WO2012147397A1 - Élément électroluminescent organique et appareil d'éclairage - Google Patents

Élément électroluminescent organique et appareil d'éclairage Download PDF

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WO2012147397A1
WO2012147397A1 PCT/JP2012/054124 JP2012054124W WO2012147397A1 WO 2012147397 A1 WO2012147397 A1 WO 2012147397A1 JP 2012054124 W JP2012054124 W JP 2012054124W WO 2012147397 A1 WO2012147397 A1 WO 2012147397A1
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健 波木井
宏 石代
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Konica Minolta Inc
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Definitions

  • the present invention relates to an organic electroluminescence element and an illumination device applied to various displays, display devices, illuminations, and the like.
  • organic electroluminescence element (hereinafter also referred to as “organic EL element”) that emits light by using electric energy from positive and negative electrodes using an organic material is about several V to several tens V. It has been attracting attention in recent years because it is capable of emitting light at a low voltage, is a thin-film type complete solid-state device, and is space-saving.
  • Patent Document 1 discusses a cathode electrode composed of a laminate of a transparent conductive metal layer and a transparent conductive oxide. This is intended to achieve both the transmittance and conductivity of the cathode electrode by laminating a transparent conductive oxide on the thin film metal layer.
  • the transparent conductive oxide is formed by sputtering, It had the problem of damaging the light emitting layer.
  • a magnesium-silver alloy has been studied as a thin film metal, but the magnesium-silver alloy has improved electron injection properties compared to silver, but the improvement is insufficient and the drive voltage is sufficiently high. I found that there was a problem that did not go down.
  • Patent Document 2 the use of a magnesium-calcium alloy for the cathode electrode has been studied with the aim of further improving the electron injection property of the magnesium-silver alloy.
  • calcium has low stability as a material, the element can be operated at a high temperature. It was found that the performance fluctuation when stored was large.
  • Silver is an example of a material having high stability.
  • the layer thickness of the silver layer is reduced to 10 nm or less when the layer thickness of the silver layer is reduced to improve the transmittance. In this case, it has been found that it is difficult to maintain conductivity. Further, as another problem when silver is used for the cathode (cathode), since silver has a work function deeper than that of magnesium or calcium, there is a problem that the shortage of electron injectability becomes larger.
  • JP 2006-59818 A Japanese Patent No. 4292246
  • the present invention has been made in view of the above-mentioned problems and situations, and a problem to be solved is to provide an organic electroluminescence element and a lighting device having a low driving voltage and a high element transmittance.
  • An organic electroluminescent device having a light emitting layer containing an organic compound between an anode and a cathode, wherein the cathode contains a layer containing potassium or a potassium compound and silver or a silver compound from the side close to the light emitting layer
  • An organic electroluminescence device characterized in that it has a laminated structure with a layer, and the layer thickness of the layer containing silver or a silver compound is in the range of 1 to 10 nm.
  • E1 to E8 each represent —C (R1) ⁇ or N ⁇ .
  • R, R ′ and R1 each independently represent a hydrogen atom, a substituent or a linking site with Y1.
  • the symbol * represents a connecting site with Y1.
  • Y2 represents a simple bond or a divalent linking group.
  • Y3 and Y4 each represent a group derived from a 5-membered or 6-membered aromatic ring, and at least one represents a group derived from an aromatic heterocycle containing a nitrogen atom as a ring-constituting atom.
  • n2 represents an integer of 1 to 4. ] 4).
  • Y5 represents the bivalent coupling group which consists of an arylene group, heteroarylene group, or those combination.
  • E51 to E66 each represent —C (R3) ⁇ or N ⁇ , and R3 represents a hydrogen atom or a substituent.
  • Y6 to Y9 each represents a group derived from an aromatic hydrocarbon ring or a group derived from an aromatic heterocycle, and at least one of Y6 or Y7 and at least one of Y8 or Y9 is an aromatic group containing an N atom.
  • n3 and n4 represent an integer of 0 to 4, and n3 + n4 is an integer of 2 or more.
  • 5. 5 The organic electroluminescent device according to item 4, wherein the electron transporting compound represented by the general formula (2) is a compound represented by the following general formula (3).
  • Y5 represents the bivalent coupling group which consists of an arylene group, heteroarylene group, or those combination.
  • E51 to E66 and E71 to E88 each represent —C (R3) ⁇ or N ⁇ , and R3 represents a hydrogen atom or a substituent.
  • R3 represents a hydrogen atom or a substituent.
  • n3 and n4 represent an integer of 0 to 4, and n3 + n4 is an integer of 2 or more.
  • the said light emitting layer contains the compound represented by following General formula (4), The organic electroluminescent element as described in any one of said 1st term
  • A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC.
  • A2 represents an atomic group that forms an aromatic heterocycle with QN.
  • P1-L1-P2 represents an m2-dentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
  • L1 represents an atomic group that forms a bidentate ligand together with P1 and P2.
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M1 represents a transition metal element of Group 8 to Group 10 in the periodic table.
  • Z represents a hydrocarbon ring group or a heterocyclic group.
  • P and Q each represent a carbon atom or a nitrogen atom.
  • A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC.
