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WO2015129714A1 - Matériau électroluminescent, élément électroluminescent organique, et composé - Google Patents

Matériau électroluminescent, élément électroluminescent organique, et composé Download PDF

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WO2015129714A1
WO2015129714A1 PCT/JP2015/055313 JP2015055313W WO2015129714A1 WO 2015129714 A1 WO2015129714 A1 WO 2015129714A1 JP 2015055313 W JP2015055313 W JP 2015055313W WO 2015129714 A1 WO2015129714 A1 WO 2015129714A1
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general formula
compound
light emitting
group
represent
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将嗣 種田
功將 志津
田中　啓之
大貴 野田
一 中野谷
安達　千波矢
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Kyushu University NUC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/14—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a compound useful as a light emitting material and an organic light emitting device using the compound.
  • organic light emitting devices such as organic electroluminescence devices (organic EL devices)
  • organic electroluminescence devices organic electroluminescence devices
  • various efforts have been made to increase the light emission efficiency by newly developing and combining electron transport materials, hole transport materials, light emitting materials, and the like constituting the organic electroluminescence element.
  • compounds having a substituted amino group such as a carbazolyl group and a diphenylamino group are known as materials for the light emitting layer, and some of them have a fluorine atom.
  • Patent Document 1 describes that a compound having a carbazolyl group and a fluorine atom represented by the following formula can be used as a dopant material (light emitting material) of a light emitting layer.
  • Patent Document 2 describes that a compound having a diphenylamino group substituted with a methyl group and a fluorine atom, or a compound having a carbazolyl group and a fluorine atom, represented by the following formula, can be used as a light emitting material.
  • Patent Documents 1 and 2 describe that a compound having a diphenylamino group or carbazolyl group substituted with a methyl group and a fluorine atom can be used as a light emitting material.
  • the present inventors actually evaluated the light emission characteristics of a compound having a diphenylamino group or a carbazolyl group and a fluorine atom, the light emission characteristics were not sufficiently satisfactory (see Comparative Examples 1 and 2 below). ), It has been found that there is a need to provide a luminescent material with better luminescent properties.
  • Patent Documents 1 and 2 describe a compound having a fluorine atom with a diphenylamino group or carbazolyl group substituted with a methyl group, but a substituted amino group having a structure in which three 6-membered rings are condensed and fluorine. It does not describe compounds having atoms. For this reason, the usefulness of these compounds as luminescent materials is completely unpredictable.
  • the present inventors have further investigated the usefulness of a compound having a substituted amino group having a structure in which three 6-membered rings are condensed and a fluorine atom as a luminescent material, and has excellent luminescent properties. Research was conducted with the aim of finding compounds. And the general formula of the compound useful as a luminescent material was derived, and the earnest examination was advanced for the purpose of generalizing the structure of the organic light emitting element with high luminous efficiency.
  • the present inventors have found that a compound having a specific structure among compounds having a substituted amino group having a structure in which three 6-membered rings are condensed and a fluorine atom has excellent properties as a luminescent material. Found to have. In addition, it has been found that such a group of compounds is useful as a delayed fluorescent material, and it has been clarified that an organic light-emitting device having high emission efficiency can be provided at low cost. Based on these findings, the present inventors have provided the following present invention as means for solving the above problems.
  • a light emitting material comprising a compound represented by the following general formula (1).
  • R 1 , R 3 and R 5 represent a fluorine atom, or R 1 , R 2 , R 4 and R 5 represent a fluorine atom, and the remaining R 1 to R 6 are each independently Represents a group represented by any one of the following general formulas (2) to (6).
  • L 14 to L 18 represent a single bond or a substituted or unsubstituted arylene group, and * represents a bonding site to the benzene ring in the general formula (1).
  • R 31 to R 38 , R 3a , R 3b , R 41 to R 48 , R 4a , R 51 to R 58 , R 61 to R 68 , and R 71 to R 78 each independently represent a hydrogen atom or a substituent. .
