JP2006193678A - Organic electroluminescent element, lighting system and display unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element and a display unit having a high fetch yield and a long life. <P>SOLUTION: The organic electroluminescent element has at least one light-emitting layer or component layer between an anode and a cathode wherein a light emission includes at least a phosphorescence emission and contains a compound represented by formula (1) and the compound has not the center of symmetry (in the formula, each of Ar<SB>1</SB>-Ar<SB>4</SB>represents an aromatic hydrocarbon group or aromatic heterocyclic group and L represents a bivalent connecting group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic electroluminescence element, a lighting device, and a display device.

  Conventionally, there is an electroluminescence display (ELD) as a light-emitting electronic display device. Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL element has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode. By injecting electrons and holes into the light emitting layer and recombining them, excitons (exciton) are obtained. Is a device that emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several V to several tens of V, and further self-emission. Since it is a type, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving, portability, and the like.

  For the development of organic EL elements for practical use in the future, organic EL elements that emit light efficiently and with high luminance with lower power consumption are desired. For example, stilbene derivatives, distyrylarylene derivatives, or tris A technique for doping a styrylarylene derivative with a small amount of a phosphor to improve emission luminance and extend the lifetime of the device (see, for example, Patent Document 1), and 8-hydroxyquinoline aluminum complex as a host compound. A device having an organic light-emitting layer doped with a trace amount of phosphor (for example, see Patent Document 2), a device having an organic light-emitting layer doped with a quinacridone-based dye as an 8-hydroxyquinoline aluminum complex as a host compound (for example, , See Patent Document 3).

  In the technique disclosed in the above-mentioned patent document, when the emission from the excited singlet is used, the generation ratio of the singlet exciton and the triplet exciton is 1: 3, so the generation probability of the luminescent excited species is 25%. Since the light extraction efficiency is about 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University has reported on organic EL devices that use phosphorescence from excited triplets (see, for example, Non-Patent Document 1), research on materials that exhibit phosphorescence at room temperature has become active. (For example, refer nonpatent literature 2 and patent literature 4.).

  When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so in principle the luminous efficiency is four times that of excited singlets, and the performance is almost the same as that of cold cathode tubes. It can be applied to and attracts attention. 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).

As a dopant, studies using tris (2-phenylpyridine) iridium have been made (for example, see Non-Patent Document 2). In addition, L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac) is used as a dopant. ) (See, for example, Non-Patent Document 4) and tris (2- (p-tolyl) pyridine) iridium (Ir (ptpy) ₃ ), tris (benzo [h] quinoline) iridium (Ir ( bzq) ₃ ), Ir (bzq) ₂ ClP (Bu) _{3 and the} like have been studied (for example, see Non-Patent Document 5).

  In order to obtain high luminous efficiency, a hole transporting compound is used as a host of a phosphorescent compound (see, for example, Non-Patent Document 6), and various electron transporting materials are used as a host of a phosphorescent compound. There are examples in which an iridium complex is doped and used (for example, see Non-Patent Document 4), and examples in which high luminous efficiency is obtained by introducing a hole blocking layer (for example, see Non-Patent Document 5). In addition, a chemical structure including a partial structure of a nitrogen-containing aromatic ring compound and extending in three or four directions with a nitrogen atom or aryl as a center, and a thermally stable hole transport material is disclosed (For example, refer to Patent Document 5).

  In addition, there is an example (for example, see Patent Document 6) in which a light-emitting material having high luminance is disclosed using a nitrogen-containing aromatic ring compound.

  Currently, further improvement in light emission efficiency and long life of organic EL devices using phosphorescence emission are being studied, but the green light emission has achieved an external extraction efficiency of nearly 20%, which is the theoretical limit. However, only the low current region (low luminance region) is present, and the theoretical limit has not yet been achieved in the high current region (high luminance region). Furthermore, sufficient efficiency has not yet been obtained for other luminescent colors, and improvements are required. In addition, organic EL devices for practical use in the future will emit light efficiently and with high brightness. Development of the organic EL element which does is desired. In particular, there is a demand for an element that emits light with high efficiency in a blue phosphorescent organic EL element.

  In addition, recently, organic EL elements after elapse of time due to driving or storage under high temperature conditions tend to cause changes in emission color, decrease in emission efficiency, increase in drive voltage, decrease in emission lifetime, etc. In order to overcome such problems, it has been devised to use an asymmetrical compound having a high glass transition point. As an example of such a compound, the molecular structure is different at both ends of the arylene group. An aromatic amine derivative having a diarylamino group has been developed, and an organic EL device using the aromatic amine derivative has been developed (for example, see Patent Document 7).

However, even if the above technique is used, the increase in the light emission efficiency of the organic EL element is not sufficient from a practical point of view, and further improvement is required.
Japanese Patent No. 3093796 Japanese Unexamined Patent Publication No. 63-264692 JP-A-3-255190 US Pat. No. 6,097,147 Japanese Patent Publication No.7-110940 JP 2001-160488 A JP 2004-262761 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) M.M. E. Thompson et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu) Moon-Jae Youn. 0 g, Tsutsuo Tsutsui et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu) Ikai et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu)

  The objective of this invention is providing the organic electroluminescent element, display apparatus, and illuminating device with high luminous efficiency, and also providing the organic electroluminescent element, display apparatus, and illuminating device of long life.

  The above object of the present invention has been achieved by the following configurations 1 to 11.

(Claim 1)
In the organic electroluminescence device having at least one light emitting layer or constituent layer between the anode and the cathode,
An organic electroluminescence device characterized in that light emission includes at least phosphorescence light emission, contains a compound represented by the following general formula (1), and the compound does not have a symmetry center.

[Wherein, Ar _{1 to} Ar ₄ each represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and L represents a divalent linking group. ]
(Claim 2)
2. The organic electroluminescence device according to claim 1, wherein the L does not have a symmetry center.

(Claim 3)
The organic electroluminescence device according to claim 1, wherein L is an arylene group.

(Claim 4)
The organic electroluminescence element according to claim 3, wherein the L is represented by the following general formula (2).

General formula (2)
-L1-L2-
[Wherein, L 1 and L 2 each independently represent an arylene group. ]
(Claim 5)
The organic electroluminescence device according to claim 4, wherein the L1 and L2 are arylene groups having different molecular structures.

(Claim 6)
The organic electroluminescent element according to any one of claims 1 to 5, comprising a compound represented by the following general formula (3).

General formula (3)
A1-L3-A2
[Wherein, A1 and A2 each represent a substituent, at least one of A1 and A2 has an aromatic carbocycle or aromatic heterocycle as a partial structure, and A1 and A2 are different molecules from each other. It has a structure. L3 represents a divalent linking group. ]
(Claim 7)
The organic electroluminescence device according to claim 6, wherein the compound represented by the general formula (3) is a light emitting host.

(Claim 8)
8. The structure according to claim 1, wherein the constituent layer includes a hole transport layer, and at least one layer of the hole transport layer contains a compound represented by the general formula (1). The organic electroluminescent element of the item.

(Claim 9)
The phosphorescent light-emitting material is contained, and the phosphorescent light-emitting material contains a metal of Group 8 to Group 10 or an ion of the metal in a molecular structure. The organic electroluminescent element of description.

(Claim 10)
A display device comprising the organic electroluminescence element according to claim 1.

(Claim 11)
An illuminating device comprising the organic electroluminescence element according to any one of claims 1 to 9 or the display device according to claim 10.

  According to the present invention, an organic electroluminescence element, a display device, and a lighting device with high luminous efficiency can be provided, and a long-life organic electroluminescence element, a display device, and a lighting device can be provided.

  In the organic EL device of the present invention, an organic EL device having a high luminous efficiency and a long life could be obtained by adopting the configuration defined in any one of claims 1 to 8. . In addition, a display device or lighting device with high luminance and long life could be obtained using the organic EL element exhibiting the above characteristics.

  Hereinafter, details of each component according to the present invention will be sequentially described.

  As a result of various investigations on the above problems, the present inventors have incorporated an element configuration including a compound represented by the general formula (1), in which the emission includes at least phosphorescence emission in the configuration of the organic EL element. As a result, an organic EL element having a high light emission efficiency and a long lifetime, which is the object of the present invention, was obtained.

  The inventors of the present invention are directed to molecular design that enhances the amorphousness further than conventionally known aromatic amine derivatives, and the obtained compound represented by the general formula (1) is excellent in durability and heat resistance. In addition, since it has a high Tg and is excellent in morphological stability, it is considered that effects such as a significant increase in light emission efficiency and a longer lifetime of the device were obtained.

  The compound represented by the general formula (1) according to the present invention may be used in any of the constituent layers of the organic EL element, but from the viewpoint of preferably obtaining the effects described in the present invention, the hole of the organic EL element. It is preferable to be contained in the transport layer (the hole transport layer will be described in detail in the configuration of the organic EL device described later).

<< Compound Represented by Formula (1) >>
The compound represented by the general formula (1) according to the present invention will be described.

The feature of the compound represented by the general formula (1) according to the present invention is that it does not have a center of symmetry, but in the present invention, a compound that does not have a center of symmetry is a chemical dictionary such as Michinori Ohki. 1st edition 1st edition Published on October 20, 1989 (Tokyo Kagaku Dojin Co., Ltd.), page 1329, compounds with no center of symmetry (also called center of symmetry) It can be defined as a compound having no axis (S ₂ ).

  Specifically, for example, trans-1,3-dichlorocyclobutane is a compound having a point symmetry (i), but the compound represented by the general formula (1) according to the present invention is a point symmetry (i). It is a compound that does not have

  Furthermore, in this invention, it is preferable that the divalent coupling group represented by L of the compound represented by General formula (1) does not have a symmetry center.

In the general formula (1), examples of the aromatic hydrocarbon group represented by Ar _{1 to} Ar ₄ include a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, Examples include an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, and a biphenylyl group.

  Each of these groups may further have a substituent described later.

In the general formula (1), examples of the aromatic heterocyclic group represented by Ar _{1 to} Ar ₄ include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, and a pyrazinyl group. , Triazolyl group (for example, 1,2,4-triazol-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, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (composing carboline ring of carbonyl group) One of the carbon atoms replaced by a nitrogen atom), quinoxa Group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, and the like.

  Each of these groups may further have a substituent described later.

  In the general formula (1), examples of the divalent linking group represented by L include hydrocarbon groups such as alkylene groups, alkenylene groups, alkynylene groups, and arylene groups, as well as the alkylene groups, the alkenylene groups, and the alkynylene groups. In addition, each group such as the arylene group may contain a heteroatom (for example, a nitrogen atom, a sulfur atom, a silicon atom, etc.), a thiophene-2,5-diyl group, a pyrazine It may be a divalent linking group derived from a compound having an aromatic heterocycle (also referred to as a heteroaromatic compound) such as a -2,3-diyl group, or a chalcogen atom such as oxygen or sulfur. May be. In addition, examples include an alkylimino group, a dialkylsilanediyl group and a diarylgermandiyl group that are linked via a heteroatom, preferably an arylene group, and more preferably the above general formula (2). The arylene group represented by general formula (2) is particularly preferably an arylene group in which L1 and L2 each have a different molecular structure.

  In the general formula (2), the arylene groups independently represented by L1 and L2 are the arylene groups (specific examples of the arylene groups) used as the divalent linking group represented by L in the general formula (1). An example is synonymous with later.)

  In the general formula (2), the arylene groups represented by L1 and L2 have different molecular structures from each other when the substituents of the arylene groups are different from each other. And the like (for example, one of them represents a phenylene group and the other represents a naphthylene group, etc.).

  In the present invention, the divalent linking group represented by L preferably has no center of symmetry, but as described above, the arylene groups represented by L1 and L2 have molecular structures different from each other. By designing the molecule, the divalent linking group represented by L can be prevented from having a center of symmetry.

  In the general formula (1), examples of the alkylene group used as the divalent linking group represented by L include, for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene. Group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.) ), A cyclopentylene group (for example, 1,5-cyclopentanediyl group, etc.) and the like.

  In the general formula (1), examples of the alkenylene group used as the divalent linking group represented by L include a propenylene group, a vinylene group (also referred to as an ethynylene group), a 4-propyl-2-pentenylene group, and the like. It is done.

  In the general formula (1), examples of the alkynylene group used as the divalent linking group represented by L include an ethynylene group and a 3-pentynylene group.

  In the general formula (1), the arylene group used as the divalent linking group represented by L includes an o-phenylene group, an m-phenylene group, a p-phenylene group, a naphthalenediyl group, an anthracenediyl group, and a naphthacenediyl group. , Pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group (o-terphenyldiyl group, m-terphenyl) Diyl group, p-terphenyldiyl group, etc.), quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octylphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group, etc. Is mentioned.

  Examples of the arylene group represented by the general formula (2) include a naphthylnaphthalenediyl group and a biphenyldiyl group (for example, among the arylene groups used as the divalent linking group represented by L in the general formula (1)). 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group (o-terphenyldiyl group, m-terphenyldiyl group, p-terphenyldiyl group, etc.), quater Examples thereof include a phenyldiyl group, a kinkphenyldiyl group, a sexiphenyldiyl group, a septiphenyldiyl group, an octylphenyldiyl group, a nobiphenyldiyl group, and a deciphenyldiyl group.