  • R01 and R02 each represents a hydrogen atom or a substituent.
  • P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom.
  • L1 represents an atomic group that forms a bidentate ligand together with P1 and P2.
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M1 represents a group 8-10 transition metal element in the m-element periodic table. ] 8).
  • the organic electroluminescence device according to any one of items 1 to 8, further comprising an auxiliary electrode on the layer containing silver or a silver compound.
  • the above-mentioned means of the present invention can provide an organic electroluminescence element and a lighting device with low driving voltage and high element transmittance.
  • the means of the present invention is a technique in which both cathode transmittance and conductivity are satisfied by using a cathode in which a layer having potassium or a potassium compound and a layer made of silver or a silver compound are laminated, and further satisfying electron injection properties. It is.
  • silver since silver has a tendency to take the former-Weber growth mode in film growth, it has a characteristic that it is more likely to be a sea-island shape than a continuous film, but contains potassium or a potassium compound according to the present invention.
  • a layer containing silver or a silver compound is formed on the layer to be formed, it becomes easy to form a continuous film. As a result, even if the layer thickness of silver is reduced, conductivity can be maintained, so that the transmittance can be increased. It becomes possible.
  • the layer having potassium or potassium compound according to the present invention has an effect of compensating for the lack of electron injection property of silver, and as a result, it becomes possible to easily inject electrons from silver.
  • the organic electroluminescent device of the present invention is an organic electroluminescent device having a light emitting layer containing an organic compound between an anode and a cathode, and the cathode contains potassium or a potassium compound from the side close to the light emitting layer.
  • the layer is composed of a layer and a layer containing silver or a silver compound, and the layer thickness of the layer containing silver or a silver compound is in the range of 1 to 10 nm. This feature is a technical feature common to the inventions according to claims 1 to 11.
  • the layer containing potassium or a potassium compound further contains an electron transporting compound from the viewpoint of manifesting the effects of the present invention.
  • the electron transporting compound is preferably a compound represented by the general formula (1).
  • the electron transporting compound represented by the general formula (1) is preferably a compound represented by the general formula (2). Moreover, it is preferable that the electron transport compound represented by the general formula (2) is a compound represented by the general formula (3).
  • the light emitting layer preferably contains a compound represented by the general formula (4).
  • the compound represented by the said General formula (4) is a compound represented by the said General formula (5).
  • M1 in the general formula (4) or (5) represents iridium.
  • the auxiliary electrode is provided on the silver or silver compound-containing layer. Moreover, it is preferable that it is a double-sided emission type.
  • the organic electroluminescence element of the present invention can be suitably used for a lighting device.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the organic electroluminescence device of the present invention (hereinafter also referred to as “organic EL device”) is an organic electroluminescence device having a light emitting layer containing an organic compound between an anode and a cathode, and the cathode is the light emitting layer.
  • a layer containing a layer containing potassium or a potassium compound and a layer containing silver or a silver compound from the side near the surface, and the layer thickness of the layer containing silver or a silver compound is in the range of 1 to 10 nm It is characterized by that.
  • the layer structure of the organic EL element of the present invention can take various forms, and preferred specific examples are shown below.
  • Anode / hole injection layer / hole transport layer light emitting layer / electron transport layer / cathode layer containing potassium or potassium compound / layer containing silver or silver compound
  • Anode / hole injection layer / hole transport layer light emitting layer / electron transport layer / electron injection layer / cathode layer containing potassium or potassium compound / layer containing silver or silver compound
  • Anode / hole injection layer / hole transport layer light emitting layer / electron transport layer / hole blocking layer / cathode layer containing potassium or potassium compound / layer containing silver or silver compound
  • Anode / hole injection layer / hole transport layer light emitting layer / electron transport layer / electron injection layer / hole blocking layer / cathode layer containing potassium or potassium compound / layer containing silver or silver compound
  • the organic EL device of the present invention is characterized in that the cathode is substantially transparent, and the opposing electrode can be selected from either transparent or
  • the light emitting layer preferably contains at least two kinds of light emitting materials having different emission colors, and a single layer or a light emitting layer unit composed of a plurality of light emitting layers may be formed.
  • the hole transport layer also includes a hole injection layer and an electron blocking layer.
  • the cathode according to the present invention (hereinafter also referred to as “cathode”) has a laminated structure of a layer containing potassium or a potassium compound and a layer containing silver or a silver compound from the side close to the light emitting layer, and
  • the layer made of silver or a silver compound has a layer thickness in the range of 1 to 10 nm.
  • the cathode may be further provided outside the layer containing potassium or potassium compound, the layer containing silver or silver compound, the layer containing potassium or potassium compound, silver or
  • the layer containing a silver compound may be composed of a plurality of layers.
  • the layer containing potassium or a potassium compound according to the present invention is preferably formed by a vapor deposition method.
  • the potassium compound according to the present invention include potassium halides such as potassium chloride and potassium fluoride, and potassium salts such as potassium carbonate.
  • potassium fluoride is preferred.
  • the layer containing potassium or potassium compound according to the present invention is preferably formed by co-evaporation of potassium or potassium compound and an electron transporting material.
  • Preferred materials for the electron transporting material according to the present invention are compounds represented by the following general formulas (1) to (3).
