WO2014034584A1 - Élément électroluminescent organique, illuminateur, et dispositif d'affichage - Google Patents

Élément électroluminescent organique, illuminateur, et dispositif d'affichage Download PDF

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WO2014034584A1
WO2014034584A1 PCT/JP2013/072664 JP2013072664W WO2014034584A1 WO 2014034584 A1 WO2014034584 A1 WO 2014034584A1 JP 2013072664 W JP2013072664 W JP 2013072664W WO 2014034584 A1 WO2014034584 A1 WO 2014034584A1
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organic
carbon atoms
atom
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西関　雅人
大野　香織
三浦　紀生
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コニカミノルタ株式会社
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Definitions

  • the present invention relates to an organic electroluminescence element, an illuminating device, and a display device, and more particularly, to a compound that can be preferably used for an organic electroluminescence element.
  • ELD electroluminescence display
  • an inorganic electroluminescence element and an organic electroluminescence element (hereinafter also referred to as an organic EL element) can be given.
  • Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.
  • an organic EL element has a configuration in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer to recombine excitons. It is an element that emits light by utilizing the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type complete solid-state device, it is attracting attention from the viewpoints of space saving and portability.
  • Organic EL elements that use phosphorescence emission can in principle achieve light emission efficiency about 4 times that of elements that use previous fluorescence emission. Research and development of electrodes and electrodes are conducted all over the world.
  • the phosphorescence emission method is a method having a very high potential, but in an organic EL device using phosphorescence emission, a method for controlling the position of the emission center, in particular, recombination inside the emission layer, How to stably emit light and how to improve the light emitting property of the phosphorescent material itself is an important technical issue from the viewpoint of the efficiency and life of the device.
  • iridium complexes having ligands such as phenylpyrazole, imidazophenanthridine, and phenylimidazole are known. It is very difficult to satisfy all of light emission and high durability at the same time.
  • a metal complex having imidazophenanthridine as a ligand is a light-emitting material having a short emission wavelength (see, for example, Patent Documents 2 and 3).
  • a metal complex of phenylimidazole is a light emitting material having a relatively short emission wavelength (see, for example, Patent Documents 4, 5, 6, and 7).
  • a wet method (also referred to as a wet process) has been attracting attention as a method for manufacturing organic EL elements.
  • this wet method film formation can be performed at a lower temperature than film formation by a vacuum process, so that damage to the organic layer located in the lower layer can be reduced, and luminous efficiency and device lifetime are improved.
  • the host material and the electron transport material of the organic EL element using blue phosphorescence are insufficient in solubility in a solvent and solution stability, and are difficult to manufacture by a wet method.
  • the organic EL element manufactured using the said host material and electron transport material also has a problem that a drive voltage is high.
  • the present invention has been made in view of the above-mentioned problems and circumstances, and the problem to be solved is organic electroluminescence that has a low driving voltage, high light emission efficiency, excellent durability, and excellent dark spot and light emission unevenness prevention effects. It is to provide an element. Moreover, it is providing the illuminating device and display apparatus with which it was comprised.
  • the present inventor has found that the cause of the above-mentioned problem, etc., of the organometallic complex having phenylimidazole as a ligand, the effect of improving the luminous efficiency at the phenylimidazole moiety and the N-phenyl group of the imidazole ring Coordination represented by the general formula (1) or the general formula (2) as a result of intensive investigation of the chemical structure from the viewpoint of efficiently achieving the function of separating the carrier transfer effect from the bonded aryl group. It has been found that the above problems can be solved by an organic EL device containing a phosphorescent organic metal whose child is coordinated to a metal atom.
  • An organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode, wherein at least one of the organic layers is represented by the following general formula (1) or general formula (2):
  • the organic electroluminescent element characterized by containing the phosphorescence-emitting organometallic complex in which the ligand represented by this coordinated to the metal atom.
  • Ring B represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle.
  • the ring E represents an aromatic hydrocarbon ring having 6 to 30 carbon atoms or an aromatic heterocyclic ring having 1 to 30 carbon atoms bonded to the ring D through G representing a carbon atom, a silicon atom, or a nitrogen atom.
  • R 1 and R 2 are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, non-group It represents an aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. At least one of R 1 and R 2 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • R 3 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • Ra, Rb, Rc, Rd and Re are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, hetero group It represents an aryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent.
  • Nb and nd represent integers of 1 to 4, and na and nc represent 1 or 2.
  • ne represents an integer of 1 to 20.
  • Adjacent ring A and ring D, and ring D and ring E may be bonded to each other at two points to form a condensed ring. Furthermore, ring A, ring D, and ring E may form one condensed ring.
  • the phosphorescent organometallic complex in which the ligand represented by the general formula (1) or the general formula (2) is coordinated to a metal atom is represented by the following general formula (3) or the general formula (4). 2.
  • Ring B represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle.
  • the ring E represents an aromatic hydrocarbon ring having 6 to 30 carbon atoms or an aromatic heterocyclic ring having 1 to 30 carbon atoms bonded to the ring D through G representing a carbon atom, a silicon atom, or a nitrogen atom.
  • R 1 and R 2 are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, non-group It represents an aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. At least one of R 1 and R 2 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • R 3 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • Ra, Rb, Rc, Rd and Re are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, hetero group It represents an aryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent.
  • Nb and nd represent integers of 1 to 4, and na and nc represent 1 or 2.
  • ne represents an integer of 1 to 20.
  • Adjacent ring A and ring D, ring D and ring E may be bonded to each other at two points to form a condensed ring. Furthermore, ring A, ring D, and ring E may form one condensed ring.
  • L represents one or more of monoanionic bidentate ligands coordinated to M.
  • M represents an atomic number of 40 or more and a transition metal atom of Group 8 to 10 in the periodic table, and m represents an integer of 0 to 2.
  • n is at least 1 and m + n is 2 or 3.
  • the phosphorescent organometallic complex represented by the general formula (3) or (4) is a phosphorescent organometallic complex represented by the following general formula (5) or (6), The organic electroluminescent element according to item 2.