  In the general formula (1), examples of the divalent heterocyclic group used as the divalent linking group represented by L include an oxazolediyl group, a pyrimidinediyl group, a pyridazinediyl group, a pyrandiyl group, a pyrrolindiyl group, Examples include imidazoline diyl group, imidazolidine diyl group, pyrazolidine diyl group, pyrazoline diyl group, piperidine diyl group, piperazine diyl group, morpholine diyl group, quinuclidine diyl group, and thiophene-2,5-diyl group. Alternatively, it may be a divalent linking group derived from a compound having an aromatic heterocyclic ring (also referred to as a heteroaromatic compound) such as a pyrazine-2,3-diyl group.

  Here, each of the divalent linking groups represented by L may be further substituted with a substituent shown below.

(Substituent)
The aromatic hydrocarbon group represented by Ar _{1 to} Ar ₄ of the compound represented by the above general formula (1), the aromatic heterocyclic group, the divalent linking group represented by the above L, etc. The substituent may have 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 etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.) , Aryl groups (eg, phenyl groups, naphthyl groups, etc.), aromatic heterocyclic groups (eg, furyl groups, thienyl groups, pyridyl groups, pyridazinyl groups, pyrimidinyl groups) Pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (eg, methoxy group) , Ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxyl group (eg, cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy group (eg, phenoxy group) , Naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group) Group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group) Group), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl) Group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyrid Aminosulfonyl groups, etc.), acyl groups (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl) Group, pyridylcarbonyl group, etc.), acyloxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methyl Carbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2 Ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group) Pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, , Methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, Phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, Naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group ( Phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, Ruamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated carbonization Hydrogen group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxyl group, mercapto group, silyl group (eg, trimethylsilyl group, triisopropylsilyl group) , Triphenylsilyl group, phenyldiethylsilyl group, etc.).

  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.

  Hereinafter, although the specific example of a compound represented by General formula (1) based on this invention is shown, this invention is not limited to these.

  Next, although an example of the synthesis example of the compound represented by General formula (1) based on this invention is shown, this invention is not limited to these.

  << Synthesis Example 1: Synthesis of Compound (1) >>

In a 300 ml three-necked flask, 5.0 g of N, N-diphenylamine, 5.0 g of compound (1a) (Chem. Ber., 28, 1985, page 2551), dimethylacetamide 200 ml, potassium carbonate 5.0 g, copper powder 2.6 g was added and heated to reflux for 10 hours. After completion of the reaction, insoluble matters were removed by diatomaceous earth filtration, the reaction solution was added to 1 L of water, and the organic matter was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then dried under reduced pressure on a rotary evaporator. The residue was purified by column chromatography to obtain 3.5 g of a white solid. ^The compound (1) was identified using ¹ H-NMR (nuclear magnetic resonance spectrum) and mass spectrum.

  << Synthesis Example 2: Synthesis of Compound (12) >>

To a 300 ml three-necked flask, 6.5 g of N-phenyl-1-naphthylamine, 5.0 g of compound (1b), 200 ml of dimethylacetamide, 5.0 g of potassium carbonate, and 2.6 g of copper powder were added and heated to reflux for 10 hours. After completion of the reaction, insoluble matters were removed by diatomaceous earth filtration, the reaction solution was added to 1 L of water, and the organic matter was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then dried under reduced pressure on a rotary evaporator. The residue was purified by column chromatography to obtain 3.5 g of a white solid. ^The compound (12) was identified using ¹ H-NMR (nuclear magnetic resonance spectrum) and mass spectrum.

<< Compound preferably used in combination with the compound represented by the general formula (1) >>
In order to further increase the luminous efficiency of the organic EL device of the present invention and to further extend the lifetime of the device, compounds other than the compound represented by the general formula (1) can be used. It is preferable to use the compound represented by the general formula (3).

  Although the compound preferably used in combination with the compound represented by the general formula (1) can be used in any layer of the organic EL device, it is preferably used as a light emitting host, particularly preferably. The light emitting layer (the light emitting layer will be described in detail in the configuration of the organic EL element) is contained as a light emitting host.

  Here, when the compound preferably used in combination with the compound represented by the general formula (1) is used as a light-emitting host (also referred to as a host compound), it is room temperature (25 ° C.) among the compounds contained in the light-emitting layer. ) Is defined as a compound having a phosphorescence quantum yield of phosphorescence of less than 0.01. Here, the phosphorescence quantum yield will be described in the phosphorescent compound described later.

In the compound preferably used in combination with the compound represented by the general formula (1), the substituents represented by A1 and A2 are Ar _{1 to} Ar ₄ of the compound represented by the general formula (1). An aromatic hydrocarbon group, an aromatic heterocyclic group, a divalent linking group represented by L described above, and the like have the same meaning as the substituent that may be further included.

  Moreover, in General formula (3), the bivalent coupling group represented by L3 is synonymous with the bivalent coupling group represented by L which the compound represented by General formula (1) has.

  Hereinafter, specific examples of compounds preferably used in combination with the compound represented by the general formula (1) according to the present invention are represented by H-1 to H-30 (in the following specific examples, represented by the general formula (3)). Specific examples of such compounds are H-27 to H-30.), But the present invention is not limited thereto.

  Moreover, the compound preferably used in combination with the compound represented by the general formula (1) in the present invention can be obtained by a conventionally known synthesis method of an organic compound.

Next, the constituent layers of the organic EL device of the present invention will be described in detail.
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 << 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 electrode materials 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, a thin film may be formed by depositing these electrode materials 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 the pattern accuracy is not required (100 μm or more) Degree), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, 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, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc. / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

  The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal with a film thickness of 1-20 nm on a cathode, a transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

  Next, an injection layer, a blocking layer, an electron transport layer, and the like used as a constituent layer of the organic EL element of the present invention will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. You may let them.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes 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 desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

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

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

The hole blocking layer of the organic EL device of the present invention is provided adjacent to the light emitting layer.
In this invention, it is preferable to contain the compound which concerns on this invention mentioned above as a hole blocking material of a hole blocking layer. Thereby, it can be set as an organic EL element with much higher luminous efficiency. Furthermore, the lifetime can be further increased.

  On the other hand, the electron blocking layer is a hole transport layer in a broad sense, made of a material that has a function of transporting holes and has a very small ability to transport electrons, and blocks electrons while transporting holes. Thus, the probability of recombination of electrons and holes can be improved.

<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 in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

<Light emitting host (host compound)>
The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host (also referred to as a host compound) and a phosphorescent light emitting material (also referred to as a phosphorescent compound) shown below. By using the compound, the luminous efficiency can be further increased.

  The light-emitting host (host compound) according to the present invention is defined as a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.01 at room temperature (25 ° C.) among compounds contained in the light-emitting layer.

  As described above, the compound represented by the general formula (3) is preferably used as the light emitting host according to the present invention.

  In the present invention, a plurality of known host compounds may be used in combination. 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. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  As the host compound, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable. Specific examples of the host compound used in the present invention 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.

  Moreover, the light emitting layer may contain the host compound which has a fluorescence maximum wavelength further as a host compound. In this case, the energy transfer from the other host compound and the phosphorescent compound to the fluorescent compound allows electroluminescence as an organic EL element to be emitted from the other host compound having a fluorescence maximum wavelength. A host compound having a fluorescence maximum wavelength is preferably a compound having a high fluorescence quantum yield in a solution state. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more. Specific host compounds having a maximum fluorescence wavelength include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, and pyrylium dyes. Perylene dyes, stilbene dyes, polythiophene dyes, and the like. The fluorescence quantum yield can be measured by the method described in 362 (1992, Maruzen) of Spectroscopic II of the Fourth Edition Experimental Chemistry Course 7.

<< Phosphorescent Luminescent Material (Phosphorescent Compound) >>
The phosphorescent light-emitting material used for the light-emitting layer (hereinafter also referred to as a light-emitting material or a phosphorescent compound) preferably contains a phosphorescent compound at the same time as containing the host compound. Thereby, it can be set as an organic EL element with higher luminous efficiency.

  The phosphorescent compound according to the present invention is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0.2 at 25 ° C. 01 or more compounds. The phosphorescence quantum yield is preferably 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 quantum yield used in the present invention only needs to achieve the above phosphorescence quantum yield in any solvent.

  There are two types of light emission of phosphorescent compounds 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 phosphorescent. Energy transfer type to obtain light emission from the phosphorescent compound by transferring to the compound, the other is that the phosphorescent compound becomes a carrier trap, carrier recombination occurs on the phosphorescent compound, and from the phosphorescent compound In any case, the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

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

  The phosphorescent compound used in the present invention is preferably a complex compound having at least one metal of Group 8 to Group 10 in the periodic table, more preferably an iridium compound, an osmium compound, or platinum. Compounds (platinum complex compounds) and rare earth complexes, most preferably iridium compounds.

  Although the specific example of a phosphorescent compound is shown below, this invention is not limited to these. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like.

  In the present invention, the phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited. In principle, the phosphorescent compound can be obtained by selecting a central metal, a ligand, a ligand substituent, and the like. However, it is preferable that the phosphorescent compound has a maximum phosphorescence emission wavelength of 380 nm to 480 nm. With such a blue phosphorescent organic EL element and a white phosphorescent organic EL element, the luminous efficiency can be further increased.

  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 Minolta) is applied to the CIE chromaticity coordinates.

  The light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5 nm-200 nm. The light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are composed of one or more kinds, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Good.

《Hole transport layer》
The hole transport layer is made of a 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.

  As the hole transport material according to the present invention, the compound represented by the general formula (1) according to the present invention is preferably used from the viewpoints of improving the external extraction quantum efficiency of the organic EL element and extending the light emission lifetime. It is done.

  In addition to the compound represented by the general formula (1) according to the present invention, a conventionally known hole transport material, a material commonly used as a hole charge injection / transport material, a hole injection layer, a hole transport Known materials used for the layer may be used in combination, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted Examples include chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. Furthermore, a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, especially an aromatic tertiary amine compound can be used in combination.

  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 ′ Di (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-diphenylaminostilbene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, 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 publication No. 8 are linked in a starburst type (MTDATA).

  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.

  In the present invention, the hole transport material of the hole transport layer preferably has a fluorescence maximum wavelength at 415 nm or less. That is, the hole transport material is preferably a compound that has a hole transport ability, prevents the emission of light from becoming longer, and has a high Tg.

  Furthermore, in the present invention, it is preferable that the phosphorescence 0-0 band of the hole transport material is 480 nm or less, so that it has higher emission luminance, better quantum efficiency, and even higher durability. In particular, it is to provide an organic electroluminescence element having a small luminance drop in the early stage of light emission, and a display device or illumination device comprising the same.

  A method for measuring the 0-0 band of the phosphorescence spectrum in the present invention will be described.

First, a method for measuring a phosphorescence spectrum will be described.
The compound to be measured was dissolved in a well-deoxygenated mixed solvent of ethanol / methanol = 4/1 (vol / vol), put into a phosphorescence measurement cell, and irradiated with excitation light at a liquid nitrogen temperature of 77 ° K. The emission spectrum at 100 ms after the excitation light irradiation is measured. Since phosphorescence has a longer emission lifetime than fluorescence, it can be considered that light remaining after 100 ms is almost phosphorescence.

  For compounds with a phosphorescence lifetime shorter than 100 ms, measurement may be performed with a shorter delay time, but phosphorescence and fluorescence cannot be separated if the delay time is shortened so that it cannot be distinguished from fluorescence. Since this is a problem, it is necessary to select a delay time that can be separated.

  In addition, for a compound that cannot be dissolved in the solvent system, any solvent that can dissolve the compound may be used (substantially, the solvent effect of the phosphorescence wavelength is negligible in the above measurement method).

  Next, the 0-0 band is determined. In the present invention, the emission maximum wavelength that appears on the shortest wavelength side in the phosphorescence spectrum chart obtained by the above-described measurement method is defined as the 0-0 band.

  Since the phosphorescence spectrum usually has a low intensity, when it is enlarged, it may be difficult to distinguish between noise and peak. In such a case, the steady light spectrum is expanded, and the peak wavelength is read from the portion of the steady light spectrum derived from the phosphorescence spectrum by superimposing it with the emission spectrum 100 ms after irradiation with the excitation light (for convenience, this is called the phosphorescence spectrum). Can be determined. Further, by performing a smoothing process on the phosphorescence spectrum, it is possible to separate the noise and the peak and read the peak wavelength. As the smoothing process, a smoothing method of Savitzky & Golay can be applied.

  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, an ink jet method, an LB method, a transfer method, or a printing method. be able to. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, it is about 5-5000 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

《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.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above 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.

  In addition, 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 , Ca, Sn, Ga, or Pb can also be used as an electron transport material. 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 similarly to the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC can be used. A semiconductor can also be used as an electron transport 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 nm-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

<Substrate>
The organic EL device of the present invention is preferably formed on a substrate. The substrate (hereinafter also referred to as a substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc. Although there is no restriction | limiting in particular, As a board | substrate used preferably, glass, quartz, and a transparent resin film can be mentioned, for example. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples include films made of triacetate (TAC), cellulose acetate propionate (CAP), and the like. On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed.

  The external extraction efficiency at room temperature for light emission of the organic electroluminescence device of 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. 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.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode will be described.

  First, a thin film made of a desired electrode material, for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm. Make it. Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, is formed thereon.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (for example, a spin coating method, a casting method, an ink jet method, a printing method) as described above. From the viewpoint of difficulty in generating pinholes, vacuum deposition, spin coating, ink jet, and printing are particularly preferable. Further, a different film forming method may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 ° C. to 450 ° C., a vacuum degree of 10 ⁻⁶ Pa to 10 ⁻² Pa, and a vapor deposition rate of 0 It is desirable to select appropriately within the range of 0.01 nm / second to 50 nm / second, substrate temperature −50 ° C. to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 nm to 200 nm.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL element 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.

  The multi-color display device of the present invention is provided with a shadow mask only at the time of forming a light emitting layer, and other layers are common, so patterning such as a shadow mask is unnecessary, and vapor deposition, casting, spin coating, inkjet A film can be formed by a method or a printing method.

  When patterning is performed only on the light-emitting layer, the method is not limited, but a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.

  In addition, it is possible to reverse the production order and produce the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode 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 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The display device of the present invention can be used as a display device, a display, and various light emission sources. In a display device or a 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.

  Illumination devices 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, it is not limited to these. Moreover, you may use as an organic EL element which gave the organic EL element of this invention the resonator structure.

  Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.

  The organic EL material used in 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 three primary colors of blue, green, and blue, or two using a complementary color relationship 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 that emit light, and a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material. Any combination with a dye material that emits light as excitation light may be used. However, in the white organic electroluminescence device according to the present invention, it is only necessary to mix and combine a plurality of light-emitting dopants. It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, or the like, and simply arrange them separately by 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, an ortho metalated complex (Ir complex, so that it may suit the wavelength range corresponding to CF (color filter) characteristic) Pt complex etc.) or any known light emitting material may be selected and combined to whiten.

  As described above, the white light-emitting organic EL device according to the present invention is a kind of lamp such as a home lighting, an interior lighting, or an exposure light source as various light emitting light sources and lighting devices in addition to the display device and the display. It is also useful for display devices such as backlights for liquid crystal display devices.

  Others such as backlights for watches, signboard 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. There are a wide range of uses such as household appliances.

<Display device>
The organic EL element of the present invention may be used as one 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). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using three or more organic EL elements of the present invention having different emission colors. Alternatively, it is possible to make a single color emission color, for example, white emission, into BGR using a color filter to achieve full color. Furthermore, it is possible to convert the emission color of the organic EL to another color by using a color conversion filter, and in this case, λmax of the organic EL emission is preferably 480 nm or less.

  An example of a display device composed of 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 the plurality of pixels based on image information from the outside. The pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display 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. FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  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 grid pattern and are connected to the pixels 3 at orthogonal positions (details are shown in FIG. Not shown).

  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 that emit light 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 on / off of a predetermined light emission amount by a binary image data signal. But you can.

  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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

  Here, a list of compounds used in Examples is shown.

Example 1
<< Production of Organic EL Element 1-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of α-NPD is put into a molybdenum resistance heating boat, and CBP (H-8) is used as a host compound in another resistance heating boat made of molybdenum. 200 mg, 200 mg of bathocuproin (BCP) in another molybdenum resistance heating boat, 100 mg of Ir-12 as a dopant (also referred to as a light-emitting dopant) in another molybdenum resistance heating boat, and another molybdenum resistance heating 200 mg of Alq ₃ was placed in a boat and attached to a vacuum deposition apparatus.

Next, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is heated by heating, vapor-deposited on a transparent support substrate at a vapor deposition rate of 0.1 nm / second, and hole transport A layer was provided. Further, the heating boat containing CBP (H-8) and Ir-12 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively. A light emitting layer was provided.

In addition, the substrate temperature at the time of vapor deposition was room temperature. Furthermore, the heating boat containing BCP was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer. Further, the heating boat containing Alq ₃ is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-13 >>
In the production of the organic EL element 1-1, except that the CBP used as the light emitting host and the α-NPD used as the hole transport compound were replaced with the hole transport materials shown in Table 1, Similarly, 1-2 to 1-13 were produced.

<< Evaluation of Organic EL Elements 1-1 to 1-13 >>
The following evaluation was performed about obtained organic EL element 1-1 to 1-13.