  • the content of potassium or potassium compound according to the present invention is preferably in the range of 1 to 50% by mass relative to the total mass of the layer containing potassium or potassium compound. A more preferable range of the content of the potassium or potassium compound is 5 to 20%.
  • the layer containing silver or a silver compound according to the present invention is preferably formed by vapor deposition.
  • the layer containing the silver or silver compound has a layer thickness in the range of 1 to 10 nm.
  • the layer thickness is greater than 10 nm, the absorption of the layer containing silver or a silver compound increases, which is not desirable because the transmittance of the device decreases. On the other hand, if the layer thickness is less than 1 nm, the conductivity of the layer is insufficient and the voltage increases, which is not desirable.
  • the layer containing silver or a silver compound according to the present invention may be co-evaporated with other metal elements as necessary.
  • the shape of the layer containing silver or silver compound can be controlled, and the conductivity can be maintained even with a thinner layer thickness compared to the case without co-evaporation. It becomes possible to improve.
  • the metal element co-deposited with silver is not particularly limited, but a metal element having a deposition temperature of 1000 ° C. or less, such as magnesium, indium, or copper, is preferable.
  • the electron transporting compound is preferably a compound represented by the following general formula (1).
  • Formula (1) (Ar1) n1-Y1 [Wherein n1 represents an integer of 1 or more. Y1 represents a substituent when n1 is 1, and represents a simple bond or an n1-valent linking group when n1 is 2 or more.
  • Ar1 represents a group represented by the following general formula (A). When n1 is 2 or more, a plurality of Ar1s may be the same or different. However, the compound represented by the general formula (1) has at least two condensed aromatic heterocycles in which three or more rings are condensed in the molecule. ]
  • X represents —N (R) —, —O—, —S— or Si (R) (R ′) —.
  • E1 to E8 each represent —C (R1) ⁇ or N ⁇ .
  • R, R ′ and R1 each independently represent a hydrogen atom, a substituent or a linking site with Y1.
  • the symbol * represents a connecting site with Y1.
  • Y2 represents a simple bond or a divalent linking group.
  • Y3 and Y4 each represent a group derived from a 5-membered or 6-membered aromatic ring, and at least one represents a group derived from an aromatic heterocycle containing a nitrogen atom as a ring-constituting atom.
  • n2 represents an integer of 1 to 4.
  • examples of the substituent represented by Y1 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 etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl etc.) Group), aromatic hydrocarbon group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group
  • alkyl group for
  • Aryloxy groups for example, phenoxy group, naphthyloxy group, etc.
  • alkylthio groups for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.
  • cycloalkylthio groups for example, Cyclopentylthio group, cyclohexylthio group, etc.
  • arylthio group eg, phenylthio group, naphthylthio group, etc.
  • alkoxycarbonyl group eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyl
  • aryloxycarbonyl group eg, phenyloxycarbonyl group, naph
  • substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • n1-valent linking group represented by Y1 in the general formula (1) examples include a divalent linking group, a trivalent linking group, and a tetravalent linking group.
  • an alkylene group 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.), Cyclopentylene group (for example, 1,5-cyclopentanediyl group and the like), alkenylene group (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, 3-methyl Pentenylene group, 1-ethylvinylene group, 1-
  • Ring specifically, acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, cyclazine ring, kindrin ring, tepenidine ring, quinindrin ring, triphenodi A thiazine ring, a triphenodioxazine ring, a phenanthrazine ring, an anthrazine ring, a perimidine ring, a diazacarbazole ring (representing any one of the carbon atoms constituting the carboline ring replaced by a nitrogen atom), a phenanthroline ring, Dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene , Benzodifuran ring, benzodithiophene ring, naphthodifuran
  • examples of the trivalent linking group represented by Y1 include ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, and octanetriyl.
  • the tetravalent linking group represented by Y1 is a group in which one trivalent group is further added to the above trivalent group.
  • each of the divalent linking group, the trivalent linking group, and the tetravalent linking group may further have a substituent represented by Y1 in the general formula (1).
  • Y1 preferably represents a group derived from a condensed aromatic heterocyclic ring formed by condensation of three or more rings, and the three or more rings.
  • a condensed aromatic heterocyclic ring formed by condensing a dibenzofuran ring or a dibenzothiophene ring is preferable.
  • n1 is preferably 2 or more.
  • the compound represented by the general formula (1) has at least two condensed aromatic heterocycles formed by condensation of three or more rings in the molecule.
  • Y1 represents an n1-valent linking group
  • Y1 is preferably non-conjugated in order to keep the triplet excitation energy of the compound represented by the general formula (1) high, and further Tg (glass transition point). From the point of improving the glass transition temperature, it is preferably composed of an aromatic ring (aromatic hydrocarbon ring + aromatic heterocycle).
  • non-conjugated means that the linking group cannot be expressed by repeating a single bond (also referred to as a single bond) and a double bond, or the conjugate of aromatic rings constituting the linking group is sterically cleaved. Means.
  • Ar1 represents a group represented by the general formula (A).
  • R1 has the same meaning as the substituent represented by Y1 in the general formula (1).