  • R 31 and R 32, R 32 and R 33, R 33 and R 34, R 35 and R 36, R 36 and R 37, R 37 and R 38, R 3a and R 3b, R 41 and R 42, R 42 And R 43 , R 43 and R 44 , R 45 and R 46 , R 46 and R 47 , R 47 and R 48 , R 51 and R 52 , R 52 and R 53 , R 53 and R 54 , R 55 and R 56 , R 56 and R 57 , R 57 and R 58 , R 61 and R 62 , R 62 and R 63 , R 63 and R 64 , R 65 and R 66 , R 66 and R 67 , R 67 and R 68 , R 71 and R 72 , R 72 and R 73 , R 73 and R 74 , R 75 and R 76 , R 76 and R 77 , and R 77 and R 78 may be bonded to each other to form a cyclic structure. . ]
  • R 1 ′, R 3 ′ and R 5 ′ represent a fluorine atom, or R 1 ′, R 2 ′, R 4 ′ and R 5 ′ represent a fluorine atom, R 1 ′ to R 6 ′ each independently represents a group represented by any one of the following general formulas (2 ′) to (6 ′).
  • L 14 ′ to L 18 ′ represent a single bond or a substituted or unsubstituted arylene group, and * represents a bonding site to the benzene ring in the general formula (1). Represents.
  • the compound of the present invention is useful as a light emitting material.
  • the compounds of the present invention include those that emit delayed fluorescence.
  • An organic light emitting device using the compound of the present invention as a light emitting material can realize high luminous efficiency.
  • 2 is an absorption emission spectrum of a toluene solution of compound 1 of Example 1.
  • 2 is an absorption emission spectrum of a toluene solution of compound 2 of Example 2.
  • 2 is an absorption spectrum of a thin film type organic photoluminescence device of Compound 2 of Example 2.
  • 2 is an emission spectrum of a thin film type organic photoluminescence device of Compound 2 of Example 2. It is an emission spectrum of the thin film type organic photoluminescence element of the compound 2 of Example 2 and mCP. It is an emission spectrum of the thin film type organic photoluminescence element of the compound 2 of Example 2 and DPEPO.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be 1 H, or a part or all of them are 2 H. (Deuterium D) may be used.
  • the luminescent material of the present invention is characterized by comprising a compound represented by the following general formula (1).
  • R 1 , R 3 and R 5 represent a fluorine atom, or R 1 , R 2 , R 4 and R 5 represent a fluorine atom, and the remaining R 1 to R 6 are each independently It represents a group represented by any one of the following general formulas (2) to (6). That is, when R 1 , R 3 and R 5 are fluorine atoms, the remaining R 2 , R 4 and R 6 are each independently a group represented by any one of the following general formulas (2) to (6). is there.
  • R 1 , R 2 , R 4 and R 5 are fluorine atoms
  • the remaining R 3 and R 6 are each independently a group represented by any one of the following general formulas (2) to (6). is there.
  • the remaining R 1 to R 6 may all be represented by any one of the general formulas (2) to (6), or may be represented by different general formulas. May be.
  • all of the remaining R 1 to R 6 are represented by any one of the general formulas (2) to (6)
  • all of the remaining R 1 to R 6 are groups having the same structure. It is preferable.
  • the compound represented by the general formula (1) has a rotationally symmetric structure.
  • a compound in which all of the remaining R 1 to R 6 have the same structure is useful, for example, when used as a dopant.
  • compounds in which some or all of the remaining R 1 to R 6 have different structures are also useful.
  • Such a compound is useful, for example, when a layer (neat film) made of only the compound is formed and used as a light emitting layer.
  • L 14 to L 18 represent a single bond or a substituted or unsubstituted arylene group, and * represents a bonding site to the benzene ring in the general formula (1).
  • the arylene group is preferably an arylene group having 6 to 18 carbon atoms. Examples of the arylene group having 6 to 18 carbon atoms include a phenylene group, a biphenylene group, a fluorenylene group, and a triphenylenylene group.
  • a more preferable linking group is a phenylene group, and a more preferable linking group is 1,4- A phenylene group.
  • L 14 to L 18 are preferably single bonds.
  • R 31 to R 38 , R 3a , R 3b , R 41 to R 48 , R 4a , R 51 to R 58 , R 61 to R 68 , and R 71 to R 78 each independently represent a hydrogen atom or a substituent. .
  • the number of substituents is not particularly limited, and all of R 31 to R 38 , R 3a , R 3b , R 41 to R 48 , R 4a , R 51 to R 58 , R 61 to R 68 , R 71 to R 78 May be unsubstituted (ie, a hydrogen atom).
  • R 31 to R 38 , R 3a , R 3b , R 41 to R 48 , R 4a , R 51 to R 58 , R 61 to R 68 , R 71 to R When two or more of 78 are substituents, the plurality of substituents may be the same as or different from each other.
  • R 31 to R 38 , R 3a , R 3b , R 41 to R 48 , R 4a , