula (1) which is a material for organic electronics elements of this invention is shown, this invention is not limited to these.

  Hereinafter, although the specific example of the compound represented by General formula (2) which is a material for organic electronics elements of this invention is shown, this invention is not limited to these.

  Hereinafter, although the specific example of a compound represented by General formula (3) which is a material for organic electronics elements of this invention is shown, this invention is not limited to these.

(Organic electronics element)
Although various aspects can be taken as an aspect of the organic electronics element of the present invention, an organic electroluminescence (EL) element, an organic thin-film solar cell, an organic transistor, and the like are preferable examples.

  In the following, an organic electroluminescence (EL) element will be described in detail as a representative example.

<< Method for Manufacturing Organic EL Element >>
As an example of a method for producing an organic EL device, a device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode Will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate so as to have a thickness of 1 μm or less, preferably 10 to 200 nm, and an anode is manufactured.

  Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, or a cathode buffer layer, which is an element material, is formed thereon.

  The thin film formation method is roughly classified into a dry method and a wet method. Examples of the dry method include a vacuum deposition method and a sputtering method. Examples of the wet method include a spin coating method, a casting method, a die coating method, and a blade. There are coating method, roll coating method, ink jet method, printing method, spray coating method, curtain coating method, LB method, etc., but it is possible to form a precise thin film and from the point of high productivity, vacuum deposition method and die coating A method having high suitability for a roll-to-roll method such as a method, a roll coating method, an ink jet method, or a spray coating method is preferable. Different film forming methods may be applied for each layer.

  After the formation of these layers, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a desired organic EL device can be obtained by providing a cathode. .

  Further, the order can be reversed, and the cathode, cathode buffer layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order.

  When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element according to the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode // hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode Buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode The light emitting layer may form a unit to form a light emitting layer unit.

  Further, a non-light emitting intermediate layer may be provided between the light emitting layers, and the intermediate layer may include a charge generation layer. The organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these. Each layer which comprises the organic EL element of this invention is demonstrated.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is not a layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The thickness of the light emitting layer is not particularly limited, but from the viewpoint of the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color with respect to the drive current. It is preferable to adjust to the range of 2-200 nm, More preferably, it adjusts to the range of 5-100 nm.

  The light emitting layer of the organic EL device of the present invention preferably contains at least one of a host compound (also referred to as a light emitting host) and a light emitting dopant as a guest material, and contains a host compound and three or more kinds of light emitting dopants. Is more preferable. A host compound and a light emitting dopant (also referred to as a light emitting dopant compound) contained in the light emitting layer will be described below.

(Host compound and luminescent dopant)
(Host compound)
In the present invention, the “host compound” means that the content (mass%) in the layer of the compound contained in the light emitting layer is 20% or more and phosphorescence emission occurs at room temperature (25 ° C.). A phosphorescence quantum yield is defined as a compound having a value of less than 0.1. Preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the content rate (mass%) in the layer is 20% or more in the compound contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  The light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). Light emitting host).

  The compound represented by the general formula (1) according to the present invention is preferably used as the host compound according to the present invention.

When the compound represented by the general formula (1) according to the present invention is used as a host compound, the 6-membered aromatic ring represented by Ar ₂ is preferably a group derived from a benzene ring.

  As the known host compound that may be used in combination, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable.

  Specific examples of known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Hereinafter, although the specific example of the conventionally well-known compound used as a host compound of the light emitting layer of the organic EL element of this invention is given, this invention is not limited to these.

(Luminescent dopant)
As the light-emitting dopant, a fluorescent light-emitting dopant (also referred to as “fluorescent compound”), a phosphorescent light-emitting dopant (also referred to as “phosphorescent material”, “phosphorescent compound”, “phosphorescent dopant”, or the like). Can be used.

(Fluorescent dopant)
Fluorescent light emitting dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes. And dyes having a high fluorescence quantum yield, such as laser dyes, and other dyes, polythiophene dyes, rare earth complex phosphors, and the like.