  • the divalent linking group represented by Y2 has the same meaning as the divalent linking group represented by Y1 in the general formula (1).
  • a 5-membered or 6-membered aromatic ring used for forming a group derived from a 5-membered or 6-membered aromatic ring represented by Y3 and Y4, respectively, includes a benzene ring, oxazole Examples include a ring, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a diazine ring, a triazine ring, an imidazole ring, an isoxazole ring, a pyrazole ring, and a triazole ring.
  • At least one of the groups derived from a 5-membered or 6-membered aromatic ring represented by Y3 and Y4 represents a group derived from an aromatic heterocycle containing a nitrogen atom as a ring-constituting atom
  • the aromatic heterocycle containing a nitrogen atom as the ring atom include an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a diazine ring, a triazine ring, an imidazole ring, an isoxazole ring, a pyrazole ring, Examples include a triazole ring.
  • the group represented by Y3 is preferably a group derived from the above 6-membered aromatic ring, and more preferably a group derived from a benzene ring.
  • the group represented by Y4 is preferably a group derived from the 6-membered aromatic ring, more preferably an aromatic heterocycle containing a nitrogen atom as a ring constituent atom. Particularly preferably, Y4 is a group derived from a pyridine ring.
  • X represents —N (R) —, —O—, —S— or Si (R) (R ′) —.
  • E1 to E8 each represent —C (R1) ⁇ or N ⁇ .
  • R, R ', and R1 represent a hydrogen atom, a substituent, or a connection part with Y1.
  • Y2 represents a simple bond or a divalent linking group.
  • E11 to E20 each represent —C (R2) ⁇ or N ⁇ , and at least one represents —N ⁇ .
  • R2 represents a hydrogen atom, a substituent or a linking site. However, at least one of E11 and E12 represents —C (R2) ⁇ , and R2 represents a linking site.
  • n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (1).
  • X represents —N (R) —, —O—, —S— or Si (R) (R ′) —.
  • E1 to E8 each represent —C (R1) ⁇ or N ⁇ .
  • R, R ', and R1 represent a hydrogen atom, a substituent, or a connection part with Y1.
  • Y2 represents a simple bond or a divalent linking group.
  • R2 represents a hydrogen atom, a substituent or a linking site
  • R3 and R4 represent a hydrogen atom or a substituent.
  • at least one of E21 or E22 represents —C (R2) ⁇
  • R2 represents a linking site
  • n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (1).
  • X represents —N (R) —, —O—, —S— or Si (R) (R ′) —.
  • E1 to E8 each represent —C (R1) ⁇ or N ⁇ .
  • R, R ', and R1 represent a hydrogen atom, a substituent, or a connection part with Y1.
  • Y2 represents a simple bond or a divalent linking group.
  • R2 represents a hydrogen atom, a substituent or a linking site
  • R3 and R4 represent a hydrogen atom or a substituent.
  • at least one of E32 or E33 is represented by —C (R2) ⁇
  • R2 represents a linking site
  • n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (1).
  • X represents —N (R) —, —O—, —S— or Si (R) (R ′) —.
  • E1 to E8 each represent —C (R1) ⁇ or N ⁇ .
  • R, R ', and R1 represent a hydrogen atom, a substituent, or a connection part with Y1.
  • Y2 represents a simple bond or a divalent linking group.
  • E41 to E50 each represents —C (R2) ⁇ , —N ⁇ , —O—, —S— or Si (R3) (R4) —, and at least one of them represents —N ⁇ .
  • R2 represents a hydrogen atom, a substituent or a linking site
  • R3 and R4 represent a hydrogen atom or a substituent.
  • n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (1).
  • the divalent linking group represented by Y2 is a divalent group represented by Y1 in the general formula (1). It is synonymous with the linking group.
  • Y5 represents the bivalent coupling group which consists of an arylene group, heteroarylene group, or those combination.
  • E51 to E66 each represent —C (R3) ⁇ or N ⁇ , and R3 represents a hydrogen atom or a substituent.
  • Y6 to Y9 each represents a group derived from an aromatic hydrocarbon ring or a group derived from an aromatic heterocycle, and at least one of Y6 or Y7 and at least one of Y8 or Y9 is an aromatic group containing an N atom.
  • n3 and n4 represent an integer of 0 to 4, and n3 + n4 is an integer of 2 or more.
  • the arylene group and heteroarylene group represented by Y5 are the arylene group and heteroarylene group described as an example of the divalent linking group represented by Y1 in general formula (1). Are synonymous with each other.
  • the divalent linking group consisting of an arylene group, a heteroarylene group or a combination thereof represented by Y5
  • a condensed aromatic heterocycle formed by condensation of three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable.
  • Y6 to Y9 are each an aromatic hydrocarbon ring used for forming a group derived from an aromatic hydrocarbon ring, such as a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring Phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring , Pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring, and the like.
  • aromatic hydrocarbon ring may have a substituent represented by Y1 in the general formula (1).
  • Y6 to Y9 are each an aromatic heterocycle used for forming a group derived from an aromatic heterocycle, such as a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, or a pyridine ring.
  • aromatic hydrocarbon ring may have a substituent represented by Y1 in the general formula (1).
  • an aromatic heterocycle containing an N atom used for forming a group derived from an aromatic heterocycle containing an N atom represented by at least one of Y6 or Y7 and at least one of Y8 or Y9.
  • the ring include, for example, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, Indole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyr
  • the groups represented by Y7 and Y9 each preferably represent a group derived from a pyridine ring.
  • the groups represented by Y6 and Y8 each preferably represent a group derived from a benzene ring.
  • Y5 represents the bivalent coupling group which consists of an arylene group, heteroarylene group, or those combination.
  • E51 to E66 and E71 to E88 each represent —C (R3) ⁇ or N ⁇ , and R3 represents a hydrogen atom or a substituent.
  • R3 represents a hydrogen atom or a substituent.
  • n3 and n4 represent an integer of 0 to 4, and n3 + n4 is an integer of 2 or more.
  • the arylene group and heteroarylene group represented by Y5 are the arylene group and heteroarylene group described as an example of the divalent linking group represented by Y1 in general formula (1). Are synonymous with each other.
  • the divalent linking group consisting of an arylene group, a heteroarylene group or a combination thereof represented by Y5
  • a condensed aromatic heterocycle formed by condensation of three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable.
  • DMAc dimethylacetamide
  • Step 2 (Synthesis of Intermediate 2) Intermediate 1 (0.5 mol) was dissolved in 100 ml of DMF at room temperature under air, NBS (2.0 mol) was added, and the mixture was stirred overnight at room temperature. The resulting precipitate was filtered and washed with methanol, yielding intermediate 2 in 92% yield.
  • Step 3 (Synthesis of Compound 5) Under a nitrogen atmosphere, intermediate 2 (0.25 mol), 2-phenylpyridine (1.0 mol), ruthenium complex [( ⁇ 6 -C 6 H 6 ) RuCl 2 ] 2 (0.05 mol), triphenyl Phosphine (0.2 mol) and potassium carbonate (12 mol) were mixed in 3 L of NMP (N-methyl-2-pyrrolidone) and stirred at 140 ° C. overnight.
  • NMP N-methyl-2-pyrrolidone
  • an auxiliary electrode can be provided on the transparent conductive layer for the purpose of reducing the resistance.
  • a material for forming the auxiliary electrode a metal having low resistance such as gold, platinum, silver, copper, and aluminum is preferable.
  • the method for forming the auxiliary electrode include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method.
  • the line width of the auxiliary electrode according to the present invention is preferably 50 ⁇ m or less from the viewpoint of the aperture ratio of the transparent conductive layer, and the thickness of the auxiliary electrode is preferably 1 ⁇ m or more from the viewpoint of conductivity.
  • the light emitting layer according to the present invention is characterized in that a phosphorescent compound is contained as a light emitting material.
  • the light-emitting layer 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 the light-emitting layer even in the layer of the light-emitting layer. It may be an interface with an adjacent layer.
  • the light emitting layer is not particularly limited in its configuration as long as the light emitting material included satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. Moreover, it is preferable to have a non-light emitting intermediate
  • the total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, more preferably 1 nm or more and 30 nm or less because a lower driving voltage can be obtained. Note that the sum of the thicknesses of the light emitting layers is a layer thickness including the intermediate layers when a non-light emitting intermediate layer exists between the light emitting layers.
  • each light emitting layer is preferably adjusted to a range of 1 to 50 nm, more preferably adjusted to a range of 1 to 20 nm. There is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.
  • a light-emitting material or a host compound which will be described later, is formed by forming a film by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an inkjet method. it can.
  • Each light emitting layer may be a mixture of a plurality of light emitting materials, or a phosphorescent light emitting material and a fluorescent light emitting material may be mixed and used in the same light emitting layer.
  • the structure of the light emitting layer preferably contains a host compound and a light emitting material (also referred to as a light emitting dopant compound) and emits light from the light emitting material.
  • a light emitting material also referred to as a light emitting dopant compound
  • a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.
  • known host compounds may be used alone or in combination of two or more.
  • the organic EL element can be made highly efficient.
  • the host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .
  • Tg glass transition temperature
  • DSC Different Scanning Colorimetry
  • a phosphorescent compound also referred to as a phosphorescent compound or a phosphorescent material
  • the light-emitting material can be used as the light-emitting material.
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C.
  • a preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, when the phosphorescent compound is used in the present invention, the above phosphorescence quantum yield (0.01 or more) is obtained in any solvent. It only has to be achieved.
  • phosphorescent compounds There are two types of light emission principles of phosphorescent compounds. One is the recombination of carriers on the host compound to which carriers are transported, generating an excited state of the host compound, and this energy is phosphorescent.
  • the energy transfer type is to obtain light emission from the phosphorescent compound by transferring to the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, and recombination of carriers on the phosphorescent compound is performed.
  • This is a carrier trap type in which light emission from the phosphorescent compound can be obtained, but in any case, the excited state energy of the phosphorescent compound must be lower than the excited state energy of the host compound. It is.
  • the phosphorescent compound can be appropriately selected from known compounds used for the light-emitting layer of the organic EL device, and preferably a complex system containing a metal of group 8 to 10 in the periodic table of elements.
  • a compound more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound.
  • At least one phosphorescent compound may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the phosphor layer varies in the thickness direction of the phosphor layer. May be.
  • the phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer.
  • the phosphorescent compound according to the present invention is preferably a compound represented by the following general formula (4).
  • P and Q each represent a carbon atom or a nitrogen atom.
  • A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC.
  • A2 represents an atomic group that forms an aromatic heterocycle with QN.
  • P1-L1-P2 represents an m2-dentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
  • L1 represents an atomic group that forms a bidentate ligand together with P1 and P2.
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M1 represents a transition metal element of Group 8 to Group 10 in the periodic table.
  • a compound represented by the general formula (4) is preferable.
  • the phosphorescent compound represented by the general formula (4) (also referred to as a phosphorescent metal complex) is preferably contained as a luminescent dopant in the light emitting layer of the organic EL device of the present invention. However, it may be contained in a constituent layer other than the light emitting layer (the constituent layer of the organic EL element of the present invention will be described in detail later).
  • the aromatic hydrocarbon ring formed by A1 together with P—C includes a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, Triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, Examples include a pyrene ring, a pyrantolen ring, and anthraanthrene ring.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • the aromatic heterocycle formed by A1 together with P—C includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, azacarbazole A ring etc. are mentioned.
  • the azacarbazole ring refers to one in which one or more carbon atoms of the benzene ring constituting the carbazole ring are replaced with nitrogen atoms.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • examples of the aromatic heterocycle formed by A2 together with QN include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, a thiatriazole ring, Examples include a thiazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, a pyrazole ring, and a triazole ring.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • examples of the bidentate ligand represented by P1-L1-P2 include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabole, acetylacetone, and picolinic acid. .
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 represents 2 or 3
  • j2 is preferably 0.
  • M1 is a transition metal element of Group 8 to Group 10 (also referred to simply as transition metal) in the periodic table of elements, and iridium is particularly preferable.
  • the phosphorescent compound according to the present invention is more preferably a compound represented by the following general formula (5).
  • Z represents a hydrocarbon ring group or a heterocyclic group.
  • P and Q each represent a carbon atom or a nitrogen atom.
  • A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC.
  • R01 and R02 each represents a hydrogen atom or a substituent.
  • P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom.
  • L1 represents an atomic group that forms a bidentate ligand together with P1 and P2.
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M1 represents a group 8-10 transition metal element in the m-element periodic table.
  • examples of the hydrocarbon ring group represented by Z include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or have a substituent described later.
  • aromatic hydrocarbon ring group examples include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl. Group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.
  • These groups may be unsubstituted or may have a substituent represented by Y1 in the general formula (1).
  • examples of the heterocyclic group represented by Z include a non-aromatic heterocyclic group and an aromatic heterocyclic group.
  • examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ⁇ -caprolactone ring, ⁇ - Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring
  • These groups may be unsubstituted or may have a substituent represented by Y1 in the general formula (1).
  • aromatic heterocyclic group examples include a pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl).
  • oxazolyl group 1,2,3-triazol-1-yl group, etc.
  • 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 (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, Nazoriniru group, phthalazinyl group, and the like.
  • These groups may be unsubstituted or may have a substituent represented by Y1 in the general formula (1).
  • the group represented by Z is an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the aromatic hydrocarbon ring that A1 forms with P—C includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring , Triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring , Pyrene ring, pyranthrene ring, anthraanthrene ring and the like.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • the aromatic heterocycle formed by A1 together with P—C includes furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzo Imidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, And azacarbazole ring.
  • the azacarbazole ring refers to one in which one or more carbon atoms of the benzene ring constituting the carbazole ring are replaced with nitrogen atoms.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • examples of the bidentate ligand represented by P1-L1-P2 include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabole, acetylacetone, and picolinic acid. .
  • J1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 represents 2 or 3
  • j2 is preferably 0.
  • transition metal elements of groups 8 to 10 in the periodic table of elements represented by M1 (also simply referred to as transition metals) in the periodic table of elements represented by M1 in the general formula (4) Synonymous with group 8-10 transition metal elements.
  • R03 represents a substituent.
  • R04 represents a hydrogen atom or a substituent, and a plurality of R04 may be bonded to each other to form a ring.
  • n01 represents an integer of 1 to 4.
  • R05 represents a hydrogen atom or a substituent, and a plurality of R05 may be bonded to each other to form a ring.
  • n02 represents an integer of 1 to 2.
  • R06 represents a hydrogen atom or a substituent, and may combine with each other to form a ring.
  • n03 represents an integer of 1 to 4.
  • Z1 represents an atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle together with C—C.
  • Z2 represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group.
  • P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
  • L1 represents an atomic group that forms a bidentate ligand together with P1 and P2.
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M1 represents a transition metal element of Group 8 to Group 10 in the periodic table.
  • R03 and R06, R04 and R06, and R05 and R06 may be bonded to each other to form a ring.
  • each of the substituents represented by R03, R04, R05, and R06 has the same meaning as the substituent represented by Y1 in the general formula (1).
  • examples of the 6-membered aromatic hydrocarbon ring formed by Z1 together with C—C include a benzene ring.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • examples of the 5-membered or 6-membered aromatic heterocycle formed by Z1 together with C—C include oxazole ring, oxadiazole ring, oxatriazole ring, isoxazole ring, tetrazole ring, thiadiazole And a ring, a thiatriazole ring, an isothiazole ring, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, a pyrazole ring, and a triazole ring.
  • These rings may further have a substituent represented by Y1 in the general formula (1).
  • examples of the hydrocarbon ring group represented by Z2 include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or have a substituent described later.
  • aromatic hydrocarbon ring group examples include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl.
  • aromatic hydrocarbon group examples include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl.
  • These groups may be unsubstituted or may have a substituent represented by Y1 in the general formula (1).
  • examples of the heterocyclic group represented by Z2 include a non-aromatic heterocyclic group and an aromatic heterocyclic group.
  • examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ⁇ -caprolactone ring, ⁇ - Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran
  • aromatic heterocyclic group examples include a pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl).
  • oxazolyl group 1,2,3-triazol-1-yl group, etc.
  • 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 (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, Nazoriniru group, phthalazinyl group, and the like.
  • These rings may be unsubstituted and may further have a substituent represented by Y1 in the general formula (1).
  • the group formed by Z1 and Z2 is preferably a benzene ring.
  • the bidentate ligand represented by P1-L1-P2 has the same meaning as the bidentate ligand represented by P1-L1-P2 in the general formula (4). .
  • the transition metal elements of groups 8 to 10 in the periodic table of elements represented by M1 are the transition metal groups of groups 8 to 10 in the periodic table of elements represented by M1 in the general formula (4). Synonymous with metal element.
  • the phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.
  • the phosphorescent compound 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 compound) ), Rare earth complexes, and most preferred are iridium compounds.
  • the above phosphorescent compound (also referred to as a phosphorescent metal complex or the like) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, pages 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, pages 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and further synthesized by applying methods such as references described in these documents. it can.
  • the non-light emitting intermediate layer is a layer provided between the light emitting layers.
  • the layer thickness of the non-light emitting intermediate layer is preferably in the range of 1 to 20 nm, and more preferably in the range of 3 to 10 nm to suppress interaction such as energy transfer between adjacent light emitting layers, and This is preferable because a large load is not applied to the voltage characteristics.
  • the material used for the non-light emitting intermediate layer may be the same as or different from the host compound of the light emitting layer, but may be the same as the host material of at least one of the adjacent two light emitting layers. preferable.
  • the non-light-emitting intermediate layer may contain a non-light-emitting layer, a compound common to each light-emitting layer (for example, a host compound), and each common host material (where a common host material is used)
  • a compound common to each light-emitting layer for example, a host compound
  • each common host material where a common host material is used
  • the injection barrier is reduced, and it is possible to obtain an effect that the injection balance of holes and electrons can be easily maintained even when the voltage (current) is changed.
  • Carrier mobility is used as a physical property representing carrier transport ability, but the carrier mobility of an organic material generally depends on the electric field strength. Since a material having a high electric field strength dependency easily breaks the balance between injection and transport of holes and electrons, it is preferable to use a material having a low electric field strength dependency of mobility for the intermediate layer material and the host material.
  • the non-light emitting intermediate layer functions as a blocking layer described later, that is, a hole blocking layer and an electron blocking layer. Can be mentioned.
  • 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 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.
  • the hole blocking layer has a function of an electron transport layer and is composed of a hole blocking material having a function of transporting electrons and having a remarkably small ability to transport holes, while transporting electrons. By blocking holes, the recombination probability of electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer is preferably provided adjacent to the light emitting layer.
  • the electron blocking layer in a broad sense, has a function of a hole transport layer, and is made of a material having a function of transporting holes while having a remarkably small ability to transport electrons, while transporting holes. By blocking electrons, the probability of recombination 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 layer thickness of the hole blocking layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.
  • 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.
  • 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.
  • 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-tolylaminoph
  • No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.
  • NPD 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the
  • polymer materials in which these materials are introduced into polymer chains or these materials are used as polymer main chains can also be used.
  • 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 described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials 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.
  • the layer thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • 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.
  • an electron transport material also serving as a hole blocking material used for an electron transport layer adjacent to the cathode side with respect to the light emitting layer is injected from the cathode.
  • an electron transport material also serving as a hole blocking material
  • any material selected from conventionally known compounds can be selected and used.
  • nitro-substituted fluorene derivatives for example, nitro-substituted fluorene derivatives, diphenylquinone Derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • 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.
  • 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.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq 3 ), 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.
  • Mg Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as electron transport materials.
  • 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.
  • the distyrylpyrazine derivatives exemplified as the material of the light emitting layer can also be used as the electron transport material, and inorganic semiconductors such as n-type-Si and n-type-SiC can be used as well as the hole injection layer and the hole transport layer. It can 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. .
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • an electron transport layer having a high n property doped with impurities 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.
  • the injection layer is provided as necessary, and includes an electron injection layer and a hole injection layer. As described above, between the anode (hereinafter also referred to as “anode”) and the light emitting layer or hole transport layer, and a cathode (hereinafter referred to as “cathode”). And a light emitting layer or an electron transport layer.
  • 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) ) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123 to 166), which has a hole injection layer and an electron injection layer.