  • the ring E is an aromatic hydrocarbon ring having 6 to 30 carbon atoms or carbon bonded to the ring D through G representing a carbon atom, a silicon atom or a nitrogen atom. Represents an aromatic heterocycle of formula 1 to 30.
  • R 1 and R 2 are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, non-group It represents an aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. At least one of R 1 and R 2 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • R 3 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • Ra, Rb, Rc, Rd and Re are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, hetero group It represents an aryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent.
  • Nb and nd represent integers of 1 to 4, and na and nc represent 1 or 2.
  • ne represents an integer of 1 to 20.
  • Adjacent ring A and ring D, ring D and ring E may be bonded to each other at two points to form a condensed ring. Furthermore, ring A, ring D, and ring E may form one condensed ring.
  • L represents one or more of monoanionic bidentate ligands coordinated to M.
  • M represents an atomic number of 40 or more and a transition metal atom of Group 8 to 10 in the periodic table, and m represents an integer of 0 to 2.
  • n is at least 1 and m + n is 2 or 3. ] 4). Any one of the adjacent ring A and ring D, ring D and ring E, or ring A, ring D and ring E of the organometallic complex forms a condensed ring.
  • the organic electroluminescence device according to any one of items 3 to 3.
  • the organic electroluminescent element according to any one of items 1 to 5, which is contained.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 8.
  • An organic electroluminescence element according to any one of items 1 to 8 is provided.
  • an organic electroluminescence device having a low driving voltage, high luminous efficiency, excellent durability, and excellent dark spot and emission unevenness prevention effect, and an illumination device and a display device equipped with the organic electroluminescent device. it can.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the D ring portion bonded to the N-phenyl group of the imidazole ring of the ligand represented by the general formula (1) or the general formula (2) protrudes to the m-position or the o-position with respect to the imidazole ring. Therefore, the interaction between the light-emitting dopants by the D ring part and the E ring part is not excessively strong, and the phenylimidazole part has an effect of improving the light emission efficiency and is bonded to the N-phenyl group of the imidazole ring. It is considered that the function separation effect of carrier transfer is more strongly expressed in the ring portion and the E ring portion.
  • Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of the display unit of the display device of FIG. Schematic diagram of the circuit of the display device of FIG. Schematic diagram of a passive matrix display device Schematic of lighting device Cross section of the lighting device
  • the organic electroluminescence device of the present invention is an organic electroluminescence device in which at least one organic layer including a light emitting layer is sandwiched between an anode and a cathode, and at least one layer of the organic layer has the general formula
  • the ligand represented by (1) or general formula (2) contains a phosphorescent organometallic complex coordinated to a metal atom. This feature is a technical feature common to the inventions according to claims 1 to 10.
  • a phosphorescent organometallic complex in which the ligand represented by the general formula (1) or the general formula (2) is coordinated to a metal atom from the viewpoint of manifesting the effect of the present invention.
  • it is preferable that it is a phosphorescence-emitting organometallic complex represented by General formula (3) or General formula (4).
  • the phosphorescent organometallic complex represented by the general formula (3) or (4) is preferably a phosphorescent organometallic complex represented by the general formula (5) or (6).
  • any of adjacent ring A and ring D, ring D and ring E, or ring A, ring D and ring E of the organometallic complex form a condensed ring. .
  • the transition metal atom of group 8 to 10 in the periodic table with the atomic number of 40 or more is preferably iridium.
  • the light emitting layer has a ring structure in which at least one of carbon atoms of a hydrocarbon ring constituting a fluorene derivative, a dibenzofuran derivative, a dibenzothiophene derivative, a carbazole derivative or a condensed ring compound derivative thereof is substituted with a nitrogen atom. It is preferable to contain the derivative
  • the organic layer containing the phosphorescent organometallic complex is a layer formed through a wet process because a homogeneous film is easily obtained and pinholes are hardly generated.
  • the luminescent color is preferably white.
  • the organic electroluminescence element of the present invention can be suitably provided in a display device and 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 layer refers to a layer containing an organic substance.
  • Anode / light emitting layer / electron transport layer / cathode ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode // hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode Buffer layer / Hole transport layer / Light emitting layer / Electron
  • an organic compound layer including a light emitting layer excluding an anode and a cathode can be used as one light emitting unit, and a plurality of light emitting units can be stacked.
  • the plurality of stacked light emitting units may have a non-light emitting intermediate layer between the light emitting units, and the intermediate layer may further include a charge generation layer.
  • the organic EL element of the present invention is preferably a white light emitting layer, and is preferably a display device and a lighting device using these.
  • the light emitting layer according to the present invention is a layer that emits light when excitons generated by recombination of electrons and holes injected from the cathode or the electron transport layer or the anode or the hole transport layer are deactivated.
  • the portion to be formed may be in the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
  • the total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferably adjusted in the range of 2 nm to 5 ⁇ m, more preferably adjusted in the range of 2 to 200 nm, particularly preferably in the range of 5 to 100 nm.
  • a light emitting dopant or host compound described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, for example, a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method,
  • the film can be formed by an inkjet method, a printing method, a spray coating method, a curtain coating method, an LB method (including Langmuir-Blodgett method)) and the like.
  • the light emitting layer is a layer formed through a wet process. By forming the layer by a wet process, damage to the light emitting layer due to heat can be reduced as compared with the vacuum deposition method.
  • the light emitting layer of the organic EL device of the present invention contains a light emitting dopant and a host compound, and at least one light emitting dopant is a ligand represented by the above general formula (1) or general formula (2).
  • a phosphorescent organometallic complex coordinated to a metal atom and is preferably a phosphorescent organometallic complex represented by any one of formulas (3) to (6).
  • the light-emitting layer according to the present invention may be used in combination with compounds described in the following patent publications.
  • Fluorescent dopants also referred to as fluorescent compounds
  • phosphorescent dopants also referred to as phosphorescent dopants, phosphorescent compounds, phosphorescent compounds, etc.
  • the light-emitting dopant can be used as the light-emitting dopant.
  • the present inventors have made phosphorescence emission in which a ligand represented by the general formula (1) or (2) is coordinated to a metal atom.
  • the present inventors have found that by using a light-emitting organometallic complex as a phosphorescent dopant, high light emission luminance, low driving voltage, and longer light emission lifetime can be achieved at the same time.
  • the organic electroluminescent element produced using the phosphorescence dopant of this invention is improved also at the point of temporal stability.
  • metal complexes have improved material efficiency due to the effect of improving luminous efficiency at the phenylimidazole part of the ligand and the function separation effect of carrier movement being carried out by the aryl group bonded to the N-phenyl group of the imidazole ring.
  • the interaction between the aryl groups bonded to the N-phenyl group becomes too strong, the decrease in light emission efficiency due to concentration quenching between the light emitting dopants cannot be overlooked, and the light emission lifetime The improvement was not enough.
  • the effect of improving the light emission efficiency in the phenylimidazole part and the function separation effect of carrier movement in the D ring part and E ring part bonded to the N-phenyl group of the imidazole ring are more strongly expressed, and the robustness of the material is improved. Further improved.
  • the shape of the light-emitting dopant molecules approaches a spherical shape, the dispersibility with respect to the host compound is improved, so that the carrier balance of the entire device can be optimized and the recombination of carriers at a more central portion of the light-emitting layer can be realized.
  • the light emission lifetime is improved and the uniformity of the light emitting layer is improved so that the occurrence of light emission unevenness is suppressed.
  • M is preferably a transition metal atom.
  • organic electroluminescence element capable of controlling light emission, and a lighting device and a display device including the organic electroluminescence element can be provided.
  • the phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and a phosphorescence quantum yield is 25 ° C.
  • the phosphorescence quantum yield is preferably 0.1 or more.
  • 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, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • phosphorescent dopants There are two types of emission of phosphorescent dopants 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 transferred to the phosphorescent dopant. It is an energy transfer type to obtain light emission from a phosphorescent dopant. The other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.
  • a phosphorescent organometallic complex in which a ligand represented by the general formula (1) or the general formula (2) described below is coordinated to a metal atom is described. Used. It is preferable to use a phosphorescent organometallic complex represented by any one of General Formula (3) to General Formula (6).
  • examples of the 5-membered or 6-membered aromatic heterocycle represented by the ring B include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, and a pyridazine.
  • Ring B is preferably a benzene ring.
  • the ring E is an aromatic hydrocarbon ring having 6 to 30 carbon atoms bonded to the ring D through G representing a carbon atom, a silicon atom, or a nitrogen atom, or Represents an aromatic heterocycle having 1 to 30 carbon atoms.
  • examples of the aromatic hydrocarbon ring having 6 to 30 carbon atoms represented by ring E include, for example, a benzene ring, naphthalene ring, phenanthrene ring, benzophenanthrene ring, chrysene ring, benzochrysene Ring, triphenylene ring, picene ring, naphthochrysene ring, phenanthrochrysene ring and the like.
  • examples of the aromatic heterocycle having 1 to 30 carbon atoms represented by ring E include, for example, a furan ring, a thiophene ring, a pyrrole ring, a silole ring, a pyridine ring, a pyridazine ring, and a pyrimidine.
  • Ring E is preferably a benzene ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring or fluorene ring.
  • R 1 and R 2 are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group Represents a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent. At least one of R 1 and R 2 represents an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • examples of the halogen atom represented by R 1 and R 2 include a fluorine atom, a chlorine atom, and a bromine atom.
  • examples of the alkyl group represented by R 1 and R 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and dodecyl.
  • examples of the alkenyl group represented by R 1 and R 2 include a vinyl group and an allyl group.
  • examples of the alkynyl group represented by R 1 and R 2 include an ethynyl group and a propargyl group.
  • examples of the alkoxy group represented by R 1 and R 2 include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group. Can be mentioned.
  • examples of the amino group represented by R 1 and R 2 include an amino group, an ethylamino group, a dimethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, and a dodecylamino group.
  • examples of the silyl group represented by R 1 and R 2 include a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, and a phenyldiethylsilyl group.
  • examples of the arylalkyl group represented by R 1 and R 2 include a benzyl group, an ⁇ -methylbenzyl group, a cinnamyl group, an ⁇ -ethylbenzyl group, an ⁇ , ⁇ -dimethylbenzyl group, Examples include 4-methylbenzyl group, 4-ethylbenzyl group, 2-tert-butylbenzyl group, 4-n-octylbenzyl group, naphthylmethyl group, diphenylmethyl group and the like.
  • examples of the aryl group represented by R 1 and R 2 include 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, And monovalent groups derived from a pyrene ring, a pyranthrene ring, an anthraanthrene ring, and the like.
  • examples of the heteroaryl group represented by R 1 and R 2 include a silole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.
  • examples of the non-aromatic hydrocarbon ring group represented by R 1 and R 2 include a cycloalkane (eg, cyclopentane ring, cyclohexane ring, etc.), a cycloalkoxy group (eg, cyclopentyloxy). Group, cyclohexyloxy group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), cyclohexylaminosulfonyl group, tetrahydronaphthalene ring, 9,10-dihydroanthracene ring, biphenylene ring, etc. The group of is mentioned.
  • examples of the non-aromatic heterocyclic group represented by R 1 and R 2 include an epoxy ring, an aziridine ring, a thiirane ring, an oxetane ring, an azetidine ring, a thietane ring, a tetrahydrofuran ring, and a dioxolane ring.
  • R 1 and R 2 are both an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms, and at least one of R 1 and R 2 is a branched alkyl group having 3 or more carbon atoms. It is also preferable. More preferably, both R 1 and R 2 are branched alkyl groups having 3 or more carbon atoms.
  • R 3 is an alkyl group having 1 or more carbon atoms or a cycloalkyl group having 3 or more carbon atoms.
  • R 3 is a branched alkyl group having 3 or more carbon atoms or a cycloalkyl group having 5 or more carbon atoms, and more preferably R 3 is a branched alkyl group having 3 or more carbon atoms.
  • Ra, Rb, Rc and Rd are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, It represents an arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, and may further have a substituent.
  • the halogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group and arylalkyl group represented by Ra, Rb, Rc and Rd are In the formula (1), the same groups as those described as the halogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, and arylalkyl group represented by R 1 and R 2 are the same. Can be mentioned.
  • the aryl group and heteroaryl group represented by Ra, Rb, Rc and Rd are the aryl group and heterocycle represented by R 1 and R 2 in the general formula (1). Examples thereof include the same groups as those exemplified as the aryl group.
  • the non-aromatic hydrocarbon ring group and non-aromatic heterocyclic group represented by Ra, Rb, Rc and Rd are represented by R 1 and R 2 in the general formula (1).
  • Examples thereof include the same groups as those exemplified as the non-aromatic hydrocarbon ring group and the non-aromatic heterocyclic group.
  • nb and nd represent an integer of 1 to 4
  • na and nc represent 1 or 2.
  • ne represents an integer of 1 to 20.
  • Adjacent ring A and ring D, or ring D and ring E may be bonded to adjacent rings at two positions to form a condensed ring. Furthermore, ring A, ring D, and ring E may form one condensed ring.
  • ring B, ring E, G, R 1 , R 2 , R 3 , Ra, Rb, Rc, Rd, Re, na, nb, nc, nd and ne are the above Synonymous with ring B, ring E, G, R 1 , R 2 , R 3 , Ra, Rb, Rc, Rd, Re, na, nb, nc, nd and ne in general formulas (1) and (2) .
  • L represents one or more of monoanionic bidentate ligands coordinated to M.
  • Specific examples of the monoanionic bidentate ligand represented by L include a ligand represented by the following formula.
  • R ′, R ′′ and R ′′ ′ represent a hydrogen atom or a substituent.
  • substituent represented by R ′, R ′′ and R ′′ ′′ 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.), alkenyl group (for example, vinyl group, allyl group, etc.) ), Alkynyl groups (for example, ethynyl group, propargyl group, etc.), non-aromatic hydrocarbon ring groups (for example, cycloalkyl groups (for example, cyclopentyl group, cyclohexyl groups, etc.)), cycloalkoxy groups (for example,
  • a monovalent group derived from the above an alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a dodecyloxy group, etc.), an aryloxy group (for example, a fluorine group).
  • an alkoxy group for example, a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a dodecyloxy group, etc.
  • an aryloxy group for example, a fluorine group
  • Nonoxy group, naphthyloxy group, etc. alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), Alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.) ), Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminos
  • M represents a transition metal atom having an atomic number of 40 or more and a group 8 to 10 in the periodic table, preferably Os, Ir, Pt, more preferably Ir. It is.
  • n an integer of 0 to 2
  • n is at least 1
  • m + n represents 2 or 3.
  • Phosphorescent organometallic complex represented by general formula (5) or general formula (6) Phosphorescent organometallic complex represented by general formula (3) or general formula (4)
  • a preferred embodiment of the complex is a phosphorescent organometallic complex represented by the following general formula (5) or general formula (6).
  • ring E, G, R 1 , R 2 , R 3 , Ra, Rb, Rc, Rd, Re, na, nb, nc, nd and ne It is synonymous with the rings E, G, R 1 , R 2 , R 3 , Ra, Rb, Rc, Rd, Re, na, nb, nc, nd and ne in the formula (1) and the general formula (2).
  • M, L, m, and n are synonymous with M, L, m, and n in General formula (3) and General formula (4).
  • adjacent ring A and ring D, ring D and ring E may be bonded to each other at two points to form a condensed ring, or ring A and ring D. And ring E may form one condensed ring.
  • the structure of the ligand is more specifically represented by the following general formulas (L1A) to (L1AA) and general formulas (L2A) to (L2Q).
  • ring B, ring E, G, R 1 , R 2 , R 3 , Ra, Rb, Rc, Rd, Re, na, nb, nc, nd and ne are the ring B, ring E, G, R 1 , R 2 , R 3 , Ra, Rb, Rc, Rd, Re, na, nb of the above general formulas (1) and (2). , Nc, nd and ne.
  • Ra 1 to Ra 4 , Rc 1 to Ra 2 and Rd 1 to Rd 4 represent the positional differences of the substituents Ra, Rc and Rd, respectively.
  • W, X, Y, and Z are carbon atoms that may have a substituent and nitrogen that may have a substituent.
  • An atom, a silicon atom having a substituent, an oxygen atom or a sulfur atom is represented.
  • W, X, Y and Z are a nitrogen atom, an oxygen atom or a sulfur atom which may have a substituent. More preferably, W, X, Y and Z are an oxygen atom or a sulfur atom.
  • H indicates that all are substituted with hydrogen atoms, and when a specific substituent is described. In addition to the substituents, the hydrogen atom is substituted.
  • phosphorescent organometallic complexes represented by any one of the general formulas (3) to (6) are shown in Tables 1-1 to 1-6 below. The invention is not limited to these.
  • the phosphorescent organometallic complex represented by any one of the general formulas (3) to (6) is represented by the general formula: (L) n -M- ( AL)
  • Each configuration is represented by m . That is, in the general formula, L represents a ligand represented by the general formula (1) or (2) according to the present invention, and AL represents a conventionally known monoanionic bidentate ligand. , N represents the number of L coordinated to M, and m represents the number of AL coordinated to M.
  • DP-1 in the table can be represented as “(L1A-4) 3 Ir”
  • DP-459 in the table is represented by “(L2M-21) 2 Ir (AL-11)”.
  • It can be expressed as.
  • the structural formulas of DP-1 and DP-459 are shown below.
  • the conventionally known ligands AL-1 to AL15 in Table 1-1 to Table 1-6 are the compounds shown below.
  • Tables 1-1 to 1-6 below show specific examples (DP-1 to DP) of phosphorescent organometallic complexes (phosphorescent dopants) represented by any of the general formulas (3) to (6) -543).
  • intermediate B-1 was hydrogenated in ethyl acetate-ethanol at room temperature in the presence of 10% palladium on carbon catalyst to obtain intermediate C-1.
  • Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamines. And dyes having a high fluorescence quantum yield such as laser dyes and the like, and dyes based on dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • the light-emitting dopant according to the present invention may be used in combination with a plurality of types of compounds, a combination of phosphorescent dopants having different structures, a phosphorescent dopant and A combination of fluorescent dopants may also be used.
  • Known phosphorescent dopants and fluorescent dopants can be used.
  • the host compound is a phosphorescent quantum that emits phosphorescence at room temperature (25 ° C.) and has a mass ratio of 20% or more in the light-emitting layer.
  • a yield is defined as a compound of less than 0.1.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • the host compound that can be used in the present invention is not particularly limited, and compounds conventionally used in organic EL devices can be used.
  • a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being longer, and has a high Tg (glass transition temperature) is preferable.
  • conventionally known host compounds may be used alone or in combination of two or more.
  • 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.
  • the host compound used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound (polymerizable host compound) having a polymerizable group such as a vinyl group or an epoxy group. Of course, one or more of such compounds may be used.
  • a compound represented by the following general formula (B) or general formula (E) is particularly preferable as the host compound of the light emitting layer of the organic EL device of the present invention.
  • Xa represents an oxygen atom or a sulfur atom.
  • Xb, Xc, Xd and Xe each represent a hydrogen atom, a substituent or a group represented by the following general formula (C).
  • At least one of Xb, Xc, Xd and Xe represents a group represented by the following general formula (C), and at least one of the groups represented by the following general formula (C) represents Ar as a carbazolyl group. .
  • L 4 represents a divalent linking group derived from an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • n represents an integer of 0 to 3, and when n is 2 or more, the plurality of L 4 may be the same or different.
  • * Represents a linking site with the general formula (B) or the general formula (E).
  • Ar represents a group represented by the following general formula (D).
  • Xf represents N (R ′′), an oxygen atom or a sulfur atom
  • E 1 to E 8 represent C (R ′′ 1 ) or N
  • R ′′ and R ′′ 1 are hydrogen atoms
  • It represents a substituent or a linking site with L 4 in formula (C).
  • * Represents a linking site with L 4 in the general formula (C).
  • a compound represented by the following general formula (B ′) is particularly preferably used as the host compound of the light emitting layer of the organic EL device of the present invention.
  • Xa represents an oxygen atom or a sulfur atom
  • Xb and Xc each represents a substituent or a group represented by the above general formula (C).
  • At least one of Xb and Xc represents a group represented by the above general formula (C), and at least one of the groups represented by the general formula (C) represents Ar as a carbazolyl group.
  • Ar in the general formula (C) represents a carbazolyl group which may have a substituent, and more preferably, in the general formula (C).
  • Ar may have a substituent, and represents a carbazolyl group linked to L 4 in formula (C) at the N-position.
  • 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, it 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. May be.
  • 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).
  • anode buffer layer (hole injection 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.
  • copper phthalocyanine is used.
  • Representative phthalocyanine buffer layer oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, polymer buffer layer using conductive polymer such as polyaniline (emeraldine) or polythiophene, tris (2-phenylpyridine) )
  • Orthometalated complex layers represented by iridium complexes and the like.
  • azatriphenylene derivatives as described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as the hole injection material.
  • cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc.
  • the buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m, although it depends on the material.
  • ⁇ Blocking layer hole blocking layer, electron blocking layer>
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258 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 in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the hole blocking layer contains the carbazole derivative, carboline derivative, or diazacarbazole derivative (shown in which any one of the carbon atoms constituting the carboline ring of the carboline derivative is replaced by a nitrogen atom). It is preferable to contain.
  • the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers.
  • 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
  • the ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.
  • Gaussian 98 Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.
  • the ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
  • the structure of the hole transport layer described later can be used as an electron blocking layer as necessary.
  • the film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 to 100 nm, 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.
  • azatriphenylene derivatives as described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.
  • 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
  • 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.
  • 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.
  • cyclometalated complexes and orthometalated complexes such as copper phthalocyanine and tris (2-phenylpyridine) iridium complex can also be used as the hole transport material.
  • JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.
  • the hole transport layer can be 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. it can.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
  • This 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, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
  • a hole transport layer having such a high p property because a device with lower power consumption can be produced.
  • 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.
  • any material can be selected from conventionally known compounds and used alone or in combination. Fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like can be mentioned.
  • 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), 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.
  • the central metals of these metal complexes are In, Mg, Cu Metal complexes replaced with Ca, Sn, Ga, or Pb can also be used as electron transport materials.
  • 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 derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 nm 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.
  • an electron transport layer having such a high n property because an element with lower power consumption can be produced.
  • 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.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • the anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • a wet film forming method such as a printing method or a coating method can be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • 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.
  • 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.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • 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 ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or translucent cathode can be manufactured by forming the above metal on the cathode with a film thickness in the range of 1 to 20 nm and then forming the conductive transparent material mentioned in the description of the anode thereon.
  • an element in which both the anode and the cathode are transmissive can be manufactured.
  • the support substrate (hereinafter also referred to as a substrate, 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., and is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by J
  • the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / (m 2 ⁇ 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987.
  • a high barrier film having a permeability of 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material for forming the barrier film may be any material that has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the method for forming the barrier film is not particularly limited.
  • the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction efficiency at room temperature of light emission of the organic EL element of the present invention is preferably 1% or more, more preferably 5% or more.
  • 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.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • the ⁇ max of light emission of the organic EL element is preferably 480 nm or less.
  • ⁇ Sealing> As a sealing means used for this invention, the method of adhere
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the element can be thinned.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured in (1) is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • Application of the adhesive to the sealing portion may be performed using a commercially available dispenser or may be printed like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma
  • a polymerization method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil
  • a vacuum is also possible.
  • a hygroscopic compound can also be enclosed inside.
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • the organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.
  • a method for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from the substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device of the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any medium is characterized by a high effect of improving light extraction efficiency.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction.
  • Bragg diffraction such as first-order diffraction and second-order diffraction.
  • light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode). I want to take it out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any interlayer or medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL element of the present invention can be processed on a light extraction side of a substrate, for example, by providing a microlens array-like structure, or combined with a so-called condensing sheet, for example in a specific direction, for example, with respect to the element light emitting surface.
  • a condensing sheet for example in a specific direction, for example, with respect to the element light emitting surface.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably within a range of 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • BEF brightness enhancement film
  • the shape of the prism sheet for example, the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • a desired electrode material for example, a thin film made of 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 ⁇ m or less, preferably in the range of 10 to 200 nm. Make it.
  • organic compound thin films such as 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, are formed thereon.
  • each of these layers there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above, but it is easy to obtain a homogeneous film and it is difficult to generate pinholes.
  • film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.
  • the organic layer containing the phosphorescent organometallic complex according to the present invention is preferably formed through a wet process for the above reason.
  • liquid medium for dissolving or dispersing the organic EL material according to the present invention examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene.
  • Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • a dispersion method it can disperse
  • 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 film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm.
  • a desired organic EL element can be obtained.
  • 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 organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • lighting devices home lighting, interior lighting
  • clock and liquid crystal backlights billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light
  • the light source of a sensor etc. are mentioned, It is not limited to this, It can use effectively for the use as a backlight of a liquid crystal display device, and an illumination light source especially.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
  • patterning only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned.
  • a conventionally known method is used. Can do.
  • the light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (manufactured by Konica Minolta Optics) is applied to the CIE chromaticity coordinates.
  • the display device of the present invention will be described.
  • the display device of the present invention has the organic EL element.
  • the display device of the present invention may be single color or multicolor, but here, the multicolor display device will be described.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by a vapor deposition method, a cast method, a spin coat method, an inkjet method, a printing method, or the like.
  • the method is not limited, but is preferably a vapor deposition method, an inkjet method, or a printing method. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light emitting sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. However, it is not limited to this.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
  • the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal.
  • the image information is sequentially emitted to scan the image and display the image information on the display unit A.
  • FIG. 2 is a schematic diagram of the display unit A.
  • the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on the substrate.
  • the main members of the display unit A will be described below.
  • FIG. 2 shows a case where the light L emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)
  • the pixel 3 When the scanning signal is applied from the scanning line 5, the pixel 3 receives the image data signal from the data line 6 and emits light according to the received image data.
  • a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 3 is a schematic diagram of the circuit.
  • 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.
  • an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
  • 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.
  • the capacitor 13 is charged according to the potential of the image data signal, and 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.
  • the power supply line 7 connects the organic EL element 10 to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 When the scanning signal moves 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, since the capacitor 13 holds the charged potential of the image data signal even when the driving of the switching transistor 11 is turned off, 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.
  • the driving transistor 12 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.
  • 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 elements 10 of the plurality of pixels, and the organic EL elements 10 of the plurality of pixels 3 emit light. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
  • the potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 4 is a schematic view of a passive matrix display device.
  • 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.
  • the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
  • the lighting device of the present invention will be described.
  • the illuminating device of this invention has the said organic EL element.
  • the organic EL element of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image ( It may be used as a display.
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • the organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.
  • 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.
  • luminescent material used for a light emitting layer For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.
  • CF color filter
  • the white light emitting organic EL element according to the present invention is used as a kind of lamp such as household illumination, interior lighting, and exposure light source as various light emitting light sources and lighting devices in addition to the display device and display. It is also useful for display devices such as backlights for liquid crystal display devices.
  • the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a 300 ⁇ m thick glass substrate is used as a sealing substrate, and an epoxy photocurable adhesive (LUX The track LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, sealed, and illuminated as shown in FIGS.
  • a device can be formed.
  • FIG. 5 shows a schematic diagram of the lighting device. As shown in FIG. 5, the organic EL element 101 is covered with a glass cover 102.
  • the sealing operation with the glass cover 102 is preferably performed in a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) without bringing the organic EL element 101 into contact with the atmosphere.
  • FIG. 6 shows a cross-sectional view of the lighting device.
  • the lighting device mainly includes a cathode 105, an organic EL layer 106, and a glass substrate 107 with a transparent electrode, and these members are covered with a glass cover 102.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • Example 1 ⁇ Vapor deposition type blue light emitting organic EL element> ⁇ Production of Blue Light-Emitting Organic EL Element 1-1 >> Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) 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.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, 200 mg of the host compound (OC-11) is put into another resistance heating boat made of molybdenum, 100 mg of the luminescent dopant (Comparative Compound 1) is put into another resistance heating boat made of molybdenum, and the electron transport material 1 is put into another resistance heating boat made of molybdenum. And 200 mg of the electron transport material 2 was put in another molybdenum resistance heating boat, and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm thick hole transport layer was provided.
  • the hole transport layer was heated by energizing the heating boat containing the host compound (OC-11) and the light emitting dopant (Comparative Compound 1) at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively.
  • a 40 nm-thick luminescent layer was provided by co-evaporation.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • organic EL element 1-1 lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 1-1 was produced.
  • the organic EL element is abbreviated as EL, for example, the organic EL element 1-1 is denoted as EL1-1.
  • FIG. 5 shows a schematic diagram of the lighting device.
  • the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover 102 is a glove box (purity of 99.999% or more in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere). In a high-purity nitrogen gas atmosphere).
  • FIG. 6 shows a cross-sectional view of the lighting device. Inside the lighting device, a glass substrate 107 with a transparent electrode as an anode, an organic EL layer 106 and a cathode 105 are laminated in this order. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the external extraction quantum yields are all expressed as relative values with the organic EL element 1-1 at an initial luminance of 2000 cd / m 2 as a reference (100).
  • Drive voltage ⁇ (drive voltage of each element / drive voltage of the organic EL element 1-1 (initial luminance 2000 cd / m 2 )) ⁇ ⁇ 100 A smaller value indicates a lower drive voltage for comparison.
  • Drive voltage increase rate (%) ⁇ [(Drive voltage after driving 200 hours for each organic EL element / V) ⁇ (Initial drive voltage for each organic EL element / V)] / (Initial drive voltage for each organic EL element) / V) ⁇ ⁇ 100 (4)
  • Half light emission lifetime (25 ° C) The half-light emission lifetime was evaluated according to the measurement method shown below.
  • Each organic EL element is driven at a constant current in a constant temperature bath at 25 ° C. and 70 ° C. with a current that gives an initial luminance of 2000 cd / m 2 , and a time that is 1 ⁇ 2 of the initial luminance (1000 cd / m 2 ) is obtained. This was taken as a measure of half-life.
  • the half-light emission lifetime was expressed as a relative value set with the reference (100) as the half-light emission lifetime of the organic EL device 1-1 obtained at 25 ° C.
  • the initial deterioration was expressed as a relative value set with the reference (100) as the half-light emission lifetime of the organic EL element 1-1.
  • the initial deterioration was calculated based on the following formula.
  • Initial degradation ⁇ (90% arrival time of luminance of organic EL element 1-1 (hr)) / (90% arrival time of each organic EL element (hr)) ⁇ ⁇ 100 That is, the smaller the initial deterioration value is, the smaller the initial deterioration is.
  • the organic EL elements 1-5 to 1-161 of the present invention have higher external extraction quantum efficiency than the comparative organic EL elements 1-1 to 1-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 1-5 to 1-161 of the present invention also suppress the generation of uneven light emission, dark spots, and increase in driving voltage.
  • Example 2 ⁇ Wet process type blue light emitting element> ⁇ Preparation of Blue Light-Emitting Organic EL Element 2-1 >> Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) 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.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • This substrate was transferred to a nitrogen atmosphere, and a solution obtained by dissolving 50 mg of the hole transport material 2 in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. . Furthermore, after irradiating with ultraviolet light for 180 seconds to perform photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to obtain a second hole transport layer.
  • a thin film was formed on the light emitting layer by spin coating using a solution obtained by dissolving 50 mg of the electron transport material 3 in 10 ml of hexafluoroisopropanol (HFIP) at 1000 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 30 nm.
  • HFIP hexafluoroisopropanol
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as a cathode buffer layer, and further 110 nm of aluminum was deposited. Thus, a cathode was formed to produce an organic EL element 2-1.
  • the organic EL elements 2-5 to 2-161 of the present invention have higher external extraction quantum efficiency than the comparative organic EL elements 2-1 to 2-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 2-5 to 2-161 of the present invention also suppress the generation of uneven light emission, dark spots, and increase in driving voltage.
  • the phosphorescent organic material according to the present invention is used as a light emitting dopant in order to improve the light emitting efficiency, reduce the driving voltage, and improve the light emitting lifetime. It can be seen that it is useful to use a metal complex.
  • Example 3 ⁇ Vapor deposition type white light emitting element-1> ⁇ Production of White Light-Emitting Organic EL Element 3-1 >> Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) 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.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of the host compound (OC-11) is added. In another molybdenum resistance heating boat, 100 mg of the luminescent dopant (Comparative Compound 1) is added.
  • the luminescent dopant (D -6) was put in 100 mg, 200 mg of the electron transport material 1 was put in another resistance heating boat made of molybdenum, and 200 mg of the electron transport material 2 was put in another resistance heating boat made of molybdenum, and attached to the vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm thick hole transport layer was provided.
  • the heating boat containing the host compound (OC-11), the luminescent dopant (Comparative Compound 1) and the luminescent dopant (D-6) was energized and heated, and the deposition rates were 0.2 nm / second and 0.020 nm, respectively.
  • a light emitting layer having a film thickness of 40 nm was provided by co-evaporation on the hole transport layer at a rate of 0.0010 nm / second.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 3-1 was produced.
  • Organic EL elements 3-2 to 3-161 were produced in the same manner as EL element 3-1.
  • the organic EL elements 3-5 to 3-161 of the present invention have higher external extraction quantum efficiency than the comparative organic EL elements 3-1 to 3-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 3-5 to 3-161 of the present invention also suppress the generation of uneven light emission, dark spots, and increase in driving voltage.
  • the invention relates to the present invention as a light emitting dopant in order to improve light emission efficiency, drive voltage, and light emission life. It can be seen that it is useful to use a phosphorescent organometallic complex.
  • Example 4 ⁇ Vapor deposition type white light emitting element-2> ⁇ Preparation of white light emitting element 4-1 >> Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) 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.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of the host compound (OC-11) is added. In another molybdenum resistance heating boat, 100 mg of the luminescent dopant (Comparative Compound 1) is added.
  • the luminescent dopant (D -3) 100 mg, 100 mg of luminescent dopant (D-6) in another molybdenum resistance heating boat, 200 mg of electron transport material 1 in another molybdenum resistance heating boat, and another molybdenum resistance heating boat 200 mg of the electron transport material 2 was put in and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm thick hole transport layer was provided.
  • the hole transport layer was heated by energizing the heating boat containing the host compound (OC-11) and the luminescent dopant (Comparative Compound 1) at a deposition rate of 0.2 nm / second and 0.020 nm / second, respectively.
  • a blue light emitting layer having a thickness of 20 nm was provided by co-evaporation.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the host compound (OC-11), the luminescent dopant (D-3), and the luminescent dopant (D-6) was energized and heated, and the deposition rates were 0.2 nm / second and 0.010 nm, respectively.
  • a yellow light emitting layer having a thickness of 20 nm was provided by co-evaporation on the hole transport layer at a rate of 0.0010 nm / sec.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 4-1 was produced.
  • Organic EL elements 4-2 to 4-161 are produced in the same manner as the EL element 4-1.
  • the organic EL elements 4-5 to 4-161 of the present invention have a higher external extraction quantum efficiency than the comparative organic EL elements 4-1 to 4-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 4-5 to 4-161 of the present invention also suppress the generation of uneven light emission, dark spots, and increase in driving voltage.
  • Example 5 ⁇ Vapor deposition type white light emitting element-3> ⁇ Preparation of white light emitting element 5-1 >> Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) 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.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of the hole injection material 1 is put into a molybdenum resistance heating boat, and 200 mg of the hole transport material 1 is put into another molybdenum resistance heating boat, 200 mg of host compound 1 (OC-11) is put into another resistance heating boat made of molybdenum, 200 mg of host compound 2 (OC-6) is put into another resistance heating boat made of molybdenum, and the luminescent dopant is put into another resistance heating boat made of molybdenum.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing the hole injection material 1, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm hole injection layer was provided.
  • the heating boat containing the hole transport material 1 was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 20 nm thick hole transport layer was provided.
  • the hole transport layer was heated by energizing the heating boat containing the host compound (OC-11) and the luminescent dopant (Comparative Compound 1) at a deposition rate of 0.2 nm / second and 0.020 nm / second, respectively.
  • a blue light emitting layer having a thickness of 20 nm was provided by co-evaporation.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the host compound (OC-6), the luminescent dopant (D-3) and the luminescent dopant (D-6) was energized and heated, and the deposition rates were 0.2 nm / second and 0.010 nm, respectively.
  • a yellow light emitting layer having a thickness of 20 nm was provided by co-evaporation on the hole transport layer at a rate of 0.0010 nm / sec.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing the electron transport material 1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing the electron transport material 2 is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further form an electron transport layer having a thickness of 20 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and an organic EL element 5-1 was produced.
  • Organic EL elements 5-2 to 5-161 In the preparation of the organic EL element 5-1, the hole injection material, the hole transport material, the host compound 1, the host compound 2, and the light emitting dopant (only the comparison compound 1) are converted into the compounds shown in Tables 6-1 to 6-6. Organic EL elements 5-2 to 5-161 were produced in the same manner as the organic EL element 5-1, except that the organic EL elements were replaced.
  • the organic EL elements 5-5 to 5-161 of the present invention have higher external extraction quantum efficiency than the comparative organic EL elements 5-1 to 5-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 5-5 to 5-161 of the present invention suppress the generation of uneven light emission, dark spots, and increase in driving voltage.
  • Example 6 ⁇ Wet process type white light emitting element-1> ⁇ Production of White Light-Emitting Organic EL Element 6-1 >> This ITO transparent electrode was provided after patterning was performed on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode.
  • the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • the substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of the hole transport material 3 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.
  • a thin film was formed on the light emitting layer by spin coating using a solution obtained by dissolving 50 mg of the electron transport material 3 in 10 ml of hexafluoroisopropanol (HFIP) at 1000 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 30 nm.
  • HFIP hexafluoroisopropanol
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as a cathode buffer layer, and further 110 nm of aluminum was deposited. Thus, a cathode was formed, and an organic EL element 6-1 was produced.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the organic EL elements 6-5 to 6-161 of the present invention have higher external extraction quantum efficiency than the comparative organic EL elements 6-1 to 6-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 6-5 to 6-161 of the present invention also suppress the generation of uneven light emission and dark spots and the increase in driving voltage.
  • Example 7 ⁇ Wet process type white light emitting element-2> ⁇ Production of White Light-Emitting Organic EL Element 7-1 >> This ITO transparent electrode was provided after patterning was performed on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode.
  • the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • the substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of the hole transport material 3 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.
  • a thin film was formed on this light emitting layer by spin coating under a condition of 1000 rpm and 30 seconds using a solution of 50 mg of electron transport material 4 dissolved in 10 ml of methanol. After irradiating with ultraviolet light for 60 seconds to perform photopolymerization / crosslinking, it was further vacuum-dried at 60 ° C. for 1 hour to obtain an electron transport layer having a film thickness of about 30 nm.
  • this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as a cathode buffer layer, and further 110 nm of aluminum was deposited. Thus, a cathode was formed, and an organic EL element 7-1 was produced.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the organic EL elements 7-5 to 7-161 of the present invention have higher external extraction quantum efficiency than the comparative organic EL elements 7-1 to 7-4, and It can be seen that there is little deterioration in luminance at the initial stage, and accordingly, the lifetime is long at both room temperature and high temperature.
  • the organic EL elements 7-5 to 7-161 of the present invention also suppress the generation of uneven light emission and dark spots and the increase in driving voltage.
  • the organic electroluminescence element of the present invention has a low driving voltage, high light emission efficiency, excellent durability, excellent dark spot and emission unevenness prevention effects, and can be suitably used for lighting devices and display devices.

Abstract

La présente invention a pour objectif de prendre en compte les problèmes de mise à disposition : d'un élément électroluminescent organique qui travaille à basse tension, qui présente un rendement luminescent élevé et une excellente durabilité, et qui s'avère très efficace dans la prévention de la génération de points sombres ou d'irrégularité de luminescence ; ainsi que d'un illuminateur et d'un dispositif d'affichage équipés de l'élément électroluminescent organique. L'élément électroluminescent organique comprend une anode et une cathode, et, prises en sandwich entre ces dernières, une ou plusieurs couches organiques incluant une couche luminescente. L'élément électroluminescent organique est caractérisé en ce qu'au moins une des couches organiques contient un complexe organométallique phosphorescent dans lequel un ligand représenté par la formule générale (1) ou par la formule générale (2) s'est coordonné à un atome de métal.
PCT/JP2013/072664 2012-08-27 2013-08-26 Élément électroluminescent organique, illuminateur, et dispositif d'affichage WO2014034584A1 (fr)

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