《External extraction quantum efficiency》
The produced organic EL device was measured for external extraction quantum efficiency (%) when a constant current of ^2.5 mA / cm ² was applied at 23 ° C. in a dry nitrogen gas atmosphere. For the measurement, a spectral radiance meter CS-1000 (manufactured by Minolta) was used.

"lifespan"
When driving at a constant current of ^2.5 mA / cm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured, and this was taken as the half-life time (τ ^0.5 ) It was used as an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Minolta) was used.

  Moreover, the measurement results of the external extraction quantum efficiency and lifetime in Table 1 are expressed as relative values when the measured value of the organic EL element 1-1 is 100. The obtained results are shown in Table 1.

  From Table 1, it is clear that the organic EL device of the present invention is superior in both external quantum efficiency and lifetime as compared with the comparison.

Example 2
<< Production of Organic EL Elements 2-1 to 2-13 >>
In the production of the organic EL element 1-1 of Example 1, an organic EL element 2-1 was produced in the same manner except that the dopant compound in the light emitting layer was replaced with Ir-1. Subsequently, in the production of the organic EL element 2-1, the organic materials were similarly obtained except that CBP used as a light emitting host and α-NPD used as a hole transport compound were replaced with hole transport materials shown in Table 2. EL elements 2-2 to 2-13 were produced.

  About each of obtained organic EL element 2-1 to 2-13, it carried out similarly to the description in Example 1, and measured and evaluated the external extraction quantum efficiency and lifetime. The measurement results of the external extraction quantum efficiency and lifetime in Table 2 were expressed as relative values when the measured value of the organic EL element 2-1 was 100.

  The obtained results are shown in Table 2.

  From Table 2, it is clear that the organic EL device of the present invention is superior in both external quantum efficiency and lifetime as compared with the comparison.

Example 3: (Example of lighting device, using white organic EL element)
In the organic EL element 2-3 produced in Example 2, the same as the organic EL element 2-3 except that Ir-1 used in the light emitting layer was changed to a mixture of Ir-1, Ir-9, and Ir-12. The organic EL element 2-3W produced by the method was used. The non-light-emitting surface of the organic EL element 2-3W was covered with a glass case to obtain an illumination device as shown in FIGS. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life. FIG. 5 shows a schematic view of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. Lower glove box (performed in an atmosphere of high-purity nitrogen gas with a purity of 99.999% or more)). 6 shows a cross-sectional view of the lighting device. In FIG. 6, reference numeral 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.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

Explanation of symbols

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 107 Glass substrate with a transparent electrode 106 Organic EL layer 105 Cathode 102 Glass cover 108 Nitrogen gas 109 Water catcher

Claims (11)

In the organic electroluminescence device having at least one light emitting layer or constituent layer between the anode and the cathode,
An organic electroluminescence device characterized in that light emission includes at least phosphorescence light emission, contains a compound represented by the following general formula (1), and the compound does not have a symmetry center.

[Wherein, Ar _{1 to} Ar ₄ each represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and L represents a divalent linking group. ] 2. The organic electroluminescence device according to claim 1, wherein the L does not have a center of symmetry. The organic electroluminescence device according to claim 1, wherein L is an arylene group. The organic electroluminescence element according to claim 3, wherein the L is represented by the following general formula (2).
General formula (2)
-L1-L2-
[Wherein, L 1 and L 2 each independently represent an arylene group. ] The organic electroluminescence device according to claim 4, wherein the L1 and L2 are arylene groups having different molecular structures. The organic electroluminescent element according to any one of claims 1 to 5, comprising a compound represented by the following general formula (3).
General formula (3)
A1-L3-A2
[Wherein, A1 and A2 each represent a substituent, at least one of A1 and A2 has an aromatic carbocycle or aromatic heterocycle as a partial structure, and A1 and A2 are different molecules from each other. It has a structure. L3 represents a divalent linking group. ] The organic electroluminescence device according to claim 6, wherein the compound represented by the general formula (3) is a light emitting host. 8. The structure according to claim 1, wherein the constituent layer includes a hole transport layer, and at least one layer of the hole transport layer contains a compound represented by the general formula (1). The organic electroluminescent element of the item. The phosphorescent light-emitting material is contained, and the phosphorescent light-emitting material contains a metal of Group 8 to Group 10 or an ion of the metal in a molecular structure. The organic electroluminescent element of description. A display device comprising the organic electroluminescence element according to claim 1. An illuminating device comprising the organic electroluminescence element according to claim 1 or the display device according to claim 10.

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