WO2011040343A1 - 有機電界発光素子用材料、及び有機電界発光素子 - Google Patents
有機電界発光素子用材料、及び有機電界発光素子 Download PDFInfo
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- WO2011040343A1 WO2011040343A1 PCT/JP2010/066605 JP2010066605W WO2011040343A1 WO 2011040343 A1 WO2011040343 A1 WO 2011040343A1 JP 2010066605 W JP2010066605 W JP 2010066605W WO 2011040343 A1 WO2011040343 A1 WO 2011040343A1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
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- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Definitions
- the present invention relates to an organic electroluminescent element material and an organic electroluminescent element.
- Organic electroluminescent elements (hereinafter also referred to as “elements” and “organic EL elements”) have been actively researched and developed in recent years because they can emit light with high brightness when driven at a low voltage.
- an organic electroluminescent element is composed of an organic layer including a light emitting layer and a pair of electrodes sandwiching the layer, and electrons injected from the cathode and holes injected from the anode are recombined in the light emitting layer, The generated exciton energy is used for light emission.
- Patent Document 1 describes an iridium complex that contains a fused azole ligand and is highly durable and capable of emitting blue light.
- Patent Document 2 for the purpose of improving the durability of the device, at least one of the organic compound layers contains a metal coordination compound, and the decomposition product of the metal coordination compound in the organic compound layer Or the light emitting element whose content of a raw material is 0.5 mass% or less is described.
- Patent Document 1 describes a light-emitting material having high blue purity and high durability.
- the metal complex described in Patent Document 1 is simply obtained from the synthesis of the complex. Improvement is desired because it is weak to visible light and easily oxidized so that it must be handled under light-shielding conditions until separation, and the manufacturing process becomes complicated and the productivity is poor.
- Patent Document 2 discloses a technique for increasing the purity of a light-emitting material mainly for the purpose of improving the durability of an element.
- Patent Document 2 does not discuss the stability of the light emitting material under visible light and the efficiency when the light emitting element is driven with high luminance.
- An object of the present invention is an organic electroluminescent element material that can be used for an organic EL element, can be stably stored under visible light, and has excellent efficiency when the element is driven with high brightness, An organic electroluminescence device using the material is provided.
- the inventors of the present invention mix a specific phosphorescent metal complex A and a separately synthesized phosphorescent metal complex B, or generate a phosphorescent metal complex B when synthesizing the phosphorescent metal complex A.
- the method for synthesizing the organic electroluminescent element material containing the metal complex A and the metal complex B in a specific range the storage stability under visible light and high brightness
- the inventors have found that there is an effect of excellent efficiency when the element is driven, and have reached the present invention. That is, the said subject can be solved by the following means.
- a material for an organic electroluminescence device comprising at least a phosphorescent metal complex A and a phosphorescent metal complex B, wherein the phosphorescent metal complex A includes a partial structure represented by the following general formula (1), and the phosphorescence In the metal complex B, in at least one substituent of R 1 and R 2 in the general formula (1), one or more of the atoms directly bonded to Q 1 or Q 2 have the same homologous and atomic weight of the atom
- the phosphorescent metal complex A has the same structure as that of the phosphorescent metal complex A except that the phosphorescent metal complex A is replaced by a large atom, and the content ratio of the phosphorescent metal complex B to the phosphorescent metal complex A is 0.005 mass% or more and 2 mass%.
- the material for organic electroluminescent elements which is the following.
- R 1 and R 2 each independently represent a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different. R 1 and R 2 may be bonded to each other to form a ring, M represents a metal having an atomic weight of 40 or more, and X 1 to X 3 each independently represent a carbon atom or a nitrogen atom, provided that X 1 to X 3 are not all nitrogen atoms, Q 1 represents a 5- or 6-membered aromatic heterocyclic ring, and Q 2 represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring.
- N1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is not 0.
- the bidentate ligand containing Q 1 and Q 2 is different from other ligands. combined with it may form a tridentate or higher-dentate ligand .Q 1 and Q 2 are linked by a linking group, to form a ring And it may be.)
- the metal complex A has a fluorine atom as at least one of R 1 and R 2 in the general formula (1), and the metal complex B has a halogen other than the fluorine atom, at least one of the fluorine atoms of the metal complex A.
- M represents a metal having an atomic weight of 40 or more, and represents an X 2 carbon atom or a nitrogen atom.
- Q 1 represents a 5-membered or 6-membered aromatic heterocyclic ring.
- E 1 to E 3 represent Each independently represents a carbon atom or a nitrogen atom, provided that E 1 to E 3 do not all represent a nitrogen atom, and n1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is
- the bidentate ligand containing a ring containing the rings Q 1 and E 1 to E 3 may combine with other ligands to form a tridentate or higher ligand.
- [6] The material for an organic electroluminescent element according to any one of [1] to [5], wherein the metal complex A includes a partial structure represented by the following general formula (3).
- M represents a metal having an atomic weight of 40 or more
- E 3 represents a carbon atom or a nitrogen atom
- n3 represents an integer of 1 to 4.
- Bidentate containing a ring containing pyridine and E 3 (The ligand may combine with other ligands to form a tridentate or higher ligand.)
- [7] The material for an organic electroluminescent element according to any one of the above [1] to [6], wherein E 3 is a carbon atom.
- M is Pt.
- M represents Pt.
- L 21 represents a single bond or a divalent linking group.
- Z 21 and Z 22 each independently represent a 5-membered or 6-membered nitrogen-containing aromatic heterocycle.
- Z 23 and Z 24 each independently represent Represents a benzene ring or a 5-membered or 6-membered aromatic heterocycle, each of Z 21 and Z 23 may independently have 1 to 4 substituents, which are bonded to each other to form a ring; Provided that at least one of Z 21 and Z 23 has one or more substituents, and Z 22 and Z 24 may have a substituent, and the substituents are They may combine to form a ring.
- X 21 , X 22 , X 23 and X 24 each independently represent a carbon atom or a nitrogen atom.
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- XY represents a bidentate monoanionic bidentate ligand.
- N represents 1 to 3. Represents an integer.
- R 1 and R 2 each independently represents a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different.
- N1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is not 0.
- XY represents a bidentate monoanionic ligand, where n is 1 to Represents an integer of 3.
- An organic electroluminescent device having a pair of electrodes and at least one organic layer including a light emitting layer containing a light emitting material between the electrodes on a substrate, wherein at least one of the organic layers is the above [1].
- An organic electroluminescent device comprising the material for an organic electroluminescent device according to any one of to [12].
- a material for an organic electroluminescence device comprising at least a phosphorescent metal complex A and a phosphorescent metal complex B, wherein the phosphorescent metal complex A includes a partial structure represented by the following general formula (1), and the phosphorescence In the metal complex B, in at least one substituent of R 1 and R 2 in the general formula (1), one or more of the atoms directly bonded to Q 1 or Q 2 have the same homologous and atomic weight of the atom
- the phosphorescent metal complex A has the same structure as that of the phosphorescent metal complex A except that the phosphorescent metal complex A is replaced by a large atom, and the content ratio of the phosphorescent metal complex B to the phosphorescent metal complex A is 0.005 mass% or more and 2 mass%.
- a composition that is:
- R 1 and R 2 each independently represent a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different.
- X 1 to X 3 each independently represents a carbon atom or a nitrogen atom, provided that X 1 to X 3 do not all represent a nitrogen atom
- Q 1 is a 5-membered or 6-
- Q 2 represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle
- n1 and n2 each independently represents an integer of 0 to 4, and n1 and n2 never sum becomes 0 .
- Q 1 and a bidentate ligand containing Q 2 is other bound to ligand may be formed a tridentate or higher-dentate ligand .
- Q 1 and Q 2 may be linked by a linking group to form a ring.
- R 1 and R 2 each independently represent a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different.
- X 1 to X 3 each independently represents a carbon atom or a nitrogen atom, provided that X 1 to X 3 do not all represent a nitrogen atom
- Q 1 is a 5-membered or 6-
- Q 2 represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle
- n1 and n2 each independently represents an integer of 0 to 4, and n1 and n2 never sum becomes 0 .
- Q 1 and a bidentate ligand containing Q 2 is other bound to ligand may be formed a tridentate or higher-dentate ligand .
- Q 1 and Q 2 may be linked by a linking group to form a ring.
- an organic EL device can be stably stored under visible light, and has excellent efficiency when driven by a device with high brightness.
- An organic electroluminescent element using the material can be provided.
- the material for an organic electroluminescent element of the present invention is a material for an organic electroluminescent element of the present invention, which is a material for an organic electroluminescent element containing at least a phosphorescent metal complex A and a phosphorescent metal complex B.
- the metal complex A includes a partial structure represented by the following general formula (1), and the phosphorescent metal complex B is Q 1 or R 1 in at least one substituent of R 1 and R 2 in the general formula (1).
- the phosphorescent metal complex B is 0.005% by mass or more and 2% by mass or less.
- R 1 and R 2 each independently represent a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different. R 1 and R 2 may be bonded to each other to form a ring, M represents a metal having an atomic weight of 40 or more, and X 1 to X 3 each independently represent a carbon atom or a nitrogen atom, provided that X 1 to X 3 are not all nitrogen atoms, Q 1 represents a 5- or 6-membered aromatic heterocyclic ring, and Q 2 represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring.
- N1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is not 0.
- the bidentate ligand containing Q 1 and Q 2 is different from other ligands. combined with it may form a tridentate or higher-dentate ligand .
- Q 1 and Q 2 are linked by a linking group, to form a ring And it may be.
- the content of the decomposition product or raw material of the metal complex is preferably as small as possible, and is set to a certain amount or less.
- a specific phosphorescent metal complex A is used in a content ratio within a specific range. That is, the present invention and Patent Document 2 are based on completely different technical ideas.
- an element using the material of the present invention reduces a so-called roll-off phenomenon in which the efficiency decreases when driven with extremely high luminance, and maintains high efficiency.
- the phosphorescent metal complex containing the partial structure represented by the general formula (1) in the present invention is also referred to as a specific phosphorescent metal complex.
- the hydrogen atom in description of each general formula in this specification also includes an isotope (deuterium atom etc.), and the atom which comprises a substituent further represents the isotope.
- the material for an organic electroluminescent element of the present invention contains at least a phosphorescent metal complex A and a phosphorescent metal complex B.
- the metal complex A includes a partial structure represented by the following general formula (1) having at least one substituent in at least one ligand, and the metal complex B includes R 1 and R 2 of the general formula (1).
- R 1 and R 2 each independently represent a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different. R 1 and R 2 may be bonded to each other to form a ring, M represents a metal having an atomic weight of 40 or more, and X 1 to X 3 each independently represent a carbon atom or a nitrogen atom, provided that X 1 to X 3 are not all nitrogen atoms, Q 1 represents a 5- or 6-membered aromatic heterocyclic ring, and Q 2 represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring.
- N1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is not 0.
- the bidentate ligand containing Q 1 and Q 2 is different from other ligands. combined with it may form a tridentate or higher-dentate ligand .Q 1 and Q 2 are linked by a linking group, to form a ring
- the line connecting the good .X 2 and X 3, X 1 and the carbon atom also are represented by a single line, but binding species is not limited, may be either double bond respectively a single bond.
- R 1 and R 2 each independently represent a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different. A plurality of R 1 and R 2 may be bonded to each other to form a ring.
- the substituent is preferably selected from the following substituent group A.
- alkyl group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.
- alkenyl groups preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.
- alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl , 3-pentynyl, etc.
- aryl groups preferably having 6 to 30 carbon
- pyridyloxy pyrazyloxy, pyrimidyloxy, quinolyloxy and the like
- an acyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms.
- Benzoyl, formyl, pivaloyl, etc. an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxy Carbonyl, etc.), an aryloxycarbonyl group (preferably It has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl.
- an alkoxycarbonyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxy Carbonyl, etc.
- an aryloxycarbonyl group preferably It has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl
- An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy, etc.), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and alkoxycarbonylamino groups (preferably having 2-2 carbon atoms).
- an aryloxycarbonylamino group preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
- an aryloxycarbonylamino group preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
- a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably 6 to 30 carbon atoms).
- Rufinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carb
- Is for example, a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, selenium atom, tellurium atom, specifically pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, And isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl group, azepinyl group, silolyl group and the like.
- a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl).
- a aryloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), phosphoryl group (for example, A diphenylphosphoryl group, a dimethylphosphoryl group, etc.).
- These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.
- R 1 and R 2 are preferably a halogen atom, a hydrocarbon substituent (preferably a substituted or unsubstituted alkyl group, cycloalkyl group, or aryl group), a cyano group, OR 2a , SR 2a , NR 2a R 2b , BR 2a R 2b , or SiR 2a R 2b R 2c , more preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a fluoroalkyl group , A cyano group, or OR 2a .
- a hydrocarbon substituent preferably a substituted or unsubstituted alkyl group, cycloalkyl group, or aryl group
- a cyano group preferably a halogen atom, a hydrocarbon substituent (preferably a substituted or unsubstituted alkyl group, cycloalkyl group
- R 2a to R 2c are each independently a hydrocarbon substituent or a hydrocarbon substituent substituted with a hetero atom.
- the hetero atom include oxygen, nitrogen, phosphorus, sulfur, selenium, and arsenic, preferably an oxygen, sulfur, and nitrogen atom, and more preferably a nitrogen atom.
- the preferred range of R 2a to R 2c is the same as when R 1 and R 2 are hydrocarbon substituents.
- R 1 and R 2 When a plurality of R 1 and R 2 are present, two of R 1 and R 2 may be bonded to each other to form a saturated or unsaturated aromatic ring or non-aromatic ring.
- R 1 and R 2 are particularly preferably a halogen atom and most preferably a fluorine atom because the emission wavelength can be controlled without lowering the durability.
- R 1 and R 2 are not limited to which part of the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Q 1 or Q 2 which is the mother skeleton of the metal complex A, and are almost equivalent. Give effect.
- it is particularly preferable that R 1 and R 2 are all fluorine atoms.
- the “carbon number” of a substituent such as an alkyl group includes a case where a substituent such as an alkyl group may be substituted by another substituent, and also includes the carbon number of the other substituent. Used to mean
- M is a metal having an atomic weight of 40 or more, and is preferably a non-radioactive metal.
- the metal is more preferably any one of Re, Ru, Os, Rh, Ir, Pd, Pt, Cu, or Au, more preferably Os, Ir, or Pt, and Ir or Pt. Particularly preferred is Pt from the viewpoint of high luminous efficiency and high complex stability.
- X 1 ⁇ X 3 independently. However, X 1 to X 3 do not all represent nitrogen atoms.
- X 1 is preferably a carbon atom.
- X 2 is preferably a carbon atom.
- X 3 is an atom having a bond with a metal, and is preferably a nitrogen atom because the chemical stability of the complex is maintained.
- Q 1 represents a 5-membered or 6-membered aromatic heterocyclic ring.
- Q 1 include pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, and a structure in which other rings are condensed to these rings.
- Examples of the structure in which the other ring is condensed include indolizine, purine, pteridine, ⁇ -carboline, naphthyridine, quinoxaline, acridine, phenanthroline, phenazine, imidazopyridine and the like.
- Q 2 represents a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle.
- Q 2 include benzene, pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, and structures in which other rings are condensed to these rings.
- benzene, pyridine, pyrazine, pyrimidine, imidazole, pyrazole and a structure in which these rings are condensed to these rings more preferably benzene, pyridine, imidazole, pyrazole and these rings have other rings. It is a condensed structure. Examples of the structure in which the other ring is condensed include indolizine, purine, pteridine, ⁇ -carboline, naphthyridine, quinoxaline, acridine, phenanthroline, phenazine, imidazopyridine and the like.
- Q 1 and Q 2 may be linked by a linking group (preferably an arylene group, more preferably a phenylene group) to form a ring. Since this ring is conjugated, it can be regarded as the same as Q 1 and Q 2, and in the substituent bonded to this ring, the atom directly bonded to the ring is replaced with an atom of the same family and high atomic weight.
- a linking group preferably an arylene group, more preferably a phenylene group
- Q 1 and Q 2 may form a condensed ring as a whole via X 1 -X 2 . Examples of such include general formulas (A1) to (A4) described later.
- n1 and n2 each independently represents an integer of 0 to 4. However, the sum of n1 and n2 never becomes zero.
- n1 is preferably 0 or 1, more preferably 0.
- n2 is preferably 1 to 3, more preferably 1 or 2.
- the general formula (1) is preferably represented by the following general formula (2).
- M represents a metal having an atomic weight of 40 or more, and represents an X 2 carbon atom or a nitrogen atom.
- Q 1 represents a 5-membered or 6-membered aromatic heterocyclic ring.
- E 1 to E 3 represent Each independently represents a carbon atom or a nitrogen atom, provided that E 1 to E 3 do not all represent a nitrogen atom, and n1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is It will never be 0.
- E 1 to E 3 are preferably carbon atoms, and E 1 and E 2 are more preferably carbon atoms.
- E 3 is a carbon atom or a nitrogen atom, and is preferably a nitrogen atom from the viewpoint of obtaining light emission with a shorter wavelength.
- the general formula (2) is preferably represented by the following general formula (3).
- M represents a metal having an atomic weight of 40 or more
- E 3 represents a carbon atom or a nitrogen atom
- n3 represents an integer of 1 to 4.
- the preferable range of M is the same as the preferable range of M in the general formula (1).
- n3 is preferably 1 to 2.
- a metal complex in which M in the general formula (1) is Pt will be described.
- the metal complex in which M in the general formula (1) is Pt is preferably represented by the following general formula (C-1).
- R 1 and R 2 respectively .R 1 and R 2 represents a substituent independently may each of R 1 and R 2 in the presence of two or more the same or different than the.
- Plurality of R 1 and R 2 may be bonded to each other to form a ring
- X 1 to X 3 each independently represents a carbon atom or a nitrogen atom, provided that X 1 to X 3 do not all represent a nitrogen atom.
- Q 1 represents a 5- or 6-membered aromatic heterocyclic ring
- Q 2 represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring
- Q 3 and Q 4 are each independently arranged on Pt.
- Q 3 and Q 4 may have a substituent, and the substituents may be bonded to each other to form a ring, and n1 and n2 are each independently 0 to 4 of represents an integer, single bond .L 1 are each independently is not the sum of n1 and n2 is 0 Represents a divalent linking group.
- Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt.
- the bond between Q 1 , Q 2 , Q 3 and Q 4 and Pt may be any of a covalent bond, an ionic bond, a coordinate bond, and the like.
- a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q ⁇ 1 >, Q ⁇ 2 >, Q ⁇ 3 > and Q ⁇ 4 >
- a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q ⁇ 1 >, Q ⁇ 2 >, Q ⁇ 3 > and Q ⁇ 4 >
- at least one is preferably a carbon atom, more preferably two are carbon atoms, particularly preferably two are carbon atoms and two are nitrogen atoms.
- X 1 is preferably a carbon atom.
- X 2 is preferably a carbon atom.
- X 3 is an atom having a bond with a metal, and is preferably a nitrogen atom because the chemical stability of the complex is maintained.
- Q 3 and Q 4 bonded to Pt by a carbon atom may be an anionic ligand or a neutral ligand, and may be a cyclic ligand or an acyclic ligand.
- Anionic ligands include vinyl ligands, aromatic hydrocarbon ring ligands (eg benzene, naphthalene, anthracene, phenanthrene), heterocyclic ligands (For example, furan ligand, thiophene ligand, pyridine ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole coordination And imidazole ligands, pyrazole ligands, triazole ligands and condensed rings containing them (for example, quinoline ligands, benzothiazole ligands, etc.).
- aromatic hydrocarbon ring ligands eg benzene, naphthalene, anthracene, phenanthrene
- heterocyclic ligands for example, furan ligand
- a carbene ligand is mentioned as a neutral ligand.
- Q 3 and Q 4 bonded to Pt with a nitrogen atom may be neutral ligands or anionic ligands.
- neutral ligands nitrogen-containing aromatic heterocyclic ligands (pyridine Ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxazole ligand, thiazole ligand and the like
- a condensed ring eg, quinoline ligand, benzimidazole ligand, etc.
- an amine ligand a nitrile ligand, and an imine ligand.
- anionic ligands include amino ligands, imino ligands, nitrogen-containing aromatic heterocyclic ligands (pyrrole ligands, imidazole ligands, triazole ligands and condensed rings containing them) (For example, indole ligand, benzimidazole ligand, etc.)).
- Q 3 and Q 4 bonded to Pt with an oxygen atom may be neutral ligands or anionic ligands, and neutral ligands include ether ligands, ketone ligands, esters Examples thereof include ligands, amide ligands, and oxygen-containing heterocyclic ligands (furan ligands, oxazole ligands and condensed rings containing them (such as benzoxazole ligands)).
- the anionic ligand include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, and the like.
- Q 3 and Q 4 bonded to Pt with a sulfur atom may be neutral ligands or anionic ligands, and neutral ligands include thioether ligands, thioketone ligands, and thioesters. Examples thereof include a ligand, a thioamide ligand, and a sulfur-containing heterocyclic ligand (thiophene ligand, thiazole ligand, and a condensed ring containing them (such as a benzothiazole ligand)).
- the anionic ligand include an alkyl mercapto ligand, an aryl mercapto ligand, and a heteroaryl mercapto ligand.