(Phosphorescent dopant)
The “phosphorescent dopant” according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.). Although the yield is defined to be a compound of 0.01 or more at 25 ° C., the preferred phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence emitting dopant according to the present invention achieves the above phosphorescence quantum yield (0.01 or more) in any solvent. It only has to be done.

  There are two types of light emission of the phosphorescent dopant in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is used as the phosphorescent dopant. The energy transfer type that obtains light emission from the phosphorescent dopant by moving to the phosphor, and the other is that the phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent dopant to cause phosphorescence emission. In any case, the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device.

  The phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex system). Compound) and rare earth complexes, and most preferred is an iridium compound.

  Hereinafter, although the specific example of the phosphorescence-emitting dopant which can be used preferably in this invention is shown, this invention is not limited to these.

<< Charge transport layer: electron transport layer, hole transport layer >>
Examples of the charge transport layer according to the present invention include an electron transport layer and a hole transport layer.

  Hereinafter, the electron transport layer and the hole transport layer according to the present invention will be described in detail.

《Electron transport layer》
The “electron transport layer” is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers. Examples of conventionally known materials used for the electron transport layer (hereinafter referred to as “electron transport materials”) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, and the like. Products, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives, and azacarbazole derivatives.

  Conventionally, an electron transport material (also serving as a hole blocking material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer. As the electron transport material, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, Anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, pyridine derivatives, azacarbazole derivatives and the like can be mentioned.

  In the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu Metal complexes replaced with Ca, Sn, Ga, or Pb can also be used as electron transport materials.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.

  In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.

  Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, an electron transport layer with high n property doped with impurities as a guest material can be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be manufactured. Hereinafter, although the specific example of the conventionally well-known compound used for formation of the electron carrying layer of the organic EL element of this invention is given, this invention is not limited to these.

《Hole transport layer》
The “hole transport layer” is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can do. About the film thickness of a positive hole transport layer, it is preferable that it is the range of 5 nm-5 micrometers, More preferably, it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced. Hereinafter, although the specific example of the conventionally well-known compound used for formation of the positive hole transport layer of the organic EL element of this invention is given, this invention is not limited to these.

<Blocking layer: hole blocking layer, electron blocking layer>
The “blocking layer” is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and a very small ability to transport holes. By blocking the holes, the probability of recombination of electrons and holes can be improved.

  Moreover, the structure of the above-mentioned electron carrying layer can be used as a hole-blocking layer concerning this invention as needed.

  The hole blocking layer of the organic EL device according to the present invention is preferably provided adjacent to the light emitting layer.

  The hole blocking layer preferably contains the carbazole derivative, azacarbazole derivative, pyridine derivative, or the like mentioned as the host compound.

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the layer.

  Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.

  (1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

<< Charge injection layer: electron injection layer, hole injection layer >>
The charge injection layer according to the present invention is provided as necessary, and includes an electron injection layer and a hole injection layer, and as described above, between the anode and the light emitting layer or the hole transport layer, and the cathode and the light emitting layer or the electron transport layer. It may be present between.

  An “injection layer” is a layer provided between an electrode and an organic layer in order to reduce driving voltage or improve light emission luminance. “Organic EL element and its industrialization front line (NST 30, November 30, 1998) (Published by the company) "Chapter 2 of Chapter 2" Electrode Materials "(pp. 123-166), which is described in detail, has a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer) .

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

  In addition, the materials used for the anode buffer layer and the cathode buffer layer can be used in combination with other materials. For example, the materials can be mixed in the hole transport layer or the electron transport layer.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode material include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.

  For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less.

  Further, the film thickness is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 200 nm, although it depends on the material.

"cathode"
As the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  In the present invention, these electrode substances (also referred to as conductive materials) are used as a conductive paste to form a thin film by a wet method to produce a cathode.

  The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is preferably in the range of 10 nm to 5 μm, and more preferably in the range of 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved. Moreover, after producing the metal with a film thickness of 1 to 20 nm on the cathode, a transparent or translucent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

"substrate"
Examples of substrates that can be used in the organic EL device according to the present invention (hereinafter also referred to as “base”, “base”, “support substrate”, “support”, etc.)) include glass and plastic. There is no particular limitation, and it may be transparent or opaque. When extracting light from the substrate side, the substrate is preferably transparent. Examples of the transparent substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable substrate is a resin film capable of giving flexibility to the organic EL element. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned. On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability measured by a method in accordance with JIS K 7129-1992 (25 ± 0.5 ° C., It is preferably a barrier film having a relative humidity (90 ± 2)% RH) of 0.01 g / (m ² · 24 h) or less, and further, oxygen permeation measured by a method according to JIS K 7126-1987. The film is preferably a high barrier film having a degree of 10 ⁻³ ml / (m ² · 24 h · MPa) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less. As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times. The method for forming the barrier film is not particularly limited. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, a plasma polymerization method, an atmospheric pressure plasma polymerization method. A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque substrate include a metal plate such as aluminum and stainless steel, a film, an opaque resin substrate, a ceramic substrate, and the like. The external extraction efficiency at room temperature of light emission of the organic EL device according to the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<Sealing>
As a sealing means of the organic EL element used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

  In the present invention, a polymer film and a metal film can be preferably used because the organic EL element can be thinned.

Furthermore, the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² / 24h) or less, and is measured by a method according to JIS K 7129-1992. is water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably that of ^{1 × 10 -3 ml / (m} 2 / 24h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  Further, it is also possible to suitably form an inorganic or organic layer as a sealing film by covering the outer side of the electrode facing the substrate with the organic layer sandwiched between the electrode and the organic layer, and in contact with the substrate. In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.

  Furthermore, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, plasma CVD method, laser CVD method, thermal CVD method, coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light within a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1), and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said that there is no. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method for forming a reflective surface on the side surface of an organic EL element (Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (Japanese Patent Laid-Open No. 62-172691), and lowering the refractive index than the substrate between the substrate and the light emitter. A method of introducing a flat layer having a structure (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer, and a light emitting layer (including between the substrate and the outside) No. 283751) .

  In the present invention, these methods can be used in combination with the organic EL device according to the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, A method of forming a diffraction grating between any layers of the transparent electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an organic EL device having further high luminance or durability.

  When a medium with a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower. .

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less, more preferably 1.35 or less. .

  Further, the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.

  This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

  However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

  At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

  The arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device according to the present invention can be processed on the light extraction side of the substrate, for example, by providing a microlens array-like structure, or combined with a so-called condensing sheet, for example, in a specific direction, for example, the device light emitting surface. On the other hand, the brightness | luminance in a specific direction can be raised by condensing in a front direction.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm.

  If it is smaller than this, the effect of diffraction occurs and the color is changed.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.

  As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

Further, when the organic EL element according to the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is measured when the front luminance at 2 ° viewing angle is measured by the above method. , X = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

<Display device>
The display device according to the present invention includes the organic EL element of the present invention. The display device according to the present invention may be single color or multicolor, but here, the multicolor display device will be described.

  In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by a vapor deposition method, a casting method, a spin coating method, an ink jet method, a printing method, or the like.

  In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.

  The configuration of the organic EL element provided in the display device is selected from the above-described configuration examples of the organic EL element as necessary.

  Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect | mode of manufacture of the organic EL element of said invention.

  In the case of applying a DC voltage to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  Light emitting sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. However, the present invention is not limited to these.

  Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic diagram illustrating an example of a display device including organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A. The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below.

  In the figure, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not) When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.

  Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 3 is a schematic diagram of a pixel. The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

  That is, the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good. The potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 4 is a schematic view of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.

  In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

《Lighting device》
The lighting device according to the present invention has the organic EL element. The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, it is possible to produce a full-color display device by using two or more organic EL elements of the present invention having different emission colors.

  The organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.

  It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved.

  According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

<< One Embodiment of Lighting Device of the Present Invention >>
The non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a 300 μm thick glass substrate is used as a sealing substrate, and an epoxy photocurable adhesive (LUX The track LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, sealed, and illuminated as shown in FIGS. A device can be formed.

  FIG. 5 shows a schematic diagram of a lighting device, and the organic EL element 101 of the present invention is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is to bring the organic EL element 101 into contact with the atmosphere. And a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more).

  FIG. 6 shows a cross-sectional view of the lighting device. In FIG. 6, 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1
(Synthesis method of general formula (3) (ET-3-3))

Under a nitrogen atmosphere, 30 mmol of compound A and 10 mmol of compound B were dissolved in dimethyl sulfoxide (DMSO; 100 ml), 2.5 mol of PdCl ₂ dppf and 40 mmol of K ₂ CO ₃ were added, and the mixture was stirred at 80 ° C. for 12 hours. Then, it returned to room temperature, 500 ml of ethyl acetate and pure water (100 ml) were added and stirred. The organic layer was washed with saturated brine and dried over magnesium sulfate. After completion of drying, the solvent was washed away under reduced pressure, washed with about 50 ml of toluene, further dissolved with 100 ml of toluene under heating, and allowed to stand overnight at room temperature for recrystallization. The target product ET-3-3 (6 mmol, 60% yield) was obtained as a white solid. The compound was identified by NMR and Mass, and the purity was measured by HPLC and confirmed to be> 99%.

  Other compounds used in the present invention could be synthesized relatively easily in the same manner as described above.

Example 2
<Preparation of organic EL element 1-13>

  After patterning a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing ITO (indium tin oxide: tin-doped indium oxide) 100 nm on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode The transparent support substrate provided with was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by HC Starck Co., Ltd., CLEVIO P VP AI 4083) with pure water on this transparent support substrate to 70%. A thin film was formed by spin coating under conditions of 3000 rpm and 30 seconds, and then dried at 200 ° C. for 1 hour to provide a 20 nm-thick hole transport layer.

This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 100 mg of CSi-7 was placed in a molybdenum resistance heating boat and mounted on the vacuum deposition apparatus. Similarly, 100 mg each of α-NPD, CBP, Ir (ppy) ₃ , and Alq ₃ was put into a boat and mounted.

Next, after the pressure in the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. A hole transport layer was provided.

Further, the heating boat containing the light emitting host CBP and Ir (ppy) ₃ is energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.1 nm / sec and 0.006 nm / sec, respectively. A 40 nm light emitting layer was provided.

Furthermore, the heating boat containing Alq ₃ was heated by energization, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / sec to provide an electron transport layer having a thickness of 30 nm. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 110nm was vapor-deposited, the cathode was formed, and the organic EL element 1-13 was produced.

  Organic EL elements 1-1 to 1-12 and 1-14 to 1-24 were produced in exactly the same manner except that the electron transport material and the ET material were changed to the materials shown in Table 1.

  Moreover, the structure of the ET material used for 1-17 to 1-24 is shown below.

  Table 1 shows electron transport materials and electron injection materials used for the organic EL elements 1-1 to 1-24.

<< Evaluation of Organic EL Elements 1-1 to 1-24 >>
When evaluating the obtained organic EL elements 1-1 to 1-24, the non-light-emitting surface of each organic EL element after production was covered with a glass cover, and the glass cover and the glass plate on which the organic EL element was produced were prepared. An epoxy-based photo-curing adhesive (Luxtrac LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the glass cover side that comes into contact with the transparent support substrate so as to overlap the cathode side, and the glass substrate side. Then, it was cured by irradiating with UV light and sealed, and the lighting device as shown in FIGS. 5 and 6 was formed and evaluated. Subsequently, the following measurement / evaluation was performed.

(External quantum efficiency)
By causing the organic EL device to emit light at room temperature (about 23 ° C. to 25 ° C.) and a constant current of ^2.5 mA / cm ² , and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of light emission, The external extraction quantum efficiency (η) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance.

(Drive voltage)
The voltage was measured when the organic EL device was driven at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² .

(Luminescent life)
The organic EL device continuously emitted light at room temperature under a constant current condition of ^2.5 mA / cm ² , and the time (τ1 / 2) required to obtain half the initial luminance was measured.

  The external extraction quantum efficiency, drive voltage, and light emission lifetime are expressed as relative values at which the organic EL element 1-13 is set to 100.

(Voltage change under constant current)
The organic EL device continuously emits light at a constant current of ^2.5 mA / cm ² at room temperature, and when the time required to reach half the initial luminance (τ1 / 2) is reached, Compared with voltage, the amount of change (increase value) was expressed as a relative value with 1-13 set to 100.

  Table 2 shows the results obtained by the measurement and evaluation.

  As is clear from the results shown in Table 2, the organic EL device of the present invention is superior to the comparative example in external extraction quantum efficiency, driving voltage, emission lifetime, and voltage change under a constant current. I understand.

Example 3
(Blue light emitting organic EL device)
As a blue light-emitting organic EL element, a blue element light-emitting organic EL element 2-1B was similarly manufactured except that Ir (ppy) ₃ was changed to D-26 in the manufacture of the organic EL element 1-4 manufactured in Example 2. Was made.

(Green light-emitting organic EL device)
The organic EL element 1-4 produced in Example 2 was used as the green light-emitting organic EL element.

(Red light emitting organic EL device)
A red light-emitting organic EL element 3-1R was produced in the same manner as in the production of the organic EL element 1-4 of Example 2, except that Ir (ppy) ₃ was changed to D-10.

  The above red, green and blue light emitting organic EL elements are juxtaposed on the same substrate to produce an active matrix type full color display device having the form shown in FIG. 1, and FIG. 2 shows a display portion of the produced display device. Only the schematic diagram of A is shown. That is, a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions ( Details are not shown.) The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. Thus, a full color display device was produced by juxtaposing the red, green, and blue pixels appropriately.

  It was confirmed that by driving the full-color display device, a full-color moving image display with high light emission efficiency and a long light emission life can be obtained.

Example 4
(Production of white light emitting lighting device)
In the production of the organic EL element 2-1B produced in Example 3, the white light-emitting organic EL element was similarly obtained except that D-26 was changed to a three-component mixture of Ir (ppy) 3, D-10, and D-26. 4-1W was produced. The obtained organic EL device 4-1W was covered with a glass case on the non-light-emitting surface in the same manner as in the above example to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 7 Power supply line 10 Organic EL element 11 Switching transistor 12 Drive transistor 13 Capacitor A Display part B Control part 101 Organic EL element 102 Glass cover 105 Cathode 106 Organic EL layer 107 Glass substrate with a transparent electrode 108 Nitrogen gas 109 Water trapping agent 201 Glass substrate 202 ITO transparent electrode 203 Partition wall 204 Hole injection layer 205B, 205G, 205R Light emitting layer

Claims (7)

An organic electronic device having an electron injection layer in contact with the cathode and a plurality of constituent layers including a light emitting layer between the anode and the cathode, wherein the constituent layer in contact with the electron injection layer is represented by the following general formula (1) A phosphorescent organometallic complex in the light emitting layer, a metal or metal compound of an element belonging to Group 1 of the periodic table in the electron injection layer, and the element The standard electrode potential of the metal ion (Mn ⁺ ) / metal (M) system of −3 Vvs. An organic electronic device characterized by being larger than SHE.

(Wherein, _{X 1} is Table to .X ₂ nitrogen atom (N) represents CR _2, the _{R 2} is a substituted or unsubstituted, .Y representing a phenyl group or a carbazolyl group, O, S, NR or represents Si RR, R represents a hydrogen atom or a _{substituent. X 3, X 4, Z} 1 and _{Z 2,} respectively, to display the CR, R represents a hydrogen atom or a substituent.) The organic electronic device according to claim 1, wherein the compound represented by the general formula (1 ) is contained in an electron transport layer. 3. The organic electronic device according to claim 1, wherein the element belonging to Group 1 of the periodic table is sodium, potassium, or cesium. The phosphorescent organic metal complex, an iridium (Ir) organic electronic device according to any one of claims 1 to 3, characterized in that the complex. The organic electronics element according to any one of claims 1 to 4 , wherein the organic electronics element is an organic electroluminescence element that emits white light. Display device in which an organic electronic device according to any one of claims 1 to 5, characterized in that it is provided. An organic electronic device according to any one of claims 1 to 5 , further comprising an illuminating device.

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