  • JP-A Nos. 9-45479, 9-260062, and 8-288069 The details of the hole injection layer are described in JP-A Nos. 9-45479, 9-260062, and 8-288069. Specific examples thereof include a phthalocyanine layer represented by copper phthalocyanine. And an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • the details of the electron injection layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically, metals represented by strontium, aluminum and the like.
  • Examples thereof include an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide.
  • the electron injection layer according to the present invention preferably has a laminated structure of a metal layer and an alkali metal halide layer or a laminated structure of an oxide layer, a metal layer and an alkali metal halide layer, and the metal oxide may be doped with an alkali metal. good.
  • the amount of alkali metal doped in the metal oxide is preferably 1 to 10% by mass.
  • the electron injection layer is preferably a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 ⁇ m although it depends on the material
  • the above-described material constituting the transparent conductivity may be used, or an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof. It can also be 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.
  • the counter electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Further, the sheet resistance as the counter electrode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • light 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, and light sources for optical sensors. Although it is not limited to this, it can be effectively used for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.
  • Example 1 Production of double-sided emission type organic EL elements >> The organic EL elements 1 to 20 were produced so that the light emitting area was 5 cm ⁇ 5 cm.
  • FIG. 1 is a conceptual diagram showing an example of the configuration of the organic electroluminescence element of the present invention.
  • the substrate provided with the ITO layer is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, and ⁇ -NPD, H4, Ir-4, BAlq, Alq 3 , potassium chloride, potassium fluoride, fluoride fluoride are mounted on a tantalum resistance heating board. Lithium was added and attached to the first vacuum chamber of the vacuum deposition apparatus.
  • silver was put into a resistance heating board made of tungsten and attached to the second vacuum chamber of the vacuum evaporation apparatus.
  • the heating board containing ⁇ -NPD was energized and heated, and the ITO layer was deposited at a deposition rate of 0.1 nm / second to 0.2 nm / second.
  • a hole injection / hole transport layer having a layer thickness of 20 nm was provided thereon.
  • the heating board containing H4 and the board containing Ir-4 are energized independently to adjust the deposition rate of H4 as a light emitting host and Ir-4 as a light emitting dopant to 100: 6. Then, a light emitting layer having a layer thickness of 30 nm was provided.
  • the heating board containing BAlq was energized and heated to provide a hole blocking layer having a layer thickness of 10 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.
  • the heating board containing Alq 3 was heated by energization to provide an electron transport layer having a layer thickness of 20 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.
  • the heating board containing lithium fluoride was energized and heated to provide an electron injection layer having a thickness of 1 nm on the electron transport layer at a deposition rate of 0.01 nm / sec to 0.02 nm / sec.
  • the obtained element was transferred to the second vacuum chamber while maintaining a vacuum, and the second vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and then the heating board containing silver was energized to obtain a deposition rate of 0.
  • a layer made of silver having a layer thickness of 15 nm was formed at 1 to 0.1 nm / second to 0.2 nm / second to obtain a cathode.
  • the heating board containing potassium chloride and the heating board containing Alq 3 were energized independently to adjust the deposition rate of potassium chloride and Alq 3 to be 1: 4.
  • An Alq 3 layer doped with 10 nm potassium chloride was provided.
  • the obtained element was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and then the heating board containing silver was energized to obtain a deposition rate of 0.1.
  • a layer made of silver having a layer thickness of 10 nm was formed at a thickness of ⁇ 0.1 nm / second to 0.2 nm / second to obtain a cathode.
  • organic EL elements 9 and 10 were produced in the same manner as the organic EL element 8 except that the compound (99) was changed to the compound (94) and the compound (10).
  • organic EL elements 11 to 13 were produced in the same manner as the organic EL element 10 except that Ir-4 was changed to Ir-12, Ir-24, and Ir-26.
  • Organic EL elements 14 to 17 were produced in the same manner as the organic EL element 13 except that the silver layer thickness was changed to the value described in Table 1.
  • an auxiliary electrode made of a line-shaped silver pattern was produced by a vapor deposition method using a shadow mask with a line width of 50 ⁇ m, a thickness of 1 ⁇ m, and a pitch of 1 mm.
  • An organic EL element 20 was produced in the same manner as the organic EL element 19 except that the film thickness of silver was changed to the value described in Table 1.
  • Table 1 shows the results obtained as described above.
  • the organic EL device according to the present invention has a lower drive voltage and higher device transmittance than the comparative example.

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Abstract

L'invention porte sur un élément électroluminescent organique, dont la tension de commande est faible et le facteur de transmission est élevé, et sur un appareil d'éclairage. Cet élément électroluminescent organique présente, entre l'anode et la cathode, une couche émettrice de lumière contenant un composé organique. L'élément électroluminescent organique est caractérisé en ce que la cathode possède une configuration stratifiée, une couche contenant du potassium ou un composé du potassium et une couche contenant de l'argent ou un composé de l'argent étant stratifiées, dans cet ordre, à partir du côté proche de la couche émettrice de lumière, et en ce que l'épaisseur de la couche contenant de l'argent ou le composé d'argent se situe dans une plage de 1 à 10 nm.
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