- Q 3 and Q 4 bonded to Pt with a phosphorus atom may be neutral ligands or anionic ligands, and neutral ligands include phosphine ligands and phosphate ester ligands.
- Phosphite ligands, phosphorus-containing heterocyclic ligands (phosphinin ligands, etc.), and anionic ligands include phosphino ligands, phosphinyl ligands, phosphoryl ligands, etc. Is mentioned.
- Q 3 and Q 4 may have a substituent, and as the substituent, those exemplified as the substituent group A can be appropriately applied. Moreover, substituents may be connected to each other (when Q 3 and Q 4 are connected, a Pt complex of a cyclic tetradentate ligand is formed).
- Q 3 and Q 4 are preferably aromatic hydrocarbon ring ligands bonded to Pt with carbon atoms, aromatic heterocyclic ligands bonded to Pt with carbon atoms, nitrogen-containing aromatics bonded to Pt with nitrogen atoms Group heterocyclic ligands, acyloxy ligands, alkyloxy ligands, aryloxy ligands, heteroaryloxy ligands, silyloxy ligands, more preferably aromatics bonded to Pt by carbon atoms Hydrocarbon ring ligand, aromatic heterocyclic ligand bonded to Pt with carbon atom, nitrogen-containing aromatic heterocyclic ligand bonded to Pt with nitrogen atom, acyloxy ligand, aryloxy ligand More preferably, an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, an aromatic heterocyclic ligand bonded to Pt with a carbon atom, a nitrogen-containing aromatic heterocyclic ring bonded to Pt with
- Examples of Q 1 include pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, and a structure in which these rings are condensed with other rings, preferably pyridine.
- Pyrazine, pyrimidine, imidazole, pyrazole, and a structure in which these rings are condensed to other rings and more preferably a structure in which pyridine, imidazole, pyrazole and these rings are condensed to other rings.
- Examples of the structure in which the other ring is condensed include indolizine, purine, pteridine, ⁇ -carboline, naphthyridine, quinoxaline, acridine, phenanthroline, phenazine, imidazopyridine and the like.
- Examples of Q 2 include benzene, pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, and structures in which other rings are condensed to these rings. Is a structure in which benzene, pyridine, pyrazine, pyrimidine, imidazole, pyrazole and other rings are condensed to these rings, more preferably benzene, pyridine, imidazole, pyrazole and other rings are condensed to these rings. Structure.
- Examples of the structure in which the other ring is condensed include indolizine, purine, pteridine, ⁇ -carboline, naphthyridine, quinoxaline, acridine, phenanthroline, phenazine, imidazopyridine and the like.
- examples of the substituent represented by R 1 and R 2 have the same meanings as the substituents represented by R 1 and R 2 in the general formula (1), and preferred ranges are also the same.
- Any one or more of Q 1 , Q 2 , Q 3 and Q 4 preferably have a fluorine substituent.
- the number of fluorine substituents is not particularly limited, but is preferably 3 or less for one ligand from the viewpoint of suppressing layer separation.
- the fluorine substituent is chemically substituted with Q 1 , Q 2 , Q 3 and Q 4 which are substituted with aromatic hydrocarbon ring ligand, heterocyclic ligand and condensed ring containing them. It is preferable from the viewpoint of stability.
- L 1 represents a single bond or a divalent linking group.
- the divalent linking group represented by L 1 include alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.), imino groups (- NR-) (phenylimino group etc.), oxy group (—O—), thio group (—S—), phosphinidene group (—PR—) (phenylphosphinidene group etc.), silylene group (—SiRR′—) (A dimethylsilylene group, a diphenylsilylene group, etc.), or a combination thereof.
- linking groups may further have a substituent.
- substituents include a substituent selected from the substituent group A, and preferred ranges are the same as those for R 1 and R 2 .
- L 1 is preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group, or a silylene group, more preferably a single bond.
- a methylene group more preferably a single bond, dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethylmethylmethylene group, methylpropylmethylene group, isobutylmethylmethylene group, diphenylmethylene group, methylphenylmethylene Group, cyclohexanediyl group, cyclopentanediyl Group, fluorenediyl group and fluoromethylmethylene group, particularly preferably a single bond, dimethylmethylene group, diphenylmethylene group and cyclohexanediyl group.
- n1 and n2 each independently represents an integer of 0 to 4. However, the sum of n1 and n2 never becomes zero.
- n1 is preferably 0 or 1, more preferably 0.
- n2 is preferably 1 to 3, more preferably 1 or 2.
- platinum complexes represented by the general formula (C-1) a platinum complex represented by the following general formula (C-2) is more preferable.
- L 21 represents a single bond or a divalent linking group.
- Z 21 and Z 22 each independently represent a 5-membered or 6-membered nitrogen-containing aromatic heterocycle.
- Z 23 and Z 24 each independently represent Represents a benzene ring or a 5-membered or 6-membered aromatic heterocycle, each of Z 21 and Z 23 may independently have 1 to 4 substituents, which are bonded to each other to form a ring; Provided that at least one of Z 21 and Z 23 has one or more substituents, and Z 22 and Z 24 may have a substituent, and the substituents are They may combine to form a ring.
- X 21 , X 22 , X 23 and X 24 each independently represent a carbon atom or a nitrogen atom.
- L 21 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
- X 21 , X 22 , X 23 and X 24 have the same meanings as X 1 and X 2 in formula (C-1), respectively, and preferred ranges are also the same.
- Z 21 and Z 22 each independently represent a 5-membered or 6-membered nitrogen-containing aromatic heterocycle.
- the nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 include a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, an oxazole ring, a thiazole ring, and a triazole ring.
- the ring represented by Z 21 and Z 22 is preferably a pyridine ring, a pyrazine ring, an imidazole ring or a pyrazole ring, more preferably a pyridine ring.
- the 5- or 6-membered nitrogen-containing aromatic heterocycle represented by Z 22 may have a substituent, and the substituent group A is a substituent on a nitrogen atom as a substituent on a carbon atom.
- the following substituent group B can be applied as the group.
- alkyl group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, and n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, trifluoromethyl, pentafluoroethyl, etc.), alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon numbers).
- alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon number
- alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon number
- aryl groups preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, and pentafluorophenyl.
- An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably having a carbon number) 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms.
- phenyloxycarbonyl and the like acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy and the like. ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, And carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
- heterocyclic groups preferably Or a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom, specifically, imidazolyl, pyridyl, quinolyl, furyl, thienyl
- heterocyclic groups preferably Or a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom, specifically, imidazolyl, pyridyl, quinolyl, furyl, thienyl
- Examples include piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like.
- the substituent on the carbon atom is preferably an alkyl group, a polyfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom.
- the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable.
- an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected.
- an electron withdrawing group is preferable, for example, a cyano group, a polyfluoroalkyl group, etc. are selected.
- the substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
- the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
- Z 23 and Z 24 each independently represent a benzene ring or a 5-membered or 6-membered aromatic heterocycle.
- the nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 include a pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadi Examples include an azole ring, a thiadiazole ring, a thiophene ring, and a furan ring.
- the ring represented by Z 23 and Z 24 is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, or a thiophene ring, More preferred are a benzene ring, a pyridine ring and a pyrazole ring, and still more preferred are a benzene ring and a pyridine ring.
- the benzene ring, 5-membered or 6-membered nitrogen-containing aromatic heterocycle represented by Z 24 may have a substituent, and the substituent group A is a nitrogen atom as a substituent on a carbon atom.
- the above substituent group B can be applied as the above substituent.
- Preferred substituents on carbon are alkyl groups, polyfluoroalkyl groups, aryl groups, aromatic heterocyclic groups, dialkylamino groups, diarylamino groups, alkoxy groups, cyano groups, and halogen atoms.
- the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected.
- an electron withdrawing group is preferable.
- a fluorine group, a cyano group, a polyfluoroalkyl group, or the like is selected.
- the substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
- the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
- examples of the substituent that Z 21 and Z 23 may have include a substituent selected from the substituent group A, and a preferred range thereof is the general formula (1).
- the preferred range of the number of substituents is the same as in the general formula (1).
- Any one or more of Z 21 and Z 23 preferably have a fluorine substituent.
- the number of fluorine substituents is not particularly limited, but is preferably 3 or less per ring from the viewpoint of suppressing layer separation.
- the preferred range of the substituent that Z 22 and Z 24 may have is the same as Z 21 and Z 23 .
- platinum complexes represented by the general formula (C-2) one of more preferred embodiments is a platinum complex represented by the following general formula (C-3).
- a 301 to A 313 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- L 31 represents a single bond or a divalent linking group.
- L 31 has the same meaning as L 21 in formula (C-2), and the preferred range is also the same.
- a 301 to A 306 each independently represents C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- substituent represented by R those exemplified as the substituent group A can be applied.
- a 301 to A 306 are preferably C—R, and Rs may be connected to each other to form a ring.
- R in A 302 and A 305 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group. More preferred are a hydrogen atom, an alkyl group, an aryl group, an amino group and a fluorine group, and particularly preferred are a hydrogen atom, a methyl group, a phenyl group, a xylyl group and a fluorine group.
- the alkyl group and aryl group may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, a cyano group, an amino group, a halogen atom, and a fluoroalkyl group.
- An alkyl group having 6 carbon atoms, a cyano group, an amino group, a halogen atom and a fluoroalkyl group (preferably a trifluoromethyl group), more preferably an alkyl group having 1 to 6 carbon atoms and a halogen atom (preferably a fluorine atom).
- R in A 302 and A 305 is preferably an aryl group from the viewpoint of improving the durability of the device, and a hydrogen atom or an alkyl group from the viewpoint of a short emission wavelength.
- An amino group, an alkoxy group, a fluorine group and a cyano group are preferred.
- R in A 301 , A 303 , A 304 and A 306 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group or a cyano group, more preferably a hydrogen atom or an amino group.
- a 307 , A 308 , A 309 and A 310 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied.
- R is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diaryl
- An amino group, an alkyloxy group, a cyano group, and a halogen atom more preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, a fluorine atom, still more preferably a hydrogen atom, An alkyl group, a trifluoromethyl group, and a fluorine atom; If possible, the substituents may be linked to form a condensed ring structure.
- a 308 is preferably a nitrogen atom.
- the 6-membered ring formed from two carbon atoms and A 307 , A 308 , A 309 and A 310 includes a benzene ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.
- a pyridazine ring and a triazine ring more preferably a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring, and particularly preferably a benzene ring and a pyridine ring.
- the 6-membered ring is a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring (particularly preferably a pyridine ring), a hydrogen atom present at a position where a metal-carbon bond is formed as compared with a benzene ring. Since the acidity is improved, it is advantageous in that a metal complex is more easily formed.
- a 311 , A 312 and A 313 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- substituent represented by R those exemplified as the substituent group A can be applied.
- R is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, An alkyloxy group, a cyano group, and a halogen atom, more preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, and a fluorine atom, more preferably a hydrogen atom, an alkyl group, A trifluoromethyl group and a fluorine atom. If possible, the substituents
- platinum complexes represented by the general formula (C-2) one of more preferred embodiments is a platinum complex represented by the following general formula (C-4).
- a 401 to A 414 each independently represents C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- L 41 represents a single bond or a divalent linking group.
- a 401 to A 414 each independently represents C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent, and a preferred range is the same as R in the general formula (C-3), but one or more preferably represents a fluorine atom.
- a 401 to A 406 and L 41 have the same meanings as A 301 to A 306 and L 31 in formula (C-3), and preferred ranges thereof are also the same.
- the number of nitrogen atoms is preferably 0 to 2, and more preferably 0 to 1.
- a 408 and A 412 are preferably nitrogen atoms, and both A 408 and A 412 are more preferably nitrogen atoms.
- R in A 408 and A 412 is preferably a hydrogen atom, alkyl group, polyfluoroalkyl group, aryl group, amino group, alkoxy group, aryloxy group, fluorine group And a cyano group, more preferably a hydrogen atom, a polyfluoroalkyl group, an alkyl group, an aryl group, a fluorine group, and a cyano group, and particularly preferably a hydrogen atom, a polyfluoroalkyl group, a fluorine group, and a cyano group.
- R of A 407 , A 409 , A 411 , and A 413 is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group, and more preferably Is a hydrogen atom, a polyfluoroalkyl group, a fluorine group or a cyano group, particularly preferably a hydrogen atom or a fluorine group.
- R in A 410 and A 414 is preferably a hydrogen atom or a fluorine group, and more preferably a hydrogen atom.
- Rs may be connected to each other to form a ring.
- platinum complexes represented by the general formula (C-2) one of the more preferred embodiments is a platinum complex represented by the following general formula (C-5).
- a 501 to A 512 each independently represents C—R or a nitrogen atom, R represents a hydrogen atom or a substituent, and L 51 represents a single bond or a divalent linkage. Represents a group.
- a 501 to A 506 and L 51 have the same meanings as A 301 to A 306 and L 31 in formula (C-3), and preferred ranges thereof are also the same.
- a 501 to A 506 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent, and a preferred range is the same as R in the general formula (C-3), but one or more preferably represents a fluorine atom.
- a 507 , A 508, A 509 and A 510 , A 511, and A 512 are each independently the same as A 311 , A 312, and A 313 in formula (C-3), and the preferred ranges are also the same. is there.
- platinum complexes represented by the general formula (C-1) another more preferable embodiment is a platinum complex represented by the following general formula (C-6).
- L 61 represents a single bond or a divalent linking group.
- Z 61 and Z 62 each independently represent a 5-membered or 6-membered nitrogen-containing aromatic heterocycle.
- Z 63 each independently represents a benzene ring.
- Y is an anionic acyclic ligand bonded to Pt, and
- Z 61 and Z 63 each independently have 1 to 4 substituents.
- the substituents may be bonded to each other to form a ring, provided that at least one of Z 61 and Z 63 has one or more substituents, and Z 62 has a substituent.
- X 61 and X 62 each independently represent a carbon atom or a nitrogen atom.
- L 61 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
- X 61 and X 62 have the same meanings as X 1 and X 2 in the general formula (C-1), and preferred ranges are also the same.
- Z 61 and Z 62 are synonymous with Z 21 and Z 22 in the general formula (C-2), respectively, and preferred ranges thereof are also the same.
- Z 63 has the same meaning as Z 23 in formula (C-2), and the preferred range is also the same.
- Y is an anionic acyclic ligand that binds to Pt.
- An acyclic ligand is one in which atoms bonded to Pt do not form a ring in the form of a ligand.
- a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, a nitrogen atom and an oxygen atom are more preferable, and an oxygen atom is the most preferable.
- a vinyl ligand is mentioned as Y couple
- Examples of Y bonded to Pt with an oxygen atom include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, a carboxyl ligand, a phosphate ligand, Examples thereof include sulfonic acid ligands.
- Examples of Y bonded to Pt with a sulfur atom include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, and thiocarboxylic acid ligands.
- the ligand represented by Y may have a substituent, and those exemplified as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other.
- the ligand represented by Y is preferably a ligand bonded to Pt with an oxygen atom, more preferably an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand. , A silyloxy ligand, and more preferably an acyloxy ligand.
- examples of the substituent that Z 61 and Z 63 may have include a substituent selected from the substituent group A, and a preferable range thereof is the general formula (1).
- the preferred range of the number of substituents is the same as in the general formula (1).
- Any one or more of Z 61 and Z 63 preferably have a fluorine substituent.
- the number of fluorine substituents is not particularly limited, but is preferably 3 or less per ring from the viewpoint of suppressing layer separation.
- Z 62 has optionally may substituent, and preferred ranges thereof are the same as Z 61 and Z 63.
- platinum complexes represented by the general formula (C-6) one of more preferred embodiments is a platinum complex represented by the following general formula (C-7).
- a 701 to A 710 each independently represents C—R or a nitrogen atom, R represents a hydrogen atom or a substituent, L 71 represents a single bond or a divalent linking group, Y represents An anionic acyclic ligand that binds to Pt.
- L 71 has the same meaning as L 61 in formula (C-6), and the preferred range is also the same.
- a 701 to A 710 have the same meanings as A 301 to A 310 in formula (C-3), and preferred ranges are also the same.
- Y has the same meaning as that in formula (C-6), and the preferred range is also the same.
- a 701 to A 706 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent, and a preferred range is the same as R in the general formula (C-3), but one or more preferably represents a fluorine atom.
- platinum complex represented by the general formula (C-1) are described in JP-A-2005-310733, [0143] to [0152], [0157] to [0158], and [0162] to [0168].
- Examples of the platinum complex compound represented by the general formula (C-1) include Journal of Organic Chemistry 53,786, (1988), G.S. R. Newkome et al. ), Page 789, the method described in left line 53 to right line 7, line 790, the method described in left line 18 to line 38, the method described in page 790, right line 19 to line 30 and The combination, Chemische Berichte 113, 2749 (1980), H.C. Lexy et al.), Page 2752, lines 26 to 35, and the like.
- a ligand or a dissociated product thereof and a metal compound are mixed with a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent,
- a solvent for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent
- a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.
- a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.
- a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine
- a metal complex (also referred to as a specific iridium complex) in which M in the general formula (1) is Ir will be described.
- the specific iridium complex preferably has a bidentate ligand represented by the following general formula (A1), general formula (A2), general formula (A3), or general formula (A4).
- A1 general formula
- A2 general formula
- A3 general formula
- A4 general formula
- * is a coordination site to iridium
- the bond between E 1a and iridium and the bond between E 1p and iridium are each independently a covalent bond. It may be a coordinate bond.
- E 1a to E 1q each independently represents a carbon atom or a hetero atom.
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- To (A4) each have a total of 18 ⁇ electronic structure, provided that in general formulas (A1) and (A3), at least one of R 1a to R 1i represents a substituent.
- At least one of R 1a to R 1h represents a substituent.
- E 1a to E 1q are selected from a carbon atom or a hetero atom, and preferably selected from a carbon atom or a nitrogen atom.
- E 1a and E 1p are preferably different atoms.
- the skeleton has an 18 ⁇ electron structure.
- * is a coordination site to a metal
- E 1a and the metal bond, and E 1q and the metal bond are each independently a covalent bond, It may be a coordinate bond.
- the bidentate ligand may be combined with another ligand to form a tridentate, tetradentate, pentadentate or hexadentate ligand.
- Heteroatom refers to an atom other than a carbon atom or a hydrogen atom.
- heteroatoms include, for example, oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon, or fluorine.
- the 5-membered ring formed from E 1a to E 1e represents a 5-membered heterocycle.
- Specific examples of the 5-membered heterocycle include oxazole, thiazole, isoxazole, isothiazole, pyrrole, imidazole, pyrazole, triazole, tetrazole and the like. Preferred is imidazole or pyrazole, and more preferred is imidazole.
- These 5-membered rings may be condensed with other rings.
- E 1a ⁇ E 1e represent at least one nitrogen atom of the E 1a ⁇ E 1e, two of E 1a ⁇ E 1e, or more preferably representing three but nitrogen atom, of the E 1a ⁇ E 1e It is particularly preferred that two represent nitrogen atoms.
- two of E 1a to E 1e represent nitrogen atoms
- two of E 1a , E 1d , and E 1e represent nitrogen atoms
- E 1a and E 1d or E 1a and E 1e are nitrogen
- E1a and E1d represent a nitrogen atom.
- the ring formed from E 1f to E 1k is a 5-membered or 6-membered aromatic hydrocarbon ring or heterocycle, preferably a 6-membered ring, more preferably a 6-membered aromatic hydrocarbon ring.
- Specific examples of the ring formed from E 1f to E 1k include benzene, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, furan, thiophene, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine , Pyridazine, triazine and the like.
- Preferred is pyridine or benzene, and more preferred is benzene.
- the ring formed from E 1l to E 1q is a 5-membered or 6-membered aromatic hydrocarbon ring or heterocycle, preferably a 6-membered ring, more preferably a 6-membered aromatic hydrocarbon ring.
- Specific examples of the ring formed from E 1l to E 1q include benzene, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, furan, thiophene, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine. , Pyridazine, triazine and the like. Preferred is pyridine or benzene, and more preferred is benzene.
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- the substituent is preferably a group selected from the substituent group A.
- at least one of R 1a to R 1i represents a substituent.
- at least one of R 1a to R 1h represents a substituent. It is preferable that at least one of R 1a , R 1b , R 1g , R 1h , and R 1i represents a substituent.
- the substituents represented by R 1a to R 1i have the same meanings as the substituents represented by R 1 and R 2 in general formula (1), and the preferred ranges are also the same.
- the substituents represented by R 1a to R 1h are the same as the substituents represented by R 1 and R 2 in the general formula (1), and the preferred ranges are also the same.
- R 1a to R 1i are preferably a hydrogen atom, a halogen atom, a hydrocarbon substituent (preferably an alkyl group, a cycloalkyl group, or an aryl group), a cyano group, OR 2a , SR 2a , NR 2a R 2b , BR 2a R 2b , or SiR 2a R 2b R 2c .
- R 2a to R 2c are each independently a hydrocarbon substituent or a hydrocarbon substituent substituted with a hetero atom, and two of R 1a to R 1i and R 2a to R 2c are bonded to each other, saturated or An unsaturated aromatic ring or non-aromatic ring may be formed. When bonded to a nitrogen atom, R 1a to R 1i are not present.
- At least one of R 1a to R 1i is preferably an aryl group having a dihedral angle of 70 degrees or more with respect to the mother skeleton, more preferably a substituent represented by the following general formula ss-1. , 6-disubstituted aryl groups are more preferred, and R 1b is most preferably a 2,6-disubstituted aryl group.
- Ra, Rb, and Rc each independently represents a hydrogen atom, an alkyl group, or an aryl group.
- the number of Rc is 0 to 3.
- the alkyl group represented by Ra, Rb and Rc preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
- the aryl group represented by Ra, Rb and Rc preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
- phenyl, o-methylphenyl, m- Examples thereof include methylphenyl, p-methylphenyl, 2,6-xylyl, p-cumenyl, mesityl, naphthyl, anthranyl, and the like.
- a phenyl group, 2,6-xylyl, and mesityl are preferable, and a phenyl group is more preferable.
- At least one of Ra and Rb is preferably selected from an alkyl group or an aryl group, more preferably at least one of Ra and Rb is selected from an alkyl group, and Ra and Rb are both alkyl groups.
- both Ra and Rb are most preferably a methyl group or an isopropyl group.
- the 2,6-disubstituted aryl group is preferably 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 2, 6-dimethyl-4-phenylphenyl group, 2,6-dimethyl-4- (2,6-dimethylpyridin-4-yl) phenyl group, 2,6-diphenylphenyl group, 2,6-diphenyl-4-isopropyl Phenyl group, 2,4,6-triphenylphenyl group, 2,6-diisopropyl-4- (4-isopropylphenyl) phenyl group, 2,6-diisopropyl-4- (3,5-dimethylphenyl) phenyl group, It is a 2,6-diisopropyl-4- (pyridin-4-yl) phenyl group or a 2,6-d
- the number of Rc is preferably 0 or 1.
- a plurality of Rc may be the same or different.
- R 1a to R 1i is preferably an alkyl group.
- R 1e is more preferably an alkyl group.
- the alkyl group is preferably an alkyl group branched from a benzylic position composed of 4 or more carbon atoms, preferably a methyl group or a neopentyl group, and more preferably a neopentyl group.
- At least one of R 1a and R 1b is preferably an electron donating group, R 1a is preferably an electron donating substituent, and R 1a is more preferably a methyl group.
- the hydrocarbon substituent is a monovalent or divalent, linear, branched or cyclic substituent, and refers to a group consisting of only a carbon atom and a hydrogen atom.
- monovalent hydrocarbon substituents include one or more groups selected from alkyl groups having 1 to 20 carbon atoms; alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and aryl groups.
- Examples of the divalent hydrocarbon group include —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, 1,2-phenylene group and the like.
- the bidentate ligand represented by any one of the general formulas (A1) to (A4) is preferably a bidentate ligand represented by the general formula (A1) or (A3).
- the bidentate ligand represented by the general formula (A1) or (A3) is a monoanionic bidentate ligand represented by the following general formula (A1-1) or (A3-1) Is preferred.
- E 1a , E 1d , E 1e to E 1q each independently represents a carbon atom or a hetero atom.
- R 1a to R 1i each independently represents a hydrogen atom.
- the skeletons represented by the general formulas (A1-1) and (A3-1) each have a total of 18 ⁇ electronic structure, provided that at least one of R 1a to R 1i represents a substituent. To express.)
- E 1a , E 1d , E 1e to E 1q and R 1a to R 1i are E 1a in general formulas (A1) and (A3), The same as E 1d , E 1e to E 1q and R 1a to R 1i .
- a monoanionic bidentate ligand represented by the general formula (A1-1) is more preferable.
- the bidentate ligand represented by the general formula (A1-1) or (A3-1) is a monoanionic bidentate coordination represented by the following general formula (A1-2) or (A3-2) It is preferable that it is a child.
- E 1f to E 1q each independently represents a carbon atom or a hetero atom
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- the skeletons represented by the general formulas (A1-2) and (A3-2) each have a total of 18 ⁇ electronic structure, provided that at least one of R 1a to R 1i represents a substituent.
- E 11 to E 1q and R 1a to R 1i are preferably E 11 to E 1q in the general formulas (A1-1) and (A3-1). And R 1a to R 1i are the same.
- the monoanionic bidentate ligands represented by general formulas (A1-1) and (A3-1) are monoanionic 2 represented by general formulas (A1-3) or (A3-3). More preferably, it is a bidentate ligand.
- E 1f to E 1q each independently represents a carbon atom or a hetero atom
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- the skeletons represented by the general formulas (A1-3) and (A3-3) each have a total of 18 ⁇ electron structure, provided that at least one of R 1a to R 1i represents a substituent.
- E 1l to E 1q and R 1a to R 1i are preferably E 1l to E 1q in the general formulas (A1-1) and (A2-1). And R 1a to R 1i are the same.
- the monoanionic bidentate ligands represented by general formulas (A1-3) and (A3-3) are monoanionic 2 represented by general formulas (A1-4) or (A3-4). More preferably, it is a bidentate ligand.
- E 1f to E 1k each independently represents a carbon atom or a hetero atom
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- the skeletons represented by the general formulas (A1-4) and (A3-4) each have a total of 18 ⁇ electron structure, provided that at least one of R 1a to R 1i represents a substituent.
- E 1f to E 1k and R 1a to R 1i are preferably E 1l to E 1q in the general formulas (A1-1) and (A2-1). And R 1a to R 1i are the same.
- the monoanionic bidentate ligands represented by the general formulas (A1-4) and (A3-4) are monoanionic bidentate ligands represented by the following general formula (A1-5) Preferably there is.
- R 1a to R 1i each independently represents a hydrogen atom or a substituent. However, at least one of R 1a to R 1i represents a substituent.
- R 1a ⁇ R 1i are the same as R 1a ⁇ R 1i in the formula (A1-3).
- the bidentate ligand represented by the general formula (A1-5) is preferably a bidentate ligand represented by the following general formula (A1-6).
- R 1a , R 1g , R 1h , and R 1i each independently represents a hydrogen atom or a substituent
- Rb and Rc each independently represent a hydrogen atom, an alkyl group, or an aryl group. Provided that at least one of R 1a to R 1g , R 1h and R 1i represents a substituent.
- R 1a, R 1g, R 1h, preferred for R 1i is, R 1a, is the same as R 1g, R 1h, R 1i in the formula (A1-1).
- the preferred Rb and Rc are the same as Rb and Rc in the general formula ss-1.
- the specific iridium complex is preferably a phosphorescent metal complex represented by the following general formula (A10).
- R 1a to R 1i each independently represents a hydrogen atom or a substituent.
- XY represents a bidentate monoanionic bidentate ligand.
- N represents 1 to 3. Represents an integer, provided that at least one of R 1a to R 1i represents a substituent.
- R 1a ⁇ R 1i are the same as those preferred for R 1a ⁇ R 1i in the formula (A1).
- (XY) represents a bidentate monoanionic subligand. These sub-ligands are believed not to contribute directly to the luminescent properties, but to control the luminescent properties of the molecules. “3-n” may be 0, 1 or 2.
- the bidentate monoanionic ligand used in the luminescent material can be selected from those known in the art. Examples of the bidentate monoanionic ligand include those described in Lamansky et al., PCT application WO 02/15645, pages 89 to 90, but the present invention is not limited thereto.
- Preferred bidentate monoanionic secondary ligands include acetylacetonate (acac) and picolinate (pic), and derivatives thereof.
- a metal complex comprising a main ligand represented by any one of the general formulas (A1) to (A1-6) is a main ligand or a tautomer thereof and a subligand or a tautomer thereof. It may be composed of a combination of mutants, or all of the ligands of the metal complex may be composed only of a partial structure represented by the main ligand or a tautomer thereof.
- the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.
- the ligand consists of two types from the viewpoint of ease of synthesis.
- ligands As sub-ligands used in conventionally known metal complexes.
- ligands eg, halogen ligands (preferably chlorine ligands), etc., published in 1987, published by Yersin, “Organometallic Chemistry-Fundamentals and Applications-” Examples thereof include nitrogen heteroaryl ligands (for example, bipyridyl, phenanthroline, etc.), diketone ligands (for example, acetylacetone, etc.)
- the secondary ligand of the present invention is preferably a diketone or a picolinic acid derivative.
- Rx, Ry and Rz each independently represent a hydrogen atom or a substituent.
- substituent include a substituent selected from the substituent group A.
- Rx and Rz are each independently an alkyl group, a perfluoroalkyl group, a halogen atom or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl having 1 to 4 carbon atoms.
- Ry is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, a halogen atom or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted phenyl group. And most preferably a hydrogen atom or a methyl group.
- Rx, Ry, and Rz may be any chemically stable substituent, and the effects of the present invention Will not be affected.
- general formula (l-1), (1-4), or (1-5) is more preferable, general formula (l-1), or (1-4) is more preferable, and general formula (l- 1) is particularly preferred.
- the bidentate monoanionic ligand is preferably acetylacetonate (acac) from the viewpoint of the stability of the complex and the high emission quantum yield.
- n is preferably 3 from the viewpoint of easiness of synthesis, but replacing n with 1 or 2 and replacing the ligand with an inexpensive sub-ligand from the viewpoint of cost reduction. Also preferred.
- the general formula (A10) is represented by the following general formula (A10-1).
- R 1a to R 1i each independently represents a hydrogen atom or a substituent. However, at least one of R 1a to R 1i represents a substituent.
- preferred ones R 1a ⁇ R 1i are the same as those preferred for R 1a ⁇ R 1i in the formula (A1).
- R 1a ⁇ R 1i is the general formula (A1) have the same meanings as R 1a ⁇ R 1i in, preferable ones are also same.
- Examples of phosphorescent metal complexes containing monoanionic bidentate ligands represented by general formulas (A1) to (A4) and a metal having an atomic weight of 40 or more include the methods described in US2007 / 0190359 and US2008 / 0297033. Can be synthesized by various methods.
- the specific iridium complex is also preferably a compound represented by the following general formula (P-1).
- R 1 and R 2 each independently represents a substituent. When a plurality of R 1 and R 2 are present, each R 1 and R 2 may be the same or different. When a plurality of R 1 and R 2 are present, they may combine with each other to form a ring, and n1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 is 0 E 3 represents a carbon atom or a nitrogen atom, XY represents a bidentate monoanionic ligand, and n represents an integer of 1 to 3.
- n is preferably from 2 to 3, and more preferably 2.
- E 3 is preferably a carbon atom for the reason of improving the chemical stability of the complex. From the viewpoint of emitting light at a short wavelength, it is also preferable that E 3 is a nitrogen atom.
- R 1, R 2, n1 and n2 have the same meanings as R 1, R 2, n1 and n2 in formula (1), and preferred ranges are also the same.
- R 1 and R 2 are preferably a substituent selected from the above substituent group A, preferably a halogen atom, a hydrocarbon substituent (preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, Heteroaryl group), OR 2a , SR 2a , NR 2a R 2b , BR 2a R 2b , or SiR 2a R 2b R 2c .
- substituent group A preferably a halogen atom, a hydrocarbon substituent (preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, Heteroaryl group), OR 2a , SR 2a , NR 2a R 2b , BR 2a R 2b , or SiR 2a R 2b R 2c .
- R 2a to R 2c are each independently a hydrocarbon substituent or a hydrocarbon substituent substituted with a hetero atom, and two of R 1a to R 1i and R 2a to R 2c are bonded to each other, saturated or An unsaturated aromatic ring or non-aromatic ring may be formed.
- R 1 and R 2 represent an alkyl group, they may further have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the following substituent Z.
- the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as a methyl group, an ethyl group, an i-propyl group, a cyclohexyl group, Examples thereof include t-butyl group.
- a halogen atom —R ′, —OR ′, —N (R ′) 2 , —SR ′, —C (O) R ′, —C (O) OR ′, —C (O) N (R ') 2, -CN , -NO 2, -SO 2, -SOR', - SO 2 R ', or -SO 3 R'
- R ' are each independently a hydrogen atom
- an alkyl group Represents a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
- R 1 and R 2 represent a cycloalkyl group, they may further have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-mentioned substituents Z can be mentioned.
- the cycloalkyl group is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total, and examples thereof include a cyclopentyl group and a cyclohexyl group.
- R 1 and R 2 represent an alkenyl group, it preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 1-propenyl, -Isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
- R 1 and R 2 represent an alkynyl group, it preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as ethynyl, propargyl, 1-propynyl, 3 -Pentynyl and the like.
- R 1 and R 2 represent a heteroalkyl group
- a group in which at least one carbon of the alkyl group is replaced with O, NR, or S can be exemplified.
- R 1 and R 2 represent an aryl group
- a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group are preferable.
- R 1 and R 2 represent a heteroaryl group, it is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group.
- R 1 and R 2 are preferably an alkyl group, a cycloalkyl group, a cyano group, a perfluoroalkyl group, a dialkylamino group, an aryl group, a heteroaryl group, or a halogen atom, more preferably an alkyl group, a cyano group, or a perfluoro group.
- a methyl group, an aryl group, or a halogen atom more preferably an alkyl group, an aryl group, a trifluoromethyl group, or a halogen atom, and particularly preferably a methyl group, an isobutyl group, a phenyl group, or a fluorine atom. is there.
- substituent Z an alkyl group, an alkoxy group, a fluoro group, a cyano group, and a dialkylamino group are preferable, and an alkyl group is more preferable.
- R 1 and R 2 when a plurality of R 1 and R 2 are present, they may be bonded to each other to form a ring.
- the ring formed is preferably a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is more preferably a cycloalkyl group, a cycloheteroalkyl group, an aryl group, or a heteroaryl group, and an aryl group More preferably.
- (XY) represents a bidentate monoanionic ligand.
- “3-n” may be 0, 1 or 2.
- the bidentate monoanionic ligand used in the luminescent material can be selected from those known in the art. Examples of the bidentate monoanionic ligand include those described in Lamansky et al., PCT application WO 02/15645, pages 89 to 90, but the present invention is not limited thereto.
- Preferred bidentate monoanionic ligands include acetylacetonate (acac) and picolinate (pic), and derivatives thereof.
- the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.
- the ligand consists of two types from the viewpoint of ease of synthesis.
- ligands used in the conventionally known metal complexes.
- halogen ligands preferably chlorine ligands
- Nitrogen heteroaryl ligands for example, bipyridyl, phenanthroline, etc.
- diketone ligands for example, acetylacetone, etc.
- XY is preferably a diketone or a picolinic acid derivative.
- the preferred range of the ligand is the same as (XY) in the general formula (A10).
- One preferred form of the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-2).
- R 1 and R 2 each independently represents an alkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, —NR 2 , a halogen atom, an aryl group or a heteroaryl group. May further have a substituent Z.
- Each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group. You may have. Any two adjacent R 1 and R 2 are not bonded to each other to form a condensed ring.
- Each of the substituents Z independently represents a halogen atom, —R ′, —OR ′, —N (R ′) 2 , —SR ′ or —CN, and each R ′ independently represents a hydrogen atom, an alkyl group, A haloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group; n1 and n2 each independently represents an integer of 0 to 4, but the sum of n1 and n2 never becomes 0.
- XY represents a bidentate monoanionic ligand.
- n represents an integer of 1 to 3.
- the compound represented by the general formula (P-2) is preferably a compound represented by the following general formula (P-3).
- R 1 , R 2 , R 3 , and R 4 are each independently an alkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, —NR 2 , halogen atom, aryl. Represents a group or a heteroaryl group, and may further have a substituent Z.
- Each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group. And may further have a substituent Z.
- R 1 and R 2 do not form a condensed ring by bonding any two adjacent to each other.
- Each of the substituents Z independently represents a halogen atom, —R ′, —OR ′, —N (R ′) 2 , —SR ′ or —CN, and each R ′ independently represents a hydrogen atom, an alkyl group, A haloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group; Represents a substituent.
- n1, n2, n3, and n4 each independently represents an integer of 0 to 4, but the sum of n1, n2, n3, and n4 is never 0.
- n represents 1 or 2.
- R 1 , R 2 , n1, n2, and n are the same as those in the general formula (P-1). Further, preferred ranges of R 3, R 4 is the same as R 1, R 2, preferred ranges of n3, n4 are the same as n1, n2.
- Another preferred embodiment of the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-4).
- R 1 , R 2 , and R 5 each independently represent a substituent.
- each R 1 , R 2 And R 5 may be the same or different, and when there are a plurality of R 1 , R 2 , and R 5, they may be bonded to each other to form a ring, n1 is 0 to 2, and n2 is 0. -4 and n5 represent an integer of 0 to 4, but the sum of n1, n2 and n5 is not 0.
- XY represents a bidentate monoanionic ligand, where n is 1 to 3 Represents an integer.
- R 1 , R 2 , n1, n2, XY, and n are the same as those in the general formula (P-1). Further, preferred ranges of R 5 is the same as R 1, R 2, preferred ranges of n5 is the same as n2.
- Another preferred embodiment of the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-5).
- R 1 , R 2 , and R 5 each independently represent a substituent.
- each R 1 , R 2 And R 5 may be the same or different, and when there are a plurality of R 1 , R 2 , and R 5, they may be bonded to each other to form a ring, n1 is 0 to 2, and n2 is 0. -4 and n5 represent an integer of 0 to 4, but the sum of n1, n2 and n5 is not 0.
- XY represents a bidentate monoanionic ligand, where n is 1 to 3 Represents an integer.
- R 1 , R 2 , n1, n2, XY, and n are the same as those in the general formula (P-1). Further, preferred ranges of R 5 is the same as R 1, R 2, preferred ranges of n5 is the same as n2.
- the compound represented by the general formula (P-1) can be synthesized by combining various known synthesis methods. For example, the compounds described in International Publication No. 2009/073245 and International Publication No. 2009/073246 It can be synthesized by the method.
- the material for an organic electroluminescent element of the present invention includes at least a metal complex A and a metal complex B which are specific phosphorescent metal complexes, and the content ratio of the metal complex B to the metal complex A is 0.005% by mass to 2% by mass. It is as follows. From the viewpoint of not changing the light emission characteristics of the device, the metal complex B is preferably as small as possible as long as the effects of the present invention can be obtained, preferably 0.005% by mass to 1% by mass, and if too small, the mixing ratio is maintained. Is more preferably 0.01% by mass or more and 1% by mass or less, and most preferably 0.01% by mass or more and 0.5% by mass or less.
- one or more atoms directly bonded to Q 1 or Q 2 are homologous to the atom. And it has the same structure as the metal complex A except having been replaced by atoms with a large atomic weight.
- the metal complex B is obtained by replacing the fluorine atom of the metal complex A with a halogen atom (for example, a chlorine atom) from a fluorine atom other than the fluorine atom.
- the atom directly bonded to Q 1 or Q 2 is preferably selected from Groups 14 to 17 of the periodic table.
- the group 14 atom is preferably a carbon atom or a silicon atom, more preferably a carbon atom.
- the group 15 atom is preferably a nitrogen atom or a phosphorus atom, more preferably a nitrogen atom.
- the group 16 atom is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. From the viewpoint of maintaining the emission wavelength when the device is formed, a group 17 atom, that is, a halogen atom is more preferable.
- the metal complex A has a fluorine atom as at least one of R 1 and R 2 in the general formula (1), and the metal complex B is a halogen atom in which at least one of the fluorine atoms of the metal complex A is other than a fluorine atom.
- the metal complex B is particularly preferably substituted with a chlorine atom.
- the atoms bonded to Q 1 and Q 2 in all these substituents are replaced with “atom of the same atom and having a large atomic weight”. Alternatively, only a part may be replaced.
- the organic electroluminescent device material of the present invention is excellent in stability under visible light is not known in detail, but the complex excited by visible light is not decomposed itself, but in a solid state. It is thought that decomposition occurs when energy is transferred to a complex in an existing state and photoexcitation energy concentrates on that part.
- the metal complex B having a different structure is contained in a specific range with respect to the metal complex A as in the present invention, it acts as an additive that disturbs the arrangement in the solid state, and the energy load under visible light is dispersed. Therefore, the stability is considered to be improved. If the mixing ratio of the metal complex B complex is too large, this effect is considered to be weakened.
- the metal complex B significantly works when the excluded volume in the crystalline state has a substituent larger than that of the metal complex A.
- the difference in substituent effect causes the T1 between the two metal complexes. Since the value and chemical stability are greatly different, the above effects cannot be obtained because energy and charge are trapped in the device to reduce luminous efficiency and cause deterioration in durability during driving. Further, when the device is driven with high brightness, a deactivation phenomenon generally called TT annihilation occurs, and triplet energy formed by the complex is lost.
- the present invention also relates to a composition
- a composition comprising at least the phosphorescent metal complex A and the phosphorescent metal complex B, which are the specific phosphorescent metal complexes.
- the total content of the metal complexes A and B is preferably in the range of 1% by mass to 30% by mass with respect to the total solid content in the composition, and preferably 5% by mass to 20% by mass. The following ranges are more preferable.
- the organic electroluminescent element of the present invention is an organic electroluminescent element having a pair of electrodes and at least one organic layer including a light emitting layer between the electrodes on a substrate, wherein the organic electroluminescent element is formed on at least one of the organic layers.
- a phosphorescent metal complex containing a monoanionic bidentate ligand represented by the general formula (A) and a metal having an atomic weight of 40 or more is included.
- the organic electroluminescent element of the present invention preferably contains the metal complexes A and B which are the specific phosphorescent metal complexes in the light emitting layer.
- the light emitting layer is an organic layer, but may further have a plurality of organic layers.
- at least one of the anode and the cathode is preferably transparent or translucent.
- FIG. 1 shows an example of the configuration of an organic electroluminescent device according to the present invention.
- a light emitting layer 6 is sandwiched between an anode 3 and a cathode 9 on a support substrate 2.
- a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole block layer 7, and an electron transport layer 8 are laminated in this order between the anode 3 and the cathode 9.
- Anode / hole transport layer / light emitting layer / electron transport layer / cathode Anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode, Anode / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode.
- the element configuration, the substrate, the cathode, and the anode of the organic electroluminescence element are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736, and the matters described in the publication can be applied to the present invention.
- the substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer.
- a substrate that does not scatter or attenuate light emitted from the organic layer In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.
- the anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.
- the anode is usually provided as a transparent anode.
- the cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light emitting device.
- the electrode material can be selected as appropriate.
- Organic layer in the present invention will be described.
- each organic layer is formed by a solution coating process such as a dry film forming method such as an evaporation method or a sputtering method, a transfer method, a printing method, a spin coating method, a bar coating method, an ink jet method, or a spray method. Also, it can be suitably formed.
- a solution coating process such as a dry film forming method such as an evaporation method or a sputtering method, a transfer method, a printing method, a spin coating method, a bar coating method, an ink jet method, or a spray method.
- a solution coating process such as a dry film forming method such as an evaporation method or a sputtering method, a transfer method, a printing method, a spin coating method, a bar coating method, an ink jet method, or a spray method.
- productivity can be improved and the area of the organic EL element can be increased.
- Vapor deposition, sputtering, etc. can be used as dry methods, and dipping, spin coating, dip coating, casting, die coating, roll coating, bar coating, gravure coating, and spray coating as wet methods.
- An ink jet method or the like can be used. These film forming methods can be appropriately selected according to the material of the organic layer. When the film is formed by a wet method, it may be dried after the film is formed. Drying is performed by selecting conditions such as temperature and pressure so that the coating layer is not damaged.
- the coating solution used in the above-mentioned wet film forming method usually comprises an organic layer material and a solvent for dissolving or dispersing it.
- a solvent is not specifically limited, What is necessary is just to select according to the material used for an organic layer.
- the content in the coating solution is preferably 0.1 to 50% by mass, more preferably 0.3 to 40% by mass, and more preferably based on the total solid content.
- the content is 0.3 to 30% by mass.
- the viscosity is generally 1 to 30 mPa ⁇ s, more preferably 1.5 to 20 mPa ⁇ s, and still more preferably 1.5 to 15 mPa ⁇ s.
- the coating solution is preferably used by dissolving the organic electroluminescent element material in a predetermined organic solvent, filtering the solution, and applying the solution on a predetermined support or layer.
- the pore size of the filter used for filter filtration is preferably 2.0 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.3 ⁇ m or less made of polytetrafluoroethylene (PTFE), polyethylene, or nylon.
- the solvent examples include known organic solvents such as aromatic hydrocarbon solvents, alcohol solvents, ketone solvents, aliphatic hydrocarbon solvents, amide solvents, and the like.
- aromatic hydrocarbon solvent examples include benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, cumeneethylbenzene, methylpropylbenzene, methylisopropylbenzene, and the like, and toluene, xylene, cumene, and trimethylbenzene are more preferable. preferable.
- the relative dielectric constant of the aromatic hydrocarbon solvent is usually 3 or less.
- alcohol solvents examples include methanol, ethanol, butanol, benzyl alcohol, cyclohexanol, and the like, butanol, benzyl alcohol, and cyclohexanol are more preferable.
- the relative dielectric constant of the alcohol solvent is usually 10 to 40.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methyl
- Examples include isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like, and methyl ethyl ketone, methyl isobutyl ketone, and propylene carbonate are preferable.
- the relative permittivity of the ketone solvent is usually 10 to 90.
- Examples of the aliphatic hydrocarbon solvent include pentane, hexane, octane, and decane, and octane and decane are preferable.
- the relative dielectric constant of the aliphatic hydrocarbon solvent is usually 1.5 to 2.0.
- amide solvents examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl hole muamide, 1,3-dimethyl-2-imidazolidinone, etc. N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferred.
- the relative dielectric constant of the amide solvent is usually 30 to 40.
- the above solvents may be used alone or in combination of two or more.
- an aromatic hydrocarbon solvent hereinafter also referred to as “first solvent”
- a second solvent having a relative dielectric constant higher than that of the first solvent may be mixed and used.
- an alcohol solvent, an amide solvent, or a ketone solvent is preferably used, and an alcohol solvent is more preferably used.
- the mixing ratio (mass) of the first solvent and the second solvent is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 70/30.
- a mixed solvent containing 60% by mass or more of the first solvent is preferable.
- the organic layer-forming coating solution contains a compound having a polymerizable group and forms a polymer that forms an organic layer by a polymerization reaction of the compound having a polymerizable group
- the heating temperature and time after coating are not particularly limited as long as the polymerization reaction proceeds, but the heating temperature is generally 100 ° C to 200 ° C, and more preferably 120 ° C to 160 ° C.
- the heating time is generally 1 minute to 120 minutes, preferably 1 minute to 60 minutes, and more preferably 1 minute to 30 minutes.
- a polymerization reaction by UV irradiation a polymerization reaction by a platinum catalyst, a polymerization reaction by an iron catalyst such as iron chloride, and the like can be mentioned. These polymerization methods may be used in combination with a polymerization method by heating.
- the light emitting layer in the present invention preferably contains a material for an organic electroluminescence device containing the metal complexes A and B which are the specific phosphorescent metal complexes of the present invention.
- the light emitting layer preferably contains a light emitting material, and the light emitting material is preferably the organic electroluminescent element material of the present invention.
- the light emitting material in the light emitting layer is preferably contained in an amount of 0.1% by mass to 50% by mass with respect to the mass of all compounds generally forming the light emitting layer in the light emitting layer.
- the content is more preferably 1% by mass to 50% by mass, and further preferably 2% by mass to 40% by mass.
- the specific phosphorescent metal complexes A and B in the light emitting layer are preferably contained in the light emitting layer in a total amount of 1% by mass to 30% by mass from the viewpoint of durability and light emitting hue. More preferably.
- the thickness of the light emitting layer is not particularly limited, but is usually preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.
- the light emitting layer in the element of the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material.
- the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one kind or two or more kinds.
- the host material is preferably a charge transport material.
- the host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.
- the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
- the light emitting layer may be a single layer or a multilayer of two or more layers. In addition, each light emitting layer may emit light with different emission colors.
- the host material used in the present invention may contain the following compounds.
- pyrrole indole, carbazole (eg, CBP (4,4′-di (9-carbazoyl) biphenyl)), azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, Pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, porphyrin compound, polysilane compound, poly (N-vinyl) Carbazole), aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythioph
- the host material triplet lowest excitation energy (T 1 energy) is preferably higher than the T 1 energy of the phosphorescent light emitting material in terms of color purity, light emission efficiency, and driving durability.
- the content of the host compound in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass to 95% by mass with respect to the total compound mass forming the light emitting layer. Preferably there is.
- the light emitting layer preferably contains metal complexes A and B, which are the specific phosphorescent metal complexes, and a host material.
- the host material may be a hole transporting host material or an electron transporting host material, but a hole transporting host material can be used.
- the light emitting layer contains the metal complexes A and B, which are the specific phosphorescent metal complexes, and further contains at least one compound represented by the general formula (4-1) or (4-2). Is preferred.
- the compound represented by the general formula (4-1) or (4-2) is preferably contained in the light emitting layer in an amount of 30 to 99% by mass, preferably 40 to 97% by mass, and 50 to 95% by mass. It is particularly preferred that it be included.
- each layer contains the above-mentioned range.
- the compound represented by the general formula (4-1) or (4-2) may contain only one kind in any organic layer, and a plurality of general formulas (4-1) or (4) The compound represented by -2) may be contained in combination at any ratio.
- the host material is preferably a compound represented by the following general formula (4-1) or (4-2).
- R 8 is a substituent. When a plurality of R 8 are present, R 8 may be different or the same, and at least one of R 8 represents a carbazole group represented by the following general formula (5).
- each R 9 independently represents a substituent.
- G represents an integer of 0 to 8.
- R 8 each independently represents a substituent, specifically, a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the general formula (5). is there.
- R 8 does not represent the general formula (5), it is preferably an alkyl group having 10 or less carbon atoms, a substituted or unsubstituted aryl group having 10 or less carbon atoms, and more preferably an alkyl group having 6 or less carbon atoms. is there.
- R 9 each independently represents a substituent, specifically, a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, or a heterocyclic group, preferably an alkyl group having 10 or less carbon atoms, carbon It is a substituted or unsubstituted aryl group having several tens or less, more preferably an alkyl group having six or fewer carbon atoms.
- g represents an integer of 0 to 8 and is preferably 0 to 4 from the viewpoint of not shielding too much the carbazole skeleton responsible for charge transport. From the viewpoint of ease of synthesis, when carbazole has a substituent, those having a substituent so as to be symmetric with respect to the nitrogen atom are preferable.
- the sum of d and e is preferably 2 or more from the viewpoint of maintaining the charge transport ability.
- R 8 is preferably substituted with meta for the other benzene ring. The reason for this is that in ortho substitution, the steric hindrance between adjacent substituents is large, so that the bond is easily cleaved, and the durability is lowered.
- the molecular shape approaches a rigid rod shape and is easily crystallized, so that element degradation is likely to occur under high temperature conditions.
- a compound represented by the following structure is preferable.
- each R 9 independently represents a substituent.
- g represents an integer of 0 to 8.
- f is preferably 2 or more from the viewpoint of maintaining the charge transport ability.
- R 8 is mutually substituted with meta from the same viewpoint.
- a compound represented by the following structure is preferable.
- each R 9 independently represents a substituent.
- g represents an integer of 0 to 8.
- an isotope of hydrogen (such as a deuterium atom) is also included.
- all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
- R 9 in general formula (5) is preferably substituted with deuterium, and the following structures are particularly preferable.
- the atoms constituting the substituents also include their isotopes.
- the compounds represented by the general formulas (4-1) and (4-2) can be synthesized by combining various known synthesis methods.
- carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano and Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano and Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano and Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano and Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- the compounds represented by the general formulas (4-1) and (4-2) of the present invention preferably form a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used.
- the molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.
- the general formulas (4-1) and (4-2) are preferably compounds represented by the following structures or compounds in which one or more hydrogen atoms are substituted with deuterium atoms.
- R 8 and R 9 each independently represents a substituent.
- fluorescent material examples include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives.
- Condensed aromatic compounds perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives
- complexes represented, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.
- phosphorescent material examples include US Pat. / 19373A2, JP-A No. 2001-247859, JP-A No. 2002-302671, JP-A No. 2002-117978, JP-A No. 2003-133074, JP-A No. 2002-1235076, JP-A No. 2003-123984, JP-A No. 2002-170684, EP No. 121157, JP-A No.
- Examples of such a light-emitting dopant include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, among others. Gd complex, Dy complex, and Ce complex are mentioned.
- an Ir complex, a Pt complex, or a Re complex among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.
- the content of the phosphorescent light emitting material is preferably in the range of 0.1% by mass to 50% by mass and more preferably in the range of 0.2% by mass to 50% by mass with respect to the total mass of the light emitting layer in the light emitting layer. More preferably, the range is 0.3% by mass or more and 40% by mass or less, and the most preferable range is 5% by mass or more and 30% by mass or less.
- the content of the phosphorescent material (specific phosphorescent metal complex and / or phosphorescent material used in combination) that can be used in the present invention is 0.1% by mass or more and 50% by mass or less based on the total mass of the light emitting layer.
- the range is preferable, the range of 1% by mass to 40% by mass is more preferable, and the range of 5% by mass to 30% by mass is most preferable.
- the chromaticity of light emission of the organic electroluminescent element is less dependent on the addition concentration of the phosphorescent light emitting material.
- the organic electroluminescent element of the present invention most preferably contains 5 to 30% by mass of at least one of the specific phosphorescent metal complexes based on the total mass of the light emitting layer.
- any one of the organic layers preferably further contains a hydrocarbon compound and a derivative thereof, and the light emitting layer more preferably contains a hydrocarbon compound.
- the hydrocarbon compound is preferably a compound represented by the following general formula (VI).
- the compound represented by the general formula (VI) used in the organic electroluminescence device is excellent in chemical stability, has little alteration such as decomposition of the material during device driving, and is caused by a decomposition product of the material. It is possible to prevent a decrease in the efficiency of the organic electroluminescence device and a decrease in the device life.
- the compound represented by the general formula (VI) will be described.
- R 4 , R 6 , R 8 , R 10 , and X 4 to X 15 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
- the alkyl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) may be substituted with an adamantane structure or an aryl structure, and has 1 to 70 carbon atoms. Preferably 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, still more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and linear alkyl having 2 to 6 carbon atoms. The group is most preferred.
- Examples of the alkyl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) include, for example, an nC 50 H 101 group and an nC 30 H 61 group. , 3- (3,5,7-triphenyladamantan-1-yl) propyl group (31 carbon atoms), trityl group (19 carbon atoms), 3- (adamantan-1-yl) propyl group (13 carbon atoms) 9-decalyl group (10 carbon atoms), benzyl group (7 carbon atoms), cyclohexyl group (6 carbon atoms), n-hexyl group (6 carbon atoms), n-pentyl group (5 carbon atoms), n-butyl A group (4 carbon atoms), an n-propyl group (3 carbon atoms), a cyclopropyl group (3 carbon atoms), an ethyl group (2 carbon atoms), a methyl
- the aryl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) may be substituted with an adamantane structure or an alkyl structure, and has 6 to 30 carbon atoms. Preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 10 carbon atoms, and most preferably 6 carbon atoms.
- Examples of the aryl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) include, for example, a 1-pyrenyl group (16 carbon atoms), a 9-anthracenyl group ( 14) carbon, 1-naphthyl group (10 carbon atoms), 2-naphthyl group (10 carbon atoms), pt-butylphenyl group (10 carbon atoms), 2-m-xylyl group (8 carbon atoms), 5-m-xylyl group (8 carbon atoms), o-tolyl group (7 carbon atoms), m-tolyl group (7 carbon atoms), p-tolyl group (7 carbon atoms), phenyl group (6 carbon atoms), etc. Is mentioned.
- R 4 , R 6 , R 8 and R 10 in the general formula (VI) may be a hydrogen atom, an alkyl group or an aryl group, but the above-mentioned high glass transition temperature is preferable. From the viewpoint, at least one is preferably an aryl group, more preferably at least two are aryl groups, and particularly preferably 3 to 4 are aryl groups.
- X 4 to X 15 in the general formula (VI) may be a hydrogen atom, an alkyl group, or an aryl group, but are preferably a hydrogen atom or an aryl group, Particularly preferred is an atom.
- the molecular weight of the compound represented by the general formula (VI) in the present invention is 2000 or less from the viewpoint of vapor deposition suitability and solubility since an organic electroluminescent device is prepared using a vacuum vapor deposition process or a solution coating process. Is preferable, 1200 or less is more preferable, and 1000 or less is particularly preferable. Further, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Is more preferable, and 400 or more is particularly preferable.
- the compound represented by the general formula (VI) is preferably solid at room temperature (25 ° C), more preferably solid at room temperature (25 ° C) to 40 ° C, and from room temperature (25 ° C). Particularly preferred is a solid in the range of 60 ° C.
- a solid phase can be formed at room temperature by combining with other materials.
- the use of the compound represented by the general formula (VI) is not limited, and the compound may be contained in any layer in the organic layer.
- a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer described later are used.
- it is contained in any one or more of, and more preferably contained in any one or more of the light emitting layer, hole injection layer, hole transport layer, electron transport layer, and electron injection layer, and light emission. It is particularly preferable that it is contained in any one or more of the layer, the hole injection layer, and the hole transport layer, and most preferably included in the light emitting layer.
- the content of the compound represented by the general formula (VI) needs to be limited to an amount that does not suppress the charge transport property.
- the compound represented by the general formula (VI) is preferably contained in an amount of 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, and 0.1 to 25% by mass. Is particularly preferred.
- the compound represented by the general formula (VI) may contain only one kind in any organic layer, and contains a combination of a plurality of compounds represented by the general formula (VI) in any ratio. You may do it.
- hydrocarbon compounds that can be used in the present invention and their derivatives are listed below, but are not limited thereto.
- the compound represented by the general formula (VI) can be synthesized by appropriately combining adamantane or a halogenated adamantane with an alkyl halide or an alkylmagnesium halide (Grignard reagent).
- adamantane or a halogenated adamantane with an alkyl halide or an alkylmagnesium halide (Grignard reagent).
- indium can be used to couple a halogenated adamantane and an alkyl halide (Reference Document 1).
- the alkylated alkyl can be converted into an alkyl copper reagent and coupled with an aromatic Grignard reagent (Reference 2).
- the alkylated alkyl can be coupled using a suitable aryl boric acid and a palladium catalyst (Ref. 3).
- Reference 1 Tetrahedron Lett. 39, 1998, 9557-9558.
- Reference 2 Tetrahedron Let
- the adamantane skeleton having an aryl group can be synthesized by appropriately combining adamantane or a halogenated adamantane with the corresponding arene or aryl halide.
- the organic electroluminescent element of the present invention preferably contains an aromatic hydrocarbon compound in the organic layer.
- the aromatic hydrocarbon compound is more preferably contained in the organic layer adjacent to the light emitting layer between the light emitting layer and the cathode, but its use is not limited and further contained in any layer in the organic layer. May be.
- As the introduction layer of the aromatic hydrocarbon compound according to the present invention any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer are used. It can contain.
- the organic layer adjacent to the light emitting layer between the light emitting layer and the cathode and containing the aromatic hydrocarbon compound is preferably a charge blocking layer or an electron transporting layer, and more preferably a charge blocking layer.
- the aromatic hydrocarbon compound preferably comprises only carbon atoms and hydrogen atoms from the viewpoint of ease of synthesis.
- the aromatic hydrocarbon compound is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 70 to 100% by mass, more preferably 85 to 100% by mass.
- the aromatic hydrocarbon compound is contained in the light emitting layer, it is preferably contained in an amount of 0.1 to 99% by weight, more preferably 1 to 95% by weight, based on the total weight of the light emitting layer. More preferably, it is contained by mass%.
- hydrocarbon compound As the aromatic hydrocarbon compound, a hydrocarbon compound represented by the following general formula (Tp-1) (hereinafter sometimes simply referred to as “hydrocarbon compound”) is preferable.
- the hydrocarbon compound represented by the general formula (Tp-1) consists only of carbon atoms and hydrogen atoms, and is excellent in terms of chemical stability, so it has high driving durability and hardly undergoes various changes during high luminance driving. There is an effect.
- the hydrocarbon compound represented by the general formula (Tp-1) preferably has a molecular weight in the range of 400 to 1200, more preferably 400 to 1000, and still more preferably 400 to 800. If the molecular weight is 400 or more, a high-quality amorphous thin film can be formed, and if the molecular weight is 1200 or less, it is preferable in terms of solubility in a solvent, sublimation, and appropriate deposition.
- hydrocarbon compound represented by the general formula (Tp-1) is not limited, and it may be further contained not only in the organic layer adjacent to the light emitting layer but also in any layer within the organic layer.
- R 12 to R 23 are each independently a hydrogen atom, an alkyl group or an alkyl group, a phenyl group optionally substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Represents a fluorenyl group, a naphthyl group, or a triphenylenyl group, provided that R 12 to R 23 are not all hydrogen atoms.
- Examples of the alkyl group represented by R 12 to R 23 are substituted or unsubstituted, for example, methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, n-octyl group, n-decyl group, and an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like, preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group, more preferably a methyl group, an ethyl group, or A tert-butyl group.
- R 12 to R 23 are preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, a fluorenyl group). More preferably a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, which may be substituted with a group, a naphthyl group, or a triphenylenyl group.
- a benzene ring that may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (which may be further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group); It is particularly preferred.
- the total number of aryl rings is preferably 2 to 8, and preferably 3 to 5. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.
- R 12 to R 23 each independently preferably has a total carbon number of 20 to 50, more preferably a total carbon number of 20 to 36. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.
- the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-2).
- a plurality of Ar 1 are the same, and a phenyl group, a fluorenyl group, a naphthyl group, which may be substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Or represents a triphenylenyl group.
- An alkyl group and an alkyl group represented by Ar 1 , a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group that may be substituted with a triphenylenyl group include R 12 to R 23 . It is synonymous with what was mentioned, and a preferable thing is also the same.
- the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-3).
- L represents an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group, a fluorenyl group, a naphthyl group, a triphenylenyl group which may be substituted with a triphenylenyl group, or a combination thereof.
- n represents an integer of 1 to 6.
- the alkyl group, phenyl group, fluorenyl group, naphthyl group, or triphenylenyl group that forms the n-valent linking group represented by L has the same meaning as that described for R 12 to R 23 .
- L is preferably an alkyl group or an n-valent linking group formed by combining a benzene ring, a fluorene ring, or a combination thereof, which may be substituted with a benzene ring.
- L is bonded to the triphenylene ring by *.
- N is preferably 1 to 5, and more preferably 1 to 4.
- the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-4).
- Ar 2 in the case where a plurality of Ar 2 are present is the same, and Ar 2 represents a group formed by substitution with an alkyl group, phenyl group, naphthyl group, or triphenylenyl group, or a combination thereof.
- Ar 2 represents a group formed by substitution with an alkyl group, phenyl group, naphthyl group, or triphenylenyl group, or a combination thereof.
- And q each independently represent 0 or 1, but p and q are not simultaneously 0.
- Ar 2 represents a hydrogen atom.
- Ar 2 is preferably a group formed by combining an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a triphenylenyl group, and more preferably a combination of a methyl group, a t-butyl group, a phenyl group, or a triphenylenyl group. It is a group consisting of Ar 2 is particularly preferably a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms at the meta position, a phenyl group, a naphthyl group, a triphenylenyl group, or a combination thereof.
- the hydrocarbon compound according to the present invention is used as a host material of a light emitting layer of an organic electroluminescent device or a charge transport material of a layer adjacent to the light emitting layer, an energy gap in a thin film state than the light emitting material (the light emitting material is a phosphorescent light emitting material)
- the light emitting material is a phosphorescent light emitting material
- the energy gap and T 1 energy are not too large.
- the T 1 energy in the film state of the hydrocarbon compound represented by the general formula (Tp-1) is preferably 52 kcal / mol or more and 80 kcal / mol or less, and 55 kcal / mol or more and 68 kcal / mol or less. Is more preferable, and it is still more preferable that they are 58 kcal / mol or more and 63 kcal / mol or less. In particular, when a phosphorescent light emitting material is used as the light emitting material, the T 1 energy is preferably in the above range.
- the T 1 energy can be obtained from the short wavelength end of a phosphorescence emission spectrum of a thin film of material. For example, a material is deposited on a cleaned quartz glass substrate to a film thickness of about 50 nm by a vacuum deposition method, and the phosphorescence emission spectrum of the thin film is measured under liquid nitrogen temperature F-7000 Hitachi Spectrofluorimeter (Hitachi High Technologies). Use to measure.
- the T 1 energy can be obtained by converting the rising wavelength on the short wavelength side of the obtained emission spectrum into energy units.
- the compounds exemplified as the aromatic hydrocarbon compounds according to the present invention include those disclosed in International Publication No. 05/013388, International Publication No. 06/130598, International Publication No. 09/021107, US2009 / 0009065, International Publication No. It can be synthesized by the methods described in the 09/008311 pamphlet and the international publication 04/018587 pamphlet. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.
- the aromatic hydrocarbon compound is contained in an organic layer adjacent to the light-emitting layer between the light-emitting layer and the cathode, but its use is not limited, and any layer in the organic layer It may be further contained.
- the introduction layer of the aromatic hydrocarbon compound should be contained in the light emitting layer, hole injection layer, hole transport layer, electron transport layer, electron injection layer, exciton block layer, charge block layer or a plurality of layers. Can do.
- the organic layer adjacent to the light emitting layer between the light emitting layer and the cathode containing the aromatic hydrocarbon compound is preferably a charge blocking layer or an electron transport layer, and more preferably an electron transport layer.
- the glass transition temperature (Tg) of the aromatic hydrocarbon compound according to the present invention is 60 ° C. or higher and 400 ° C. or lower from the viewpoint of stably operating the organic electroluminescent device against heat generated during high temperature driving or driving the device. It is preferably 65 ° C. or higher and 300 ° C. or lower, more preferably 80 ° C. or higher and 180 ° C. or lower.
- the electrode preferably includes an anode, and the organic layer is preferably disposed between the light emitting layer and the anode.
- the organic layer adjacent to the light emitting layer preferably contains a compound having a lowest excited triplet (T 1 ) energy in the solution of 58 kcal / mol or more, and more preferably contains a compound having a value of 62 kcal / mol to 75 kcal / mol. .
- Examples of the compound having the lowest excited triplet (T 1 ) energy of 58 kcal / mol or more include a carbazole compound.
- the carbazole compound is preferably a carbazole compound represented by the following general formula (a).
- R represents a substituent that can be substituted on the hydrogen atom of the skeleton, and when there are a plurality of R, they may be the same or different.
- N represents an integer of 0 to 8.
- the compound represented by the general formula (a) is preferably contained in an amount of 50 to 100% by mass, and contained in an amount of 80 to 100% by mass.
- the content is preferably 95 to 100% by mass.
- the compound represented by the general formula (a) may contain only one kind in any organic layer, and contains a combination of a plurality of compounds represented by the general formula (a) in an arbitrary ratio. You may do it.
- the thickness of the charge transport layer containing the compound represented by the general formula (a) is preferably 1 nm to 500 nm, more preferably 3 nm to 200 nm, and still more preferably 5 nm to 100 nm.
- the charge transport layer is preferably provided in contact with the light emitting layer.
- the charge transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
- R examples include a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, and an aromatic heterocyclic group, an alkyl group having 10 or less carbon atoms, and a carbon number of 10 or less. Or an aryl group having 6 or less carbon atoms is more preferable.
- n represents an integer of 0 to 8, preferably 0 to 4, and more preferably 0 to 2.
- the hydrogen atom constituting the general formula (a) includes a hydrogen isotope (such as deuterium atom).
- a hydrogen isotope such as deuterium atom
- all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
- the compound represented by the general formula (a) can be synthesized by combining various known synthesis methods.
- carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- the compound represented by the general formula (a) preferably forms a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used.
- the molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.
- the charge transport layer refers to a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer. If the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron block layer, or a light emitting layer, it is possible to produce an organic electroluminescent element with low cost and high efficiency.
- the organic layer preferably includes a hole injection layer or a hole transport layer containing an electron-accepting dopant.
- the electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.
- the hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side.
- a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
- organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP)) and the like.
- BAlq phenylphenolate
- BAlq phenylphenolate
- BCP phenanthroline
- the thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
- the hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.
- the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side.
- an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
- the thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
- the electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
- the entire organic EL element may be protected by a protective layer.
- the protective layer the matters described in JP-A-2008-270736, paragraphs [0169] to [0170] can be applied to the present invention.
- the element of this invention may seal the whole element using a sealing container.
- the sealing container the matters described in paragraph [0171] of JP-A-2008-270736 can be applied to the present invention.
- the organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode.
- a direct current which may include an alternating current component as necessary
- the driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047.
- the driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.
- the light emitting element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.
- the light-emitting element of the present invention may be a so-called top emission type in which light emission is extracted from the anode side.
- the organic EL element in the present invention may have a resonator structure.
- a multilayer film mirror made of a plurality of laminated films having different refractive indexes, a transparent or translucent electrode, a light emitting layer, and a metal electrode are superimposed on a transparent substrate.
- the light generated in the light emitting layer resonates repeatedly with the multilayer mirror and the metal electrode as a reflection plate.
- a transparent or translucent electrode and a metal electrode each function as a reflecting plate on a transparent substrate, and light generated in the light emitting layer repeats reflection and resonates between them.
- the optical path length determined from the effective refractive index of the two reflectors and the refractive index and thickness of each layer between the reflectors is adjusted to an optimum value to obtain the desired resonant wavelength. Is done.
- the calculation formula in the case of the first embodiment is described in JP-A-9-180883.
- the calculation formula in the case of the second embodiment is described in Japanese Patent Application Laid-Open No. 2004-127795.
- the external quantum efficiency of the organic electroluminescent element of the present invention is preferably 5% or more, more preferably 7% or more.
- the value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency near 100 to 300 cd / m 2 when the device is driven at 20 ° C. Can do.
- the internal quantum efficiency of the organic electroluminescence device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
- the internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%.
- the organic electroluminescent element of the present invention preferably has a maximum emission wavelength (maximum intensity wavelength of emission spectrum) of 350 nm to 700 nm, more preferably 350 nm to 600 nm, still more preferably 400 nm to 520 nm, particularly preferably. It is 400 nm or more and 470 nm or less.
- the light-emitting element of the present invention is a light-emitting device, pixel, display element, display device, display, backlight, electrophotography, illumination light source, illumination device, recording light source, exposure light source, reading light source, sign, signboard, interior, or optical communication It can utilize suitably for etc. In particular, it is preferably used for a device that is driven in a region where light emission luminance is high, such as a light emitting device, a lighting device, and a display device.
- FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
- the light emitting device 20 in FIG. 2 includes a transparent substrate (supporting substrate) 2, an organic electroluminescent element 10, a sealing container 11, and the like.
- the organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2.
- a protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween.
- a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate
- the adhesive layer 14 a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and for example, a thermosetting adhesive sheet can also be used.
- the use of the light-emitting device of the present invention is not particularly limited, and for example, it can be a display device such as a television, a personal computer, a mobile phone, and electronic paper in addition to a lighting device.
- FIG. 3 is a cross-sectional view schematically showing an example of a lighting device according to an embodiment of the present invention.
- the illumination device 40 according to the embodiment of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other.
- the light scattering member 30 is not particularly limited as long as it can scatter light.
- the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31.
- a glass substrate can be preferably cited.
- the fine particles 32 transparent resin fine particles can be preferably exemplified.
- the glass substrate and the transparent resin fine particles known ones can be used. In such an illuminating device 40, when light emitted from the organic electroluminescent element 10 is incident on the light incident surface 30A of the scattering member 30, the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.
- Compound 12-a was synthesized with reference to the method described in US Patent Application Publication No. 2008/297033, page 55, paragraph 129 and thereafter.
- Compound 15-a was synthesized by the method described on page 33 of WO 02/15645.
- Compound 17-a was synthesized using the method described on page 169 of WO2008 / 140114.
- Compound 16-a was synthesized by the method described in Polyhedron 2004 No. 23, page 419 et seq.
- Compounds 13-a and 14-a were synthesized according to the method described in Inorganic chemistry No. 1991, No. 30, page 1685.
- complexes represented by other than Xa can be synthesized in the same manner by changing the raw materials during the ligand synthesis.
- X represents a compound number 1 to 19
- a compound which is a ligand of compound 15-b can be synthesized as follows using chlorofluorophenylboric acid instead of difluorophenylboric acid. The same applies to the following platinum complexes.
- compounds 9-a, 9-b, 11-a and 11-b were synthesized with reference to JP-A-2006-256999.
- Compounds 5-a, 5-b and ref-5-b were synthesized with reference to JP-A-2006-261623.
- Compounds 3-a to 3-d, 4-a, 4-b, ref-4-b, 7-a and 7-b were synthesized with reference to Japanese Patent Application Laid-Open No. 2006-093542.
- Compound 2-a was synthesized as follows.
- Compounds 2-b to 2-d were synthesized in the same manner.
- Compound 1-b was obtained as a mixture with compound 1-a when synthesized by the following method, and its composition was confirmed by HPLC and mass spectrometry. The same applies to 2-b and 5-b.
- the organic materials used in this example were all purified by sublimation and analyzed by high performance liquid chromatography (Tosoh TSKgel ODS-100Z) to calculate the purity.
- Example 1 (Production of organic electroluminescence device) A glass substrate having a thickness of 100 ⁇ m and a 2.5 cm square indium tin oxide (ITO) film (manufactured by Geomat Co., Ltd., surface resistance 10 ⁇ / ⁇ ) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then UV irradiated for 30 minutes. -Ozone treatment was performed. The following organic layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition. At this time, the material was put into a crucible and evaporated without taking any time.
- ITO indium tin oxide
- First layer CuPc (copper phthalocyanine), film thickness 120 nm
- Second layer NPD (N, N′-di- ⁇ -naphthyl-N, N′-diphenyl) -benzidine), film thickness 10 nm
- Third layer light emitting layer: light emitting material (12 mass%), mCP (1,3-bis (N-carbazolyl) benzene) (host material) (88 mass%), film thickness 30 nm
- Fourth layer first electron transport material (BAlq): film thickness 30 nm On this, 1 nm of lithium fluoride and 100 nm of metal aluminum were vapor-deposited in this order, and it was set as the cathode.
- the obtained laminate is put in a glove box substituted with argon gas without being exposed to the atmosphere, and a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) are used.
- the device was fabricated by sealing. In this way, the material was put in the crucible and evaporated without taking time, and the produced element was designated as “element 1”. The same material as each element 1 was used, and the element was exposed to white light for 3 days with the material added to the crucible.
- the light emitting material in the light emitting layer the light emitting materials 1 and 2 shown in Table 16 below were used at the mixing ratio shown in Table 16.
- the content of a part of the metal complex as the luminescent material 2 in Table 16 was measured in an oxygen stream using an automatic sample combustion apparatus AQF-100 manufactured by Mitsubishi Chemical Analytech in parallel with the measurement by HPLC-MS. Burn the sample, trap the chlorine component in hydrogen peroxide water, measure the amount of chlorine, fluorine and bromine in the hydrogen peroxide containing the halogen component with the ion chromatography ICS-1500 made by Dionex, and emit light from the halogen concentration in the sample The exact content of the metal complex as material 2 is evaluated.
- the iodine content in the metal complex is measured in the same manner by using the above apparatus and using a trap as a hydrogen peroxide solution / sodium carbonate aqueous solution. From these measurement results, it was confirmed that the absorbance of each material was almost equal, and the area ratio obtained by HPLC may be used as it is.
- a source measure unit 2400 manufactured by Toyo Technica a DC voltage was applied to each element 1 to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation.
- the emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Current density them based is the external quantum efficiency at the external quantum efficiency and 250 mA / cm 2 when the 1 mA / cm 2 was calculated by the luminance conversion method.
- the values of efficiency at 250 mA / cm 2 is divided by the efficiency of the value at 1 mA / cm 2, and calculates the ratio was described as "efficiency ratio" in Table 16. It can be said that the larger the “efficiency ratio”, the better the efficiency when the element is driven with high luminance.
- the element of the present invention has a larger durability ratio and efficiency ratio than the comparative element. From this, it can be seen that the device of the present invention is more stable under visible light and more efficient at high luminance than the comparative device.
- FIG. 4 shows elements 1-1 to 1-16 of the present invention and comparative elements 1-1 to 1-3, which are examples using compound 1-a as metal complex A and compound 1-b as metal complex B. Is a graph plotting the relationship between the content (% by mass) of metal complex B with respect to metal complex A and the durability ratio (%).
- FIG. 5 shows the case of the metal complex B for the elements 1-1 and 1-2 of the present invention and the comparative elements 1-1 and 1-2 for easier understanding when the content of the metal complex B is small.
- FIG. 6 is an example in which the compound 1-a is used as the metal complex A and the compound 1-b is used as the metal complex B, and the devices 1-1 to 1-16 of the present invention and the comparative device 1-1.
- 4 is a graph plotting the relationship between the content (% by mass) of metal complex B with respect to metal complex A and the efficiency ratio for ⁇ 1-3.
- Example 2 A device was prepared in the same manner as in Example 1 except that the types and contents of the light-emitting materials 1 and 2 and the host material were materials shown in Table 17 below, and the following durability was evaluated.
- C Durability ratio
- the devices fabricated as described above were continuously made to emit light by applying a DC voltage so that the luminance was 2000 cd / m 2 , and the luminance half time was measured. With respect to this luminance half-life, when the value of the element 2-1 of the present invention is 1 for the elements 2-1 to 2-7 of the present invention, the elements 2-8 to 2-11 of the present invention are the elements of the present invention.
- the relative values when the value of 2-8 is set to 1 are shown in Table 17 below.
- Example 3 The types and contents of the luminescent materials 1 and 2 are as shown in Table 18 below, and the same manner as in Example 1 except that a layer made of the material shown in Table 18 was provided between the second layer and the third layer. An element was produced and durability was evaluated in the same manner as in Example 2 above. The results are marked as relative values when the luminance half-time value of the device 3-1 of the present invention is 1.
- Example 4 The kind and content of the luminescent materials 1 and 2 are as shown in Table 19 below, and the same manner as in Example 1 except that a layer made of the material shown in Table 19 was provided between the third layer and the fourth layer. An element was fabricated and element efficiency was evaluated. d) Efficiency Using a source measure unit 2400 manufactured by Toyo Technica, a DC voltage was applied to each element to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Based on these, the external quantum efficiency when the current density is 1 mA / cm 2 is calculated by the luminance conversion method, and the relative value when the external quantum efficiency of the element 4-1 of the present invention is set to 1 is shown in Table 19 below. is doing.
- Example 5 Preparation of coating solution for forming light emitting layer> mCP and a luminescent material (the luminescent materials 1 and 2 shown in Table 20 below were used at a mixing ratio shown in Table 20) were mixed with methyl ethyl ketone (95: 5) so that the mass ratio of mCP: luminescent material was 95: 5. It was dissolved in MEK) to a solid content concentration of 1.0% by mass. This was filtered through a PTFE filter having a pore size of 0.22 ⁇ m to prepare each light emitting layer forming coating solution.
- a glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 ⁇ / ⁇ ) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went.
- ITO film transparent anode (ITO film)
- PEDOT poly (3,4-ethylenedioxythiophene)
- PSS polystyrene sulfonic acid
- aqueous solution BaytronP (standard product)
- each light emitting layer forming coating solution was spin-coated (2000 rpm, 60 seconds) on the hole transporting buffer layer to form a light emitting layer.
- BAlq was deposited as an electron injection layer by 20 nm by vacuum deposition.
- 0.1 nm of lithium fluoride and 100 nm of metal aluminum were vapor-deposited in this order to form a cathode.
- This laminated body is put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and sealed with a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.).
- devices 5-1 to 5-8 of the present invention and comparative devices 5-1 to 5-5 were obtained.
- the obtained device was evaluated in the same manner as the device 1-1 of the present invention. The results are shown in Table 20.
- Example 6 Preparation of coating solution for forming light emitting layer>
- the host compound H-2 and the light emitting material (the light emitting materials 1 and 2 shown in Table 24 below were used in the mixing ratio shown in Table 24), H-2: the light emitting material had a mass ratio of 95: 5, and Thus, it was made to melt
- MEK methyl ethyl ketone
- a transparent support substrate was obtained by depositing ITO with a thickness of 150 nm on a glass substrate of 25 mm ⁇ 25 mm ⁇ 0.7 mm. This transparent support substrate was placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes.
- 0.5 part by mass of Compound B (described in US2008 / 0220265) represented by the following structural formula is dissolved in 99.5 parts by mass of cyclohexanone and spin-coated so that the thickness becomes about 5 nm ( (4000 rpm, 30 seconds), and then dried at 200 ° C. for 30 minutes to form a hole injection layer.
- the hole transport layer forming coating solution A is spin-coated (1500 rpm, 20 seconds) so as to have a thickness of about 10 nm, and then dried at 120 ° C. for 30 minutes. A transport layer was formed.
- the light emitting layer forming coating solution is spin-coated (1500 rpm, 20 seconds) to a thickness of about 30 nm in the glove box (dew point -68 degrees, oxygen concentration 10 ppm) on the hole transport layer to emit light. Layered. Next, 20 nm of BAlq was deposited as an electron transport layer on the light emitting layer by vacuum deposition.
- LiF lithium fluoride
- metal aluminum 100 nm was deposited as a cathode in this order to form a film.
- the laminate produced as described above is placed in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curing adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.).
- XNR5516HV ultraviolet curing adhesive
- organic electroluminescent elements of Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-5 were produced.
- the obtained device was evaluated in the same manner as the device 1-1 of the present invention. The results are shown in Table 24 below.
- Cathode 10 Organic electroluminescent device (organic EL device) DESCRIPTION OF SYMBOLS 11 ... Organic layer 12 ... Protective layer 14 ... Adhesive layer 16 ... Sealing container 20 ... Light emitting device 30 ... Light scattering member 30A ... Light incident surface 30B ... Light Outgoing surface 31 ... Transparent substrate 32 ... Fine particles 40 ... Illumination device
- an organic EL device it can be used for an organic EL device, can be stably stored under visible light, and has excellent efficiency when driven by a device with high brightness.
- An organic electroluminescent element using the material can be provided.
- This application includes a Japanese patent application filed on September 30, 2009 (Japanese Patent Application No. 2009-228690), a Japanese patent application filed on March 30, 2010 (Japanese Patent Application No. 2010-79925), and an application filed on September 3, 2010 Japanese patent application (Japanese Patent Application No. 2010-198384), the contents of which are incorporated herein by reference.
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Abstract
Description
また、発光材料をホスト材料中にドープした発光層を用いるドープ型素子が広く採用されている。
例えば、特許文献1には、縮環アゾール配位子を含み、高耐久性かつ青色発光可能なイリジウム錯体について記載されている。
例えば、特許文献2には、素子の耐久性を向上させることを目的として、有機化合物層の少なくとも1層が金属配位化合物を含有し、該有機化合物層中の金属配位化合物の分解生成物又は原料物の含有量が0.5質量%以下である発光素子が記載されている。
また、前記特許文献2では、主に素子の耐久性向上等を目的として、発光材料の純度を高める技術が開示されている。しかしながら、特許文献2では発光材料の可視光下での安定性、及び高輝度で発光素子を駆動させたときの効率については検討されていない。
すなわち、前記課題は下記手段により解決できる。
燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む有機電界発光素子用材料であって、該燐光性金属錯体Aは下記一般式(1)で表される部分構造を含み、該燐光性金属錯体Bは一般式(1)におけるR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は該燐光性金属錯体Aと同一の構造を有し、該燐光性金属錯体Aに対する該燐光性金属錯体Bの含有比が0.005質量%以上2質量%以下である有機電界発光素子用材料。
〔2〕
前記金属錯体Aは前記一般式(1)におけるR1及びR2の少なくとも1つとしてフッ素原子を有し、前記金属錯体Bは金属錯体Aの有するフッ素原子のうち少なくとも1つがフッ素原子以外のハロゲン原子に置き換えられている上記〔1〕に記載の有機電界発光素子用材料。
〔3〕
前記金属錯体Bにおけるフッ素原子以外のハロゲン原子が塩素原子である上記〔2〕に記載の有機電界発光素子用材料。
〔4〕
前記一般式(1)において、R1及びR2が全てフッ素原子である上記〔1〕~〔3〕のいずれか1項に記載の有機電界発光素子用材料。
〔5〕
前記金属錯体Aが下記一般式(2)で表される部分構造を含む上記〔1〕~〔4〕のいずれか1項に記載の有機電界発光素子用材料。
〔6〕
前記金属錯体Aが下記一般式(3)で表される部分構造を含む上記〔1〕~〔5〕のいずれか1項に記載の有機電界発光素子用材料。
〔7〕
前記E3が炭素原子である上記〔1〕~〔6〕のいずれか1項に記載の有機電界発光素子用材料。
〔8〕
前記MがPtである上記〔1〕~〔7〕のいずれか1項に記載の有機電界発光素子用材料。
〔9〕
前記一般式(1)が下記一般式(C-2)で表される上記〔1〕に記載の有機電界発光素子用材料。
〔10〕
前記MがIrである上記〔1〕~〔7〕のいずれか1項に記載の有機電界発光素子用材料。
〔11〕
前記一般式(1)が下記一般式(A10)で表される上記〔1〕に記載の有機電界発光素子用材料。
〔12〕
前記一般式(1)が下記一般式(P-1)で表される上記〔1〕に記載の有機電界発光素子用材料。
〔13〕
基板上に、一対の電極と、該電極間に発光材料を含有する発光層を含む少なくとも一層の有機層を有する有機電界発光素子であって、該有機層のうち少なくともいずれかに上記〔1〕~〔12〕のいずれか1項に記載の有機電界発光素子用材料を含む有機電界発光素子。
〔14〕
上記〔1〕~〔12〕のいずれか1項に記載の有機電界発光素子用材料を発光層に含む上記〔13〕に記載の有機電界発光素子。
〔15〕
燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む有機電界発光素子用材料であって、該燐光性金属錯体Aは下記一般式(1)で表される部分構造を含み、該燐光性金属錯体Bは一般式(1)におけるR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は該燐光性金属錯体Aと同一の構造を有し、該燐光性金属錯体Aに対する該燐光性金属錯体Bの含有比が0.005質量%以上2質量%以下である組成物。
〔16〕
燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む有機電界発光素子用材料であって、該燐光性金属錯体Aは下記一般式(1)で表される部分構造を含み、該燐光性金属錯体Bは一般式(1)におけるR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は該燐光性金属錯体Aと同一の構造を有し、該燐光性金属錯体Aに対する該燐光性金属錯体Bの含有比が0.005質量%以上2質量%以下である発光層。
〔17〕
上記〔13〕又は〔14〕に記載の有機電界発光素子を用いた発光装置。
〔18〕
上記〔13〕又は〔14〕に記載の有機電界発光素子を用いた表示装置。
〔19〕
上記〔13〕又は〔14〕に記載の有機電界発光素子を用いた照明装置。
なお、本明細書における各一般式の説明における水素原子は同位体(重水素原子等)も含み、また更に置換基を構成する原子は、その同位体も含んでいることを表す。
本発明の有機電界発光素子用材料は、燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む。金属錯体Aは少なくとも1つの配位子中に、少なくとも1つの置換基を有する下記一般式(1)で表される部分構造を含み、金属錯体Bは一般式(1)のR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は金属錯体Aと同一の構造を有する。
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメチル、エチル、イソプロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニルなどが挙げられる。)、アミノ基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~10であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノなどが挙げられる。)、アルコキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメトキシ、エトキシ、ブトキシ、2-エチルヘキシロキシなどが挙げられる。)、アリールオキシ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニルオキシ、1-ナフチルオキシ、2-ナフチルオキシなどが挙げられる。)、ヘテロ環オキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシなどが挙げられる。)、アシル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばアセチル、ベンゾイル、ホルミル、ピバロイルなどが挙げられる。)、アルコキシカルボニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニル、エトキシカルボニルなどが挙げられる。)、アリールオキシカルボニル基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルなどが挙げられる。)、アシルオキシ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセトキシ、ベンゾイルオキシなどが挙げられる。)、アシルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセチルアミノ、ベンゾイルアミノなどが挙げられる。)、アルコキシカルボニルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニルアミノなどが挙げられる。)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルアミノなどが挙げられる。)、スルホニルアミノ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルホニルアミノ、ベンゼンスルホニルアミノなどが挙げられる。)、スルファモイル基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~12であり、例えばスルファモイル、メチルスルファモイル、ジメチルスルファモイル、フェニルスルファモイルなどが挙げられる。)、カルバモイル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばカルバモイル、メチルカルバモイル、ジエチルカルバモイル、フェニルカルバモイルなどが挙げられる。)、アルキルチオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメチルチオ、エチルチオなどが挙げられる。)、アリールチオ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニルチオなどが挙げられる。)、ヘテロ環チオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばピリジルチオ、2-ベンズイミゾリルチオ、2-ベンズオキサゾリルチオ、2-ベンズチアゾリルチオなどが挙げられる。)、スルホニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメシル、トシルなどが挙げられる。)、スルフィニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルフィニル、ベンゼンスルフィニルなどが挙げられる。)、ウレイド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばウレイド、メチルウレイド、フェニルウレイドなどが挙げられる。)、リン酸アミド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばジエチルリン酸アミド、フェニルリン酸アミドなどが挙げられる。)、ヒドロキシ基、メルカプト基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基(芳香族ヘテロ環基も包含し、好ましくは炭素数1~30、より好ましくは炭素数1~12であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子、セレン原子、テルル原子であり、具体的にはピリジル、ピラジニル、ピリミジル、ピリダジニル、ピロリル、ピラゾリル、トリアゾリル、イミダゾリル、オキサゾリル、チアゾリル、イソキサゾリル、イソチアゾリル、キノリル、フリル、チエニル、セレノフェニル、テルロフェニル、ピペリジル、ピペリジノ、モルホリノ、ピロリジル、ピロリジノ、ベンゾオキサゾリル、ベンゾイミダゾリル、ベンゾチアゾリル、カルバゾリル基、アゼピニル基、シロリル基などが挙げられる。)、シリル基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリル、トリフェニルシリルなどが挙げられる。)、シリルオキシ基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリルオキシ、トリフェニルシリルオキシなどが挙げられる。)、ホスホリル基(例えばジフェニルホスホリル基、ジメチルホスホリル基などが挙げられる。)が挙げられる。
これらの置換基は更に置換されてもよく、更なる置換基としては、以上に説明した置換基群Aから選択される基を挙げることができる。
R1及びR2が複数存在する場合は、R1及びR2のうちの2つが互いに結合し、飽和又は不飽和の、芳香族環又は非芳香族環を形成していても良い。
一般式(1)において、R1及びR2としては耐久性を低下させずに発光波長を制御できるためハロゲン原子が特に好ましく、フッ素原子が最も好ましい。また、R1及びR2は金属錯体Aの母骨格となるQ1又はQ2で表される芳香族炭化水素環又は芳香族複素環のどの部分に置換されるかは限定されず、ほぼ同等の効果を与える。
また、一般式(1)において、R1及びR2が全てフッ素原子であることが特に好ましい。
X1は炭素原子であることが好ましい。
X2は炭素原子であることが好ましい。
X3は金属との結合手を有する原子であり、錯体の化学的安定性を保持するという理由から、窒素原子であることが好ましい。
すなわち一般式(1)において、Q1及びQ2は、X1-X2を介して全体で縮環を形成していても良い。このような例としては後述する一般式(A1)~(A4)などが挙げられる。
一般式(2)中、E1~E3のうち2つ以上が炭素原子であることが好ましく、E1及びE2が炭素原子であることがより好ましい。E3は炭素原子又は窒素原子であるが、より短波長な発光を得る観点からは窒素原子であることが好ましい。また、化合物の化学的安定性及び素子耐久性の観点からは炭素原子である事もまた好ましい。
一般式(1)におけるMがPtである金属錯体は下記一般式(C-1)で表されるものが好ましい。
X1は炭素原子であることが好ましい。
X2は炭素原子であることが好ましい。
X3は金属との結合手を有する原子であり、錯体の化学的安定性を保持するという理由から、窒素原子であることが好ましい。
炭素原子でPtに結合するQ3及びQ4としては、アニオン性の配位子でも中性の配位子でもよく、環状配位子であっても非環状配位子であってもよい。アニオン性の配位子としてはビニル配位子、芳香族炭化水素環配位子(例えばベンゼン配位子、ナフタレン配位子、アントラセン配位子、フェナントレン配位子など)、ヘテロ環配位子(例えばフラン配位子、チオフェン配位子、ピリジン配位子、ピラジン配位子、ピリミジン配位子、ピリダジン配位子、トリアジン配位子、チアゾール配位子、オキサゾール配位子、ピロール配位子、イミダゾール配位子、ピラゾール配位子、トリアゾール配位子及び、それらを含む縮環体(例えばキノリン配位子、ベンゾチアゾール配位子など))が挙げられる。中性の配位子としてはカルベン配位子が挙げられる。
窒素原子でPtに結合するQ3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としては含窒素芳香族ヘテロ環配位子(ピリジン配位子、ピラジン配位子、ピリミジン配位子、ピリダジン配位子、トリアジン配位子、イミダゾール配位子、ピラゾール配位子、トリアゾール配位子、オキサゾール配位子、チアゾール配位子及びそれらを含む縮環体(例えばキノリン配位子、ベンゾイミダゾール配位子など))、アミン配位子、ニトリル配位子、イミン配位子が挙げられる。アニオン性の配位子としては、アミノ配位子、イミノ配位子、含窒素芳香族ヘテロ環配位子(ピロール配位子、イミダゾール配位子、トリアゾール配位子及びそれらを含む縮環体(例えはインドール配位子、ベンゾイミダゾール配位子など))が挙げられる。
酸素原子でPtに結合するQ3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはエーテル配位子、ケトン配位子、エステル配位子、アミド配位子、含酸素ヘテロ環配位子(フラン配位子、オキサゾール配位子及びそれらを含む縮環体(ベンゾオキサゾール配位子など))が挙げられる。アニオン性の配位子としては、アルコキシ配位子、アリールオキシ配位子、ヘテロアリールオキシ配位子、アシルオキシ配位子、シリルオキシ配位子などが挙げられる。
硫黄原子でPtに結合するQ3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはチオエーテル配位子、チオケトン配位子、チオエステル配位子、チオアミド配位子、含硫黄ヘテロ環配位子(チオフェン配位子、チアゾール配位子及びそれらを含む縮環体(ベンゾチアゾール配位子など))が挙げられる。アニオン性の配位子としては、アルキルメルカプト配位子、アリールメルカプト配位子、ヘテロアリールメルカプト配位子などが挙げられる。
リン原子でPtに結合するQ3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはホスフィン配位子、リン酸エステル配位子、亜リン酸エステル配位子、含リンヘテロ環配位子(ホスフィニン配位子など)が挙げられ、アニオン性の配位子としては、ホスフィノ配位子、ホスフィニル配位子、ホスホリル配位子などが挙げられる。
Q3及びQ4は、置換基を有していてもよく、置換基としては前記置換基群Aとして挙げたものが適宜適用できる。また置換基同士が連結していても良い(Q3とQ4が連結した場合、環状四座配位子のPt錯体になる)。
Q1、Q2、Q3及びQ4のいずれか1つ以上はフッ素置換基を有することが好ましい。フッ素置換基の数は特に限定されないが、層分離を抑制する観点から一つの配位子に対し3つ以下であることが好ましい。フッ素置換基はQ1、Q2、Q3及びQ4のうち芳香族炭化水素環配位子、ヘテロ環配位子及びそれらを含む縮環体を表すものに置換されていることが化学的安定性の観点から好ましい。
錯体の安定性及び発光量子収率の観点から、L1として好ましくは単結合、アルキレン基、アリーレン基、ヘテロアリーレン基、イミノ基、オキシ基、チオ基、シリレン基であり、より好ましくは単結合、アルキレン基、アリーレン基、イミノ基であり、更に好ましくは単結合、アルキレン基、アリーレン基であり、更に好ましくは、単結合、メチレン基、フェニレン基であり、更に好ましくは単結合、ジ置換のメチレン基であり、更に好ましくは単結合、ジメチルメチレン基、ジエチルメチレン基、ジイソブチルメチレン基、ジベンジルメチレン基、エチルメチルメチレン基、メチルプロピルメチレン基、イソブチルメチルメチレン基、ジフェニルメチレン基、メチルフェニルメチレン基、シクロヘキサンジイル基、シクロペンタンジイル基、フルオレンジイル基、フルオロメチルメチレン基であり、特に好ましくは単結合、ジメチルメチレン基、ジフェニルメチレン基、シクロヘキサンジイル基である。
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメチル、エチル、イソプロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシル、トリフルオロメチル、ペンタフルオロエチルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニル、ペンタフルオロフェニルなどが挙げられる。)、アシル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばアセチル、ベンゾイル、ホルミル、ピバロイルなどが挙げられる。)、アルコキシカルボニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニル、エトキシカルボニルなどが挙げられる。)、アリールオキシカルボニル基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルなどが挙げられる。)、アシルオキシ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセトキシ、ベンゾイルオキシなどが挙げられる。)、スルファモイル基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~12であり、例えばスルファモイル、メチルスルファモイル、ジメチルスルファモイル、フェニルスルファモイルなどが挙げられる。)、カルバモイル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばカルバモイル、メチルカルバモイル、ジエチルカルバモイル、フェニルカルバモイルなどが挙げられる。)、ヘテロ環基(好ましくは炭素数1~30、より好ましくは炭素数1~12であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子であり、具体的にはイミダゾリル、ピリジル、キノリル、フリル、チエニル、ピペリジル、モルホリノ、ベンズオキサゾリル、ベンズイミダゾリル、ベンズチアゾリル、カルバゾリル基、アゼピニル基などが挙げられる。)
炭素原子上の置換基として好ましくはアルキル基、ポリフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルコキシ基、シアノ基、ハロゲン原子である。置換基は発光波長や電位の制御のために適宜選択されるが、短波長化させる場合には電子供与性基、フッ素原子、芳香環基が好ましく、例えばアルキル基、ジアルキルアミノ基、アルコキシ基、フッ素原子、アリール基、芳香族ヘテロ環基などが選択される。また長波長化させる場合には電子求引性基が好ましく、例えばシアノ基、ポリフルオロアルキル基などが選択される。
窒素原子上の置換基として好ましくは、アルキル基、アリール基、芳香族ヘテロ環基であり、錯体の安定性の観点からアルキル基、アリール基が好ましい。前記置換基同士は連結して縮合環を形成していてもよく、形成される環としては、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、チオフェン環、フラン環などが挙げられる。
炭素上の置換基として好ましくはアルキル基、ポリフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルコキシ基、シアノ基、ハロゲン原子である。置換基は発光波長や電位の制御のために適宜選択されるが、長波長化させる場合には電子供与性基、芳香環基が好ましく、例えばアルキル基、ジアルキルアミノ基、アルコキシ基、アリール基、芳香族ヘテロ環基などが選択される。また短波長化させる場合には電子求引性基が好ましく、例えばフッ素基、シアノ基、ポリフルオロアルキル基などが選択される。
窒素原子上の置換基として好ましくは、アルキル基、アリール基、芳香族ヘテロ環基であり、錯体の安定性の観点からアルキル基、アリール基が好ましい。前記置換基同士は連結して縮合環を形成していてもよく、形成される環としては、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、チオフェン環、フラン環などが挙げられる。
Z21及びZ23のいずれか1つ以上はフッ素置換基を有することが好ましい。フッ素置換基の数は特に限定されないが、層分離を抑制する観点から一つの環に対し3つ以下であることが好ましい。
Z22及びZ24が有していてもよい置換基の好ましい範囲はZ21及びZ23と同様である。
A301~A306として好ましくはC-Rであり、R同士が互いに連結して環を形成していても良い。A301~A306がC-Rである場合に、A302、A305のRとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、アルキル基、アリール基、アミノ基、フッ素基であり、特に好ましくは水素原子、メチル基、フェニル基、キシリル基、フッ素基である。該アルキル基、アリール基は更に置換基を有しても良く、該置換基としてはアルキル基、アリール基、シアノ基、アミノ基、ハロゲン原子、フルオロアルキル基が挙げられ、好ましくは炭素数1~6のアルキル基、シアノ基、アミノ基、ハロゲン原子、フルオロアルキル基(好ましくはトリフルオロメチル基)であり、更に好ましくは炭素数1~6のアルキル基、ハロゲン原子(好ましくはフッ素原子)である。A302、A305がC-Rである場合、該A302、A305のRとしては、素子の耐久性向上の観点からはアリール基が好ましく、発光波長が短いという観点では水素原子、アルキル基、アミノ基、アルコキシ基、フッ素基、シアノ基が好ましい。
A301、A303、A304、A306のRとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、アミノ基、アルコキシ基、アリールオキシ基、フッ素基であり、特に好ましくは水素原子であるが、1つ以上がフッ素原子を表すことが好ましい。
A307、A308、A309及びA310は、それぞれ独立に、C-R又は窒素原子を表す。Rは水素原子又は置換基を表す。Rで表される置換基としては、前記置換基群Aとして挙げたものが適用できる。A307、A308、A309及びA310がC-Rである場合に、Rとして好ましくは水素原子、アルキル基、ポリフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルキルオキシ基、シアノ基、ハロゲン原子であり、より好ましくは、水素原子、アルキル基、ポリフルオロアルキル基、アリール基、ジアルキルアミノ基、シアノ基、フッ素原子、更に好ましくは、水素原子、アルキル基、トリフルオロメチル基、フッ素原子である。また可能な場合は置換基同士が連結して縮環構造を形成してもよい。発光波長を短波長側にシフトさせる場合、A308が窒素原子であることが好ましい。
一般式(C-4)
A401~A414はそれぞれ独立にC-R又は窒素原子を表す。Rは水素原子又は置換基を表し、好ましい範囲は前記一般式(C-3)のRと同様であるが、1つ以上がフッ素原子を表すことが好ましい。A401~A406及びL41は、前記一般式(C-3)におけるA301~A306及びL31と同義であり、好ましい範囲も同様である。
A407~A414がC-Rを表す場合に、A408、A412のRとして好ましくは水素原子、アルキル基、ポリフルオロアルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、ポリフルオロアルキル基、アルキル基、アリール基、フッ素基、シアノ基であり、特に好ましくは、水素原子、ポリフルオロアルキル基、フッ素基、シアノ基である。A407、A409、A411、A413のRとして好ましくは水素原子、アルキル基、ポリフルオロアルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、ポリフルオロアルキル基、フッ素基、シアノ基であり、特に好ましく水素原子、フッ素基である。A410、A414のRとして好ましくは水素原子、フッ素基であり、より好ましくは水素原子である。A407~A409、A411~A413のいずれかがC-Rを表す場合に、R同士が互いに連結して環を形成していても良い。
A501~A506はそれぞれ独立にC-R又は窒素原子を表す。Rは水素原子又は置換基を表し、好ましい範囲は前記一般式(C-3)のRと同様であるが、1つ以上がフッ素原子を表すことが好ましい。
Yで表される配位子は、置換基を有していてもよく、置換基としては前記置換基群Aとして挙げたものが適宜適用できる。また置換基同士が連結していても良い。
Z61及びZ63のいずれか1つ以上はフッ素置換基を有することが好ましい。フッ素置換基の数は特に限定されないが、層分離を抑制する観点から一つの環に対し3つ以下であることが好ましい。
Z62が有していてもよい置換基、及びその好ましい範囲はZ61及びZ63と同様である。
A701~A706はそれぞれ独立にC-R又は窒素原子を表す。Rは水素原子又は置換基を表し、好ましい範囲は前記一般式(C-3)のRと同様であるが、1つ以上がフッ素原子を表すことが好ましい。
例えば、配位子、又はその解離体と金属化合物を溶媒(例えば、ハロゲン系溶媒、アルコール系溶媒、エーテル系溶媒、エステル系溶媒、ケトン系溶媒、ニトリル系溶媒、アミド系溶媒、スルホン系溶媒、スルホキサイド系溶媒、水などが挙げられる)の存在下、若しくは、溶媒非存在下、塩基の存在下(無機、有機の種々の塩基、例えば、ナトリウムメトキシド、t-ブトキシカリウム、トリエチルアミン、炭酸カリウムなどが挙げられる)、若しくは、塩基非存在下、室温以下、若しくは加熱し(通常の加熱以外にもマイクロウェーブで加熱する手法も有効である)得ることができる。
なお、本発明における配位子の一般式中、*は金属への配位部位であって、E1aと金属の結合、及びE1qと金属の結合はそれぞれ独立に共有結合であっても、配位結合であっても良い。
また、E1a~E1eのうち少なくとも1つは窒素原子を表すことが好ましく、E1a~E1eのうち2つ、又は3つが窒素原子を表すことが更に好ましく、E1a~E1eのうち2つが窒素原子を表すことが特に好ましい。E1a~E1eのうち2つが窒素原子を表す場合、E1a、E1d、及びE1eのうち2つが窒素原子を表すことが好ましく、E1aとE1d、又はE1aとE1eが窒素原子を表すことがより好ましく、E1aとE1dが窒素原子を表すことが更に好ましい。
R1a、R1b、R1g、R1h、及びR1iのうち少なくとも一つが置換基を表すことが好ましい。
一般式(A1)及び(A3)において、R1a~R1iが表す置換基としては前記一般式(1)におけるR1及びR2が表す置換基と同義であり、好ましい範囲も同様である。
一般式(A2)及び(A4)において、R1a~R1hが表す置換基としては前記一般式(1)におけるR1及びR2が表す置換基と同義であり、好ましい範囲も同様である。
2,6-ジ置換アリール基として好ましくは2,6-ジメチルフェニル基、2,4,6-トリメチルフェニル基、2,6-ジイソプロピルフェニル基、2,4,6-トリイソプロピルフェニル基、2,6-ジメチル-4-フェニルフェニル基、2,6-ジメチル-4-(2,6-ジメチルピリジン-4-イル)フェニル基、2,6-ジフェニルフェニル基、2,6-ジフェニル-4-イソプロピルフェニル基、2,4,6-トリフェニルフェニル基、2,6-ジイソプロピル-4-(4-イソプロピルフェニル)フェニル基、2,6-ジイソプロピル-4-(3,5-ジメチルフェニル)フェニル基、2,6-ジイソプロピル-4-(ピリジン-4-イル)フェニル基、又は2,6-ジ-(3,5-ジメチルフェニル)フェニル基である。
R1a及びR1bの少なくとも1つは電子供与性基であることが好ましく、R1aが電子供与性置換基であることが好ましく、R1aがメチル基であることがより好ましい。
1価の炭化水素置換基の例としては、炭素数1~20のアルキル基;炭素数1~20のアルキル基、炭素数3~8のシクロアルキル基、アリール基から選ばれる1つ以上の基によって置換された炭素数1~20のアルキル基;炭素数3~8のシクロアルキル基;炭素数1~20のアルキル基、炭素数3~8のシクロアルキル基、アリール基から選ばれる1つ以上の基によって置換された炭素数3~8のシクロアルキル基;炭素数6~18のアリール基;炭素数1~20のアルキル基、炭素数3~8のシクロアルキル基、アリール基から選ばれる1つ以上の基によって置換されたアリール基等が挙げられる。
2価の炭化水素基の例としては、-CH2-、-CH2CH2-、-CH2CH2CH2-、1,2-フェニレン基等が挙げられる。
一般式(A1-4)及び(A3-4)で表されるモノアニオン性の2座配位子は、下記一般式(A1-5)で表されるモノアニオン性の2座配位子であることが好ましい。
一般式(A1-6)中、R1a、R1g、R1h、R1iの好ましいものは、一般式(A1-1)におけるR1a、R1g、R1h、R1iと同様である。また、Rb及びRcの好ましいものは、一般式ss-1におけるRb及びRcと同様である。
上記Rx、Ry及びRzはそれぞれ独立に水素原子又は置換基を表す。該置換基としては前記置換基群Aから選ばれる置換基が挙げられる。
好ましくは、Rx、Rzはそれぞれ独立にアルキル基、パーフルオロアルキル基、ハロゲン原子、アリール基のいずれかであり、より好ましくは炭素数1~4のアルキル基、炭素数1~4のパーフルオロアルキル基、フッ素原子、置換されていても良いフェニル基であり、最も好ましくはメチル基、エチル基、トリフルオロメチル基、フッ素原子、フェニル基である。Ryは好ましくは水素原子、アルキル基、パーフルオロアルキル基、ハロゲン原子、アリール基のいずれかであり、より好ましくは水素原子、炭素数1~4のアルキル基、置換されていても良いフェニル基であり、最も好ましくは水素原子、メチル基のいずれかである。これら副配位子は素子中で電荷を輸送したり励起によって電子が集中する部位ではないと考えられるため、Rx、Ry、Rzは化学的に安定な置換基であれば良く、本発明の効果にも影響を及ぼさない。
上記のなかでも一般式(l-1)、(l-4)、又は(l-5)がより好ましく、一般式(l-1)、又は(l-4)が更に好ましく一般式(l-1)が特に好ましい。
nが3である場合、前記一般式(A10)は、下記一般式(A10-1)で表される。
一般式(A10-1)中、R1a~R1iの好ましいものは、一般式(A1)におけるR1a~R1iの好ましいものと同様である。
R1、R2、n1及びn2は前記一般式(1)におけるR1、R2、n1及びn2と同義であり、好ましい範囲も同様である。
置換基Zとしては、ハロゲン原子、-R’、-OR’、-N(R’)2、-SR’、-C(O)R’、-C(O)OR’、-C(O)N(R’)2、-CN、-NO2、-SO2、-SOR’、-SO2R’、又は-SO3R’が挙げられ、R’はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
R1、R2がアルケニル基を表す場合、好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばビニル、アリル、1-プロペニル、1-イソプロペニル、1-ブテニル、2-ブテニル、3-ペンテニルなどが挙げられる。
R1、R2がアルキニル基を表す場合、好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばエチニル、プロパルギル、1-プロピニル、3-ペンチニルなどが挙げられる。
置換基Zとしては、アルキル基、アルコキシ基、フルオロ基、シアノ基、ジアルキルアミノ基が好ましく、アルキル基がより好ましい。
配位子の好ましい範囲としては前記一般式(A10)における(X-Y)と同様である。
R1及びR2は隣り合う任意の2つが互いに結合して縮合環を形成しない。
置換基Zはそれぞれ独立に、ハロゲン原子、-R’、-OR’、-N(R’)2、-SR’又は-CNを表し、R’はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
n1及びn2はそれぞれ独立に0~4の整数を表すが、n1とn2の和が0になることはない。
X-Yは二座のモノアニオン性配位子を表す。
nは1~3の整数を表す。)
R1、及びR2は隣り合う任意の2つが互いに結合して縮合環を形成しない。
置換基Zはそれぞれ独立に、ハロゲン原子、-R’、-OR’、-N(R’)2、-SR’又は-CNを表し、R’はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。置換基を表す。
n1、n2、n3、及びn4はそれぞれ独立に0~4の整数を表すが、n1とn2とn3とn4の和が0になることはない。
nは1又は2を表す。)
本発明の有機電界発光素子用材料は、特定燐光性金属錯体である金属錯体Aと金属錯体Bとを少なくとも含み、金属錯体Aに対する金属錯体Bの含有比が0.005質量%以上2質量%以下である。素子の発光特性を変えない観点から、本発明の効果が得られる限りにおいて金属錯体Bはできるだけ少ないことが好ましく、0.005質量%以上1質量%以下が好ましく、少なすぎると混合比を保つのが難しくなるため0.01質量%以上1質量%以下がより好ましく、0.01質量%以上0.5質量%以下が最も好ましい。
本発明の組成物を用いることで、可視光下で安定に保存させることができ、また高輝度で素子を駆動させたときの効率に優れる有機電界発光素子用材料を得ることができる。
本発明の組成物には更に他の成分を添加することもできる。
本発明の有機電界発光素子について説明する。
本発明の有機電界発光素子は、基板上に、一対の電極と、該電極間に発光層を含む少なくとも一層の有機層とを有する有機電界発光素子であって、該有機層のうち少なくとも一層に前記一般式(A)で表されるモノアニオン性の2座配位子と原子量40以上の金属を含む燐光性金属錯体を含む。
発光素子の性質上、陽極及び陰極のうち少なくとも一方の電極は、透明若しくは半透明であることが好ましい。
図1は、本発明に係る有機電界発光素子の構成の一例を示している。図1に示される本発明に係る有機電界発光素子10は、支持基板2上において、陽極3と陰極9との間に発光層6が挟まれている。具体的には、陽極3と陰極9との間に正孔注入層4、正孔輸送層5、発光層6、正孔ブロック層7、及び電子輸送層8がこの順に積層されている。
前記有機層の層構成としては、特に制限はなく、有機電界発光素子の用途、目的に応じて適宜選択することができるが、前記透明電極上に又は前記背面電極上に形成されるのが好ましい。この場合、有機層は、前記透明電極又は前記背面電極上の前面又は一面に形成される。
有機層の形状、大きさ、及び厚み等については、特に制限はなく、目的に応じて適宜選択することができる。
・陽極/正孔輸送層/発光層/電子輸送層/陰極、
・陽極/正孔輸送層/発光層/ブロック層/電子輸送層/陰極、
・陽極/正孔輸送層/発光層/ブロック層/電子輸送層/電子注入層/陰極、
・陽極/正孔注入層/正孔輸送層/発光層/ブロック層/電子輸送層/陰極、
・陽極/正孔注入層/正孔輸送層/発光層/ブロック層/電子輸送層/電子注入層/陰極。
有機電界発光素子の素子構成、基板、陰極及び陽極については、例えば、特開2008-270736号公報に詳述されており、該公報に記載の事項を本発明に適用することができる。
本発明で使用する基板としては、有機層から発せられる光を散乱又は減衰させない基板であることが好ましい。有機材料の場合には、耐熱性、寸法安定性、耐溶剤性、電気絶縁性、及び加工性に優れていることが好ましい。
陽極は、通常、有機層に正孔を供給する電極としての機能を有していればよく、その形状、構造、大きさ等については特に制限はなく、発光素子の用途、目的に応じて、公知の電極材料の中から適宜選択することができる。前述のごとく、陽極は、通常透明陽極として設けられる。
陰極は、通常、有機層に電子を注入する電極としての機能を有していればよく、その形状、構造、大きさ等については特に制限はなく、発光素子の用途、目的に応じて、公知の電極材料の中から適宜選択することができる。
本発明における有機層について説明する。
本発明の有機電界発光素子において、各有機層は、蒸着法やスパッタ法等の乾式製膜法、転写法、印刷法、スピンコート法、バーコート法、インクジェット法、スプレー法等の溶液塗布プロセスによっても好適に形成することができる。液塗布プロセスを使用することで、生産性の向上、有機EL素子の大面積化などにつながることが考えられる。
第二の溶媒としては、アルコール系溶媒、アミド系溶媒、ケトン系溶媒を使用することが好ましく、アルコール系溶媒を使用することがより好ましい。
第一の溶媒と第二の溶媒との混合比(質量)は、1/99~99/1、好ましくは10/90~90/10、更に好ましくは20/80~70/30である。第一の溶媒を60質量%以上含有する混合溶媒が好ましい。
塗布後の加熱温度及び時間は、重合反応が進行する限り特に限定されないが、加熱温度は一般的に100℃~200℃であり、好ましくは120℃~160℃がより好ましい。加熱時間は一般的に1分~120分であり、1分~60分が好ましく、より好ましくは1分~30分である。
<発光材料>
本発明における発光層には本発明の前記特定燐光性金属錯体である金属錯体A及びBを含む有機電界発光素子用材料を含むことが好ましい。また、発光層には発光材料を含むことが好ましく、発光材料は本発明の有機電界発光素子用材料であることが好ましい。
発光層中の特定燐光性金属錯体A及びBは、発光層中に耐久性、発光色相の観点から合計で1質量%~30質量%含有されることが好ましく、5質量%~20質量%含有されることがより好ましい。
また、発光層は一層であっても二層以上の多層であってもよい。また、それぞれの発光層が異なる発光色で発光してもよい。
本発明に用いられるホスト材料として、以下の化合物を含有していても良い。例えば、ピロール、インドール、カルバゾール(例えばCBP(4,4’-ジ(9-カルバゾイル)ビフェニル))、アザインドール、アザカルバゾール、トリアゾール、オキサゾール、オキサジアゾール、ピラゾール、イミダゾール、チオフェン、ポリアリールアルカン、ピラゾリン、ピラゾロン、フェニレンジアミン、アリールアミン、アミノ置換カルコン、スチリルアントラセン、フルオレノン、ヒドラゾン、スチルベン、シラザン、芳香族第三級アミン化合物、スチリルアミン化合物、ポルフィリン系化合物、ポリシラン系化合物、ポリ(N-ビニルカルバゾール)、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン等の導電性高分子オリゴマー、有機シラン、カーボン膜、ピリジン、ピリミジン、トリアジン、イミダゾール、ピラゾール、トリアゾ-ル、オキサゾ-ル、オキサジアゾ-ル、フルオレノン、アントラキノジメタン、アントロン、ジフェニルキノン、チオピランジオキシド、カルボジイミド、フルオレニリデンメタン、ジスチリルピラジン、フッ素置換芳香族化合物、ナフタレンペリレン等の複素環テトラカルボン酸無水物、フタロシアニン、8-キノリノ-ル誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾ-ルやベンゾチアゾ-ルを配位子とする金属錯体に代表される各種金属錯体及びそれらの誘導体(置換基や縮環を有していてもよい)等を挙げることができる。
本発明においては、発光層に前記特定燐光性金属錯体である金属錯体A及びBと、更に一般式(4-1)又は(4-2)で表される化合物の少なくとも1つ以上を含むことが好ましい。
gは0~8の整数を表し、電荷輸送を担うカルバゾール骨格を遮蔽しすぎない観点から0~4が好ましい。また、合成容易さの観点から、カルバゾールが置換基を有する場合、窒素原子に対し、対称になるように置換基を持つものが好ましい。
本発明に使用できる蛍光発光材料の例としては、例えば、ベンゾオキサゾール誘導体、ベンゾイミダゾール誘導体、ベンゾチアゾール誘導体、スチリルベンゼン誘導体、ポリフェニル誘導体、ジフェニルブタジエン誘導体、テトラフェニルブタジエン誘導体、ナフタルイミド誘導体、クマリン誘導体、縮合芳香族化合物、ペリノン誘導体、オキサジアゾール誘導体、オキサジン誘導体、アルダジン誘導体、ピラリジン誘導体、シクロペンタジエン誘導体、ビススチリルアントラセン誘導体、キナクリドン誘導体、ピロロピリジン誘導体、チアジアゾロピリジン誘導体、シクロペンタジエン誘導体、スチリルアミン誘導体、ジケトピロロピロール誘導体、芳香族ジメチリディン化合物、8-キノリノール誘導体の錯体やピロメテン誘導体の錯体に代表される各種錯体等、ポリチオフェン、ポリフェニレン、ポリフェニレンビニレン等のポリマー化合物、有機シラン誘導体などの化合物等が挙げられる。
本発明に使用できる燐光発光材料としては、例えば、US6303238B1、US6097147、WO00/57676、WO00/70655、WO01/08230、WO01/39234A2、WO01/41512A1、WO02/02714A2、WO02/15645A1、WO02/44189A1、WO05/19373A2、特開2001-247859、特開2002-302671、特開2002-117978、特開2003-133074、特開2002-235076、特開2003-123982、特開2002-170684、EP1211257、特開2002-226495、特開2002-234894、特開2001-247859、特開2001-298470、特開2002-173674、特開2002-203678、特開2002-203679、特開2004-357791、特開2006-256999、特開2007-19462、特開2007-84635、特開2007-96259等の特許文献に記載の燐光発光化合物などが挙げられ、中でも、更に好ましい発光性ドーパントとしては、Ir錯体、Pt錯体、Cu錯体、Re錯体、W錯体、Rh錯体、Ru錯体、Pd錯体、Os錯体、Eu錯体、Tb錯体、Gd錯体、Dy錯体、及びCe錯体が挙げられる。特に好ましくは、Ir錯体、Pt錯体、又はRe錯体であり、中でも金属-炭素結合、金属-窒素結合、金属-酸素結合、金属-硫黄結合の少なくとも一つの配位様式を含むIr錯体、Pt錯体、又はRe錯体が好ましい。更に、発光効率、駆動耐久性、色度等の観点で、3座以上の多座配位子を含むIr錯体、Pt錯体、又はRe錯体が特に好ましい。
本発明の有機電界発光素子は、上記特定燐光性金属錯体の少なくとも一種を該発光層の総質量に対して5~30質量%含有することが最も好ましい。
有機電界発光素子は、有機層のいずれかの層が更に、炭化水素化合物、及びその誘導体を含むことが好ましく、発光層が炭化水素化合物を含むことがより好ましい。
また、炭化水素化合物は下記一般式(VI)で表される化合物であることが好ましい。
一般式(VI)で表される化合物を発光材料とともに適切に用いることにより、材料分子間の相互作用を適切に制御し、隣接分子間のエネルギーギャップ相互作用を均一にすることで駆動電圧を更に低下させることが可能となる。
また、有機電界発光素子において用いられる、一般式(VI)で表される化合物は、化学的な安定性に優れ、素子駆動中における材料の分解等の変質が少なく、当該材料の分解物による、有機電界発光素子の効率低下や素子寿命の低下を防ぐことが出来る。
一般式(VI)で表される化合物について説明する。
室温(25℃)において固体を形成しない一般式(VI)で表される化合物を用いる場合は、他の材料と組み合わせることにより、常温で固相を形成させることができる。
また、一般式(VI)で表される化合物を、複数の有機層に用いる場合はそれぞれの層において、上記の範囲で含有することが好ましい。
参考文献1:Tetrahedron Lett.39,1998,9557-9558.
参考文献2:Tetrahedron Lett.39,1998,2095-2096.
参考文献3:J.Am.Chem.Soc.124,2002,13662-13663.
Groups in Organic Synthesis)、グリーン(T. W. Greene)著、ジョン・ワイリー・アンド・サンズ・インコーポレイテッド(John Wiley&Sons Inc.)(1981年)等)等の手段により容易に製造が可能である。また、必要に応じて適宜置換基導入等の反応工程の順序を変化させることも可能である。
本発明の有機電界発光素子は、有機層に芳香族炭化水素化合物を含有することが好ましい。
芳香族炭化水素化合物は発光層と陰極の間の発光層に隣接する有機層に含有されることがより好ましいが、その用途が限定されることはなく、有機層内のいずれの層に更に含有されてもよい。本発明にかかる芳香族炭化水素化合物の導入層としては、発光層、正孔注入層、正孔輸送層、電子輸送層、電子注入層、励起子ブロック層、電荷ブロック層のいずれか、若しくは複数に含有することができる。
芳香族炭化水素化合物が含有される、発光層と陰極の間の発光層に隣接する有機層は電荷ブロック層又は電子輸送層であることが好ましく、電荷ブロック層であることがより好ましい。
芳香族炭化水素化合物を発光層に隣接する層に含有することで、素子の効率と耐久性が向上する。発光層が励起されると励起子が発光層と隣接層の界面に偏り、隣接層を破壊する現象が起こるが、芳香族炭化水素化合物は耐久性の高い構造を有しているため、励起子により破壊されにくいため、上記のような効果が得られると考えられる。
芳香族炭化水素化合物を発光層以外の層に含有させる場合は、70~100質量%含まれることが好ましく、85~100質量%含まれることがより好ましい。芳香族炭化水素化合物を発光層に含有させる場合は、発光層の全質量に対して0.1~99質量%含ませることが好ましく、1~95質量%含ませることがより好ましく、10~95質量%含ませることが更に好ましい。
一般式(Tp-1)で表される炭化水素化合物は炭素原子と水素原子のみからなり、化学的安定性の点で優れるため、駆動耐久性が高く、高輝度駆動時の各種変化がおきにくいという効果を奏する。
フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基(これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい)で置換されていてもよい、ベンゼン環であることが特に好ましい。
Lとして好ましくは、アルキル基又はベンゼン環で置換されていてもよいベンゼン環、フルオレン環、又はこれらを組み合わせて成るn価の連結基である。
以下にLの好ましい具体例を挙げるがこれらに限定されるものではない。なお具体例中*でトリフェニレン環と結合する。
Ar2は、メタ位が炭素数1~4のアルキル基、フェニル基、ナフチル基、トリフェニレニル基、又はこれらを組み合わせてなる基で置換されたベンゼン環であることが特に好ましい。
合成後、カラムクロマトグラフィー、再結晶等による精製を行った後、昇華精製により精製することが好ましい。昇華精製により、有機不純物を分離できるだけでなく、無機塩や残留溶媒等を効果的に取り除くことができる。
芳香族炭化水素化合物が含有される発光層と陰極の間の発光層に隣接する有機層は電荷ブロック層又は電子輸送層であることが好ましく、電子輸送層であることがより好ましい。
また、一般式(a)で表される化合物を、複数の有機層に用いる場合はそれぞれの層において、上記の範囲で含有することが好ましい。
該電荷輸送層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
nは0~8の整数を表し、0~4が好ましく、0~2がより好ましい。
電荷輸送層とは、有機電界発光素子に電圧を印加した際に電荷移動が起こる層をいう。具体的には正孔注入層、正孔輸送層、電子ブロック層、発光層、正孔ブロック層、電子輸送層又は電子注入層が挙げられる。塗布法により形成される電荷輸送層が正孔注入層、正孔輸送層、電子ブロック層又は発光層であれば、低コストかつ高効率な有機電界発光素子の製造が可能となる。
正孔注入層、正孔輸送層は、陽極又は陽極側から正孔を受け取り陰極側に輸送する機能を有する層である。
本発明に関し、有機層として、電子受容性ドーパントを含有する正孔注入層又は正孔輸送層を含むことが好ましい。
電子注入層、電子輸送層は、陰極又は陰極側から電子を受け取り陽極側に輸送する機能を有する層である。
正孔ブロック層は、陽極側から発光層に輸送された正孔が、陰極側に通りぬけることを防止する機能を有する層である。本発明において、発光層と陰極側で隣接する有機層として、正孔ブロック層を設けることができる。
正孔ブロック層を構成する有機化合物の例としては、アルミニウム(III)ビス(2-メチル-8-キノリナト)4-フェニルフェノレート(Aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate(BAlqと略記する))等のアルミニウム錯体、トリアゾール誘導体、2,9-ジメチル-4,7-ジフェニル-1,10-フェナントロリン(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline(BCPと略記する))等のフェナントロリン誘導体、等が挙げられる。
正孔ブロック層の厚さとしては、1nm~500nmであるのが好ましく、5nm~200nmであるのがより好ましく、10nm~100nmであるのが更に好ましい。
正孔ブロック層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
電子ブロック層は、陰極側から発光層に輸送された電子が、陽極側に通りぬけることを防止する機能を有する層である。本発明において、発光層と陽極側で隣接する有機層として、電子ブロック層を設けることができる。
電子ブロック層を構成する有機化合物の例としては、例えば前述の正孔輸送材料として挙げたものが適用できる。
電子ブロック層の厚さとしては、1nm~500nmであるのが好ましく、5nm~200nmであるのがより好ましく、10nm~100nmであるのが更に好ましい。
電子ブロック層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
本発明において、有機EL素子全体は、保護層によって保護されていてもよい。
保護層については、特開2008-270736号公報の段落番号〔0169〕~〔0170〕に記載の事項を本発明に適用することができる。
本発明の素子は、封止容器を用いて素子全体を封止してもよい。
封止容器については、特開2008-270736号公報の段落番号〔0171〕に記載の事項を本発明に適用することができる。
本発明の有機電界発光素子は、陽極と陰極との間に直流(必要に応じて交流成分を含んでもよい)電圧(通常2ボルト~15ボルト)、又は直流電流を印加することにより、発光を得ることができる。
本発明の有機電界発光素子の駆動方法については、特開平2-148687号、同6-301355号、同5-29080号、同7-134558号、同8-234685号、同8-241047号の各公報、特許第2784615号、米国特許5828429号、同6023308号の各明細書等に記載の駆動方法を適用することができる。
別の好ましい態様では、透明基板上に、透明又は半透明電極と金属電極がそれぞれ反射板として機能して、発光層で生じた光はその間で反射を繰り返し共振する。
共振構造を形成するためには、2つの反射板の有効屈折率、反射板間の各層の屈折率と厚みから決定される光路長を所望の共振波長の得るのに最適な値となるよう調整される。第一の態様の場合の計算式は特開平9-180883号明細書に記載されている。第2の態様の場合の計算式は特開2004-127795号明細書に記載されている。
本発明の発光素子は、発光装置、ピクセル、表示素子、表示装置、ディスプレイ、バックライト、電子写真、照明光源、照明装置、記録光源、露光光源、読み取り光源、標識、看板、インテリア、又は光通信等に好適に利用できる。特に、発光装置、照明装置、表示装置等の発光輝度が高い領域で駆動されるデバイスに好ましく用いられる。
本発明の発光装置は、前記有機電界発光素子を用いてなる。
図2は、本発明の発光装置の一例を概略的に示した断面図である。
図2の発光装置20は、透明基板(支持基板)2、有機電界発光素子10、封止容器11等により構成されている。
ここで、接着層14としては、エポキシ樹脂等の光硬化型接着剤や熱硬化型接着剤を用いることができ、例えば熱硬化性の接着シートを用いることもできる。
次に、図3を参照して本発明の実施形態に係る照明装置について説明する。
図3は、本発明の実施形態に係る照明装置の一例を概略的に示した断面図である。
本発明の実施形態に係る照明装置40は、図3に示すように、前述した有機EL素子10と、光散乱部材30とを備えている。より具体的には、照明装置40は、有機EL素子10の基板2と光散乱部材30とが接触するように構成されている。
光散乱部材30は、光を散乱できるものであれば特に制限されないが、図3においては、透明基板31に微粒子32が分散した部材とされている。透明基板31としては、例えば、ガラス基板を好適に挙げることができる。微粒子32としては、透明樹脂微粒子を好適に挙げることができる。ガラス基板及び透明樹脂微粒子としては、いずれも、公知のものを使用できる。このような照明装置40は、有機電界発光素子10からの発光が散乱部材30の光入射面30Aに入射されると、入射光を光散乱部材30により散乱させ、散乱光を光出射面30Bから照明光として出射するものである。
18-aについては以下のように合成した。
(有機電界発光素子の作製)
100μm厚み、2.5cm角の酸化インジウム錫(ITO)膜を有するガラス基板(ジオマテック社製、表面抵抗10Ω/□)を洗浄容器に入れ、2-プロパノール中で超音波洗浄した後、30分間UV-オゾン処理を行った。この透明陽極(ITO膜)上に真空蒸着法にて以下の有機層を順次蒸着した。このとき、材料をるつぼに入れ、時間をおかずに蒸着した。
第1層:CuPc(銅フタロシアニン),膜厚120nm
第2層:NPD(N,N’-ジ-α-ナフチル-N,N’-ジフェニル)-ベンジジン),膜厚10nm
第3層(発光層):発光材料(12質量%)、mCP(1,3-ビス(N-カルバゾリル)ベンゼン)(ホスト材料)(88質量%)、膜厚30nm
第4層:第一電子輸送材料(BAlq):膜厚30nm
この上に、フッ化リチウム1nm及び金属アルミニウム100nmをこの順に蒸着し陰極とした。
得られた積層体を、大気に触れさせることなく、アルゴンガスで置換したグローブボックス内に入れ、ステンレス製の封止缶及び紫外線硬化型の接着剤(XNR5516HV、長瀬チバ(株)製)を用いて封止し、素子を作製した。このように、材料をるつぼに入れ、時間をおかずに蒸着し、作製した素子を「素子1」とする。各素子1と同じ材料を用い、材料をるつぼに添加した状態で白色光に3日間暴露し、その後同様に作製した素子を「素子2」とする。
発光層における発光材料としては、下記表16に示した発光材料1及び2を表16に記載の混合比で用いた。
これらの測定結果より、各々の材料の吸光度がほぼ等しく、HPLCで得られた面積比をそのまま含有量として用いてもよいことを確認した。
(a)耐久性比(可視光に対する安定性)
上記のように作製した素子1と、該素子と同じ材料を用い、材料をるつぼに添加した状態で白色光に3日間暴露し、その後同様に作製した素子2について、それぞれ輝度が2000cd/m2になるように直流電圧を印加して発光させ続け、輝度半減時間を測定した。素子2の輝度半減時間が素子1の輝度半減時間に対して何%であるかを算出し、表16に「耐久性比」として記載した。該「耐久性比」が大きいほど、素子作製に用いた材料が可視光に対して安定であったといえる。
東陽テクニカ製ソースメジャーユニット2400を用いて、直流電圧を各素子1に印加し発光させ、その輝度をトプコン社製輝度計BM-8を用いて測定した。発光スペクトルと発光波長は浜松ホトニクス製スペクトルアナライザーPMA-11を用いて測定した。これらを元に電流密度が1mA/cm2の時の外部量子効率と250mA/cm2の時の外部量子効率を輝度換算法により算出した。250mA/cm2での効率の値を1mA/cm2での効率の値で割って、比を算出し、表16に「効率比」として記載した。該「効率比」が大きいほど、高輝度で素子を駆動した場合に効率に優れるといえる。
図4は、金属錯体Aとして化合物1-a、金属錯体Bとして化合物1-bを用いた実施例である本発明の素子1-1~1-16、及び比較素子1-1~1-3について、金属錯体Bの金属錯体Aに対する含有量(質量%)と耐久性比(%)の関係をプロットしたグラフである。また、図5は金属錯体Bの含有量が少ない場合について、よりわかりやすくするために、本発明の素子1-1及び1-2、比較素子1-1及び1-2についての金属錯体Bの金属錯体Aに対する含有量(質量%)と耐久性比(%)の関係をプロットしたグラフである。
図4及び5から、金属錯体Bの金属錯体Aに対する含有量が、0.005質量%以上2質量%以下である場合に耐久性比に優れることがわかる。
また、同様に、図6は金属錯体Aとして化合物1-a、金属錯体Bとして化合物1-bを用いた実施例である本発明の素子1-1~1-16、及び比較素子1-1~1-3について、金属錯体Bの金属錯体Aに対する含有量(質量%)と効率比の関係をプロットしたグラフである。また、図7は金属錯体Bの含有量が少ない場合について、よりわかりやすくするために、本発明の素子1-1及び1-2、比較素子1-1及び1-2についての金属錯体Bの金属錯体Aに対する含有量(質量%)と効率比の関係をプロットしたグラフである。
図6及び7から、金属錯体Bの金属錯体Aに対する含有量が、0.005質量%以上2質量%以下である場合に効率比に優れることがわかる。
発光材料1及び2の種類、含有量、並びにホスト材料を下記表17に示す材料とする以外は実施例1と同様に素子を作製し、以下の耐久性の評価を行った。
(c)耐久性比
上記のように作製した素子を、それぞれ輝度が2000cd/m2になるように直流電圧を印加して発光させ続け、輝度半減時間を測定した。この輝度半減時間を、本発明の素子2-1~2-7は本発明の素子2-1の値を1とした場合の、本発明の素子2-8~2-11は本発明の素子2-8の値を1とした場合のそれぞれ相対値として下記表17に記載している。
発光材料1及び2の種類、並びに含有量を下記表18の通りとし、第2層と第3層の間に、表18に示す材料からなる層を5nm設けた以外は実施例1と同様に素子を作製し、上記実施例2と同様の耐久性の評価を行った。結果は、本発明の素子3-1の輝度半減時間の値を1とした場合の相対値で著した。
発光材料1及び2の種類、並びに含有量を下記表19の通りとし、第3層と第4層の間に、表19に示す材料からなる層を3nm設けた以外は実施例1と同様に素子を作製し、素子効率の評価を行った。
d)効率
東陽テクニカ製ソースメジャーユニット2400を用いて、直流電圧を各素子に印加し発光させ、その輝度をトプコン社製輝度計BM-8を用いて測定した。発光スペクトルと発光波長は浜松ホトニクス製スペクトルアナライザーPMA-11を用いて測定した。これらを元に電流密度が1mA/cm2の時の外部量子効率を輝度換算法により算出し、本発明の素子4-1の外部量子効率を1とした場合の相対値として下記表19に記載している。
<発光層形成用塗布液の調製>
mCPと、発光材料(下記表20に示した発光材料1及び2を表20に記載の混合比で用いた)とを、mCP:発光材料が95:5の質量比となるように、メチルエチルケトン(MEK)に溶解させ固形分濃度1.0質量%とした。これを0.22μmのポアサイズを有するPTFEフィルターでろ過して各発光層形成用塗布液を調製した。
次いで、前記各発光層形成用塗布液を先のホール輸送性バッファ層上にスピンコート(2000rpm、60秒間)し、発光層を形成させた。この発光層の上に、電子注入層としてBAlqを真空蒸着法により20nm蒸着した。更にフッ化リチウム0.1nm及び金属アルミニウムを100nmをこの順に蒸着し陰極とした。
この積層体を、大気に触れさせること無く、窒素ガスで置換したグローブボックス内に入れ、ガラス製の封止缶及び紫外線硬化型の接着剤(XNR5516HV、長瀬チバ(株)製)を用いて封止し、本発明の素子5-1~5-8及び比較素子5-1~5-5を得た。得られた素子に対して本発明の素子1-1と同様の評価を行った。結果を表20に示す。
<発光層形成用塗布液の調製>
ホスト化合物H-2と、発光材料(下記表24に示した発光材料1及び2を表24に記載の混合比で用いた)とを、H-2:発光材料が95:5の質量比となるように、メチルエチルケトン(MEK)に溶解させ、固形分濃度1.0質量%とした。これを0.22μmのポアサイズを有するPTFEフィルターでろ過して、各発光層形成用塗布液を調製した。
下記化合物Aを電子工業用キシレンに溶解させ、全固形分濃度0.4質量%とし、これを0.22μmのポアサイズを有するPTFEフィルターでろ過して、正孔輸送層形成用塗布液Aを調製した。
25mm×25mm×0.7mmのガラス基板上にITOを150nmの厚みで蒸着し成膜したものを透明支持基板とした。この透明支持基板を洗浄容器に入れ、2-プロパノール中で超音波洗浄した後、30分間UV-オゾン処理を行った。
このITO付ガラス基板上に、下記構造式で表される化合物B(US2008/0220265記載)0.5質量部をシクロヘキサノン99.5質量部に溶解し、厚みが約5nmとなるようにスピンコート(4000rpm、30秒間)した後、200℃で30分間乾燥することで、正孔注入層を成膜した。
前記正孔輸送層上に、前記各発光層形成用塗布液をグローブボックス(露点-68度、酸素濃度10ppm)内で厚みが約30nmとなるようにスピンコート(1500rpm、20秒間)し、発光層とした。
次いで、発光層上に電子輸送層としてBAlqを真空蒸着法により20nm蒸着した。更に、電子注入層としてフッ化リチウム(LiF)を0.1nm、陰極として金属アルミニウムを100nmこの順に蒸着し、成膜した。
以上により作製した積層体を、アルゴンガスで置換したグロ-ブボックス内に入れ、ステンレス製の封止缶及び紫外線硬化型の接着剤(XNR5516HV、長瀬チバ(株)製)を用いて封止することで、実施例6-1~6-7及び比較例6-1~6-5の有機電界発光素子を作製した。得られた素子に対して本発明の素子1-1と同様の評価を行った。結果を下記表24に示す。
3・・・陽極
4・・・正孔注入層
5・・・正孔輸送層
6・・・発光層
7・・・正孔ブロック層
8・・・電子輸送層
9・・・陰極
10・・・有機電界発光素子(有機EL素子)
11・・・有機層
12・・・保護層
14・・・接着層
16・・・封止容器
20・・・発光装置
30・・・光散乱部材
30A・・・光入射面
30B・・・光出射面
31・・・透明基板
32・・・微粒子
40・・・照明装置
本出願は、2009年9月30日出願の日本特許出願(特願2009-228690)、2010年3月30日出願の日本特許出願(特願2010-79925)、及び2010年9月3日出願の日本特許出願(特願2010-198384)に基づくものであり、それらの内容はここに参照して組み込まれる。
Claims (19)
- 燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む有機電界発光素子用材料であって、該燐光性金属錯体Aは下記一般式(1)で表される部分構造を含み、該燐光性金属錯体Bは一般式(1)におけるR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は該燐光性金属錯体Aと同一の構造を有し、該燐光性金属錯体Aに対する該燐光性金属錯体Bの含有比が0.005質量%以上2質量%以下である有機電界発光素子用材料。
(一般式(1)中、R1及びR2はそれぞれ独立に置換基を表す。R1及びR2は複数存在する場合はそれぞれのR1及びR2は同一でも異なっていてもよい。複数のR1及びR2はそれぞれ互いに結合して環を形成してもよい。Mは原子量40以上の金属を表し、X1~X3はそれぞれ独立に炭素原子又は窒素原子を表す。ただし、X1~X3が全て窒素原子を表すことはない。Q1は5員又は6員の芳香族複素環を表し、Q2は5員又は6員の芳香族炭化水素環又は芳香族複素環を表す。n1及びn2はそれぞれ独立に0~4の整数を表すが、n1とn2の和が0になることはない。Q1及びQ2を含む2座配位子は他の配位子と結合して3座以上の配位子を形成しても良い。Q1とQ2は連結基により連結し、環を形成してもよい。) - 前記金属錯体Aは前記一般式(1)におけるR1及びR2の少なくとも1つとしてフッ素原子を有し、前記金属錯体Bは金属錯体Aの有するフッ素原子のうち少なくとも1つがフッ素原子以外のハロゲン原子に置き換えられている請求項1に記載の有機電界発光素子用材料。
- 前記金属錯体Bにおけるフッ素原子以外のハロゲン原子が塩素原子である請求項2に記載の有機電界発光素子用材料。
- 前記一般式(1)において、R1及びR2が全てフッ素原子である請求項1~3のいずれか1項に記載の有機電界発光素子用材料。
- 前記E3が炭素原子である請求項1~6のいずれか1項に記載の有機電界発光素子用材料。
- 前記MがPtである請求項1~7のいずれか1項に記載の有機電界発光素子用材料。
- 前記一般式(1)が下記一般式(C-2)で表される請求項1に記載の有機電界発光素子用材料。
(式中、L21は単結合又は二価の連結基を表す。Z21及びZ22はそれぞれ独立に5員又は6員の含窒素芳香族ヘテロ環を表す。Z23及びZ24はそれぞれ独立にベンゼン環又は5員又は6員の芳香族ヘテロ環を表す。Z21及びZ23はそれぞれ独立に1~4個の置換基を有していてもよく、該置換基は互いに結合して環を形成してもよい。ただし、Z21及びZ23のうち少なくともいずれかは1つ以上の置換基を有する。Z22及びZ24は置換基を有していてもよく、該置換基は互いに結合して環を形成してもよい。X21、X22、X23及びX24はそれぞれ独立に炭素原子又は窒素原子を表す。) - 前記MがIrである請求項1~7のいずれか1項に記載の有機電界発光素子用材料。
- 基板上に、一対の電極と、該電極間に発光材料を含有する発光層を含む少なくとも一層の有機層を有する有機電界発光素子であって、該有機層のうち少なくともいずれかに請求項1~12のいずれか1項に記載の有機電界発光素子用材料を含む有機電界発光素子。
- 請求項1~12のいずれか1項に記載の有機電界発光素子用材料を発光層に含む請求項13に記載の有機電界発光素子。
- 燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む有機電界発光素子用材料であって、該燐光性金属錯体Aは下記一般式(1)で表される部分構造を含み、該燐光性金属錯体Bは一般式(1)におけるR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は該燐光性金属錯体Aと同一の構造を有し、該燐光性金属錯体Aに対する該燐光性金属錯体Bの含有比が0.005質量%以上2質量%以下である組成物。
(一般式(1)中、R1及びR2はそれぞれ独立に置換基を表す。R1及びR2は複数存在する場合はそれぞれのR1及びR2は同一でも異なっていてもよい。Mは原子量40以上の金属を表し、X1~X3はそれぞれ独立に炭素原子又は窒素原子を表す。ただし、X1~X3が全て窒素原子を表すことはない。Q1は5員又は6員の芳香族複素環を表し、Q2は5員又は6員の芳香族炭化水素環又は芳香族複素環を表す。n1及びn2はそれぞれ独立に0~4の整数を表すが、n1とn2の和が0になることはない。Q1及びQ2を含む2座配位子は他の配位子と結合して3座以上の配位子を形成しても良い。Q1とQ2は連結基により連結し、環を形成してもよい。) - 燐光性金属錯体Aと燐光性金属錯体Bとを少なくとも含む有機電界発光素子用材料であって、該燐光性金属錯体Aは下記一般式(1)で表される部分構造を含み、該燐光性金属錯体Bは一般式(1)におけるR1及びR2のうちの少なくとも1つの置換基において、Q1又はQ2に直接結合している原子の1つ以上が、該原子の同族かつ原子量の大きい原子に置き換えられていること以外は該燐光性金属錯体Aと同一の構造を有し、該燐光性金属錯体Aに対する該燐光性金属錯体Bの含有比が0.005質量%以上2質量%以下である発光層。
(一般式(1)中、R1及びR2はそれぞれ独立に置換基を表す。R1及びR2は複数存在する場合はそれぞれのR1及びR2は同一でも異なっていてもよい。Mは原子量40以上の金属を表し、X1~X3はそれぞれ独立に炭素原子又は窒素原子を表す。ただし、X1~X3が全て窒素原子を表すことはない。Q1は5員又は6員の芳香族複素環を表し、Q2は5員又は6員の芳香族炭化水素環又は芳香族複素環を表す。n1及びn2はそれぞれ独立に0~4の整数を表すが、n1とn2の和が0になることはない。Q1及びQ2を含む2座配位子は他の配位子と結合して3座以上の配位子を形成しても良い。Q1とQ2は連結基により連結し、環を形成してもよい。) - 請求項13又は14に記載の有機電界発光素子を用いた発光装置。
- 請求項13又は14に記載の有機電界発光素子を用いた表示装置。
- 請求項13又は14に記載の有機電界発光素子を用いた照明装置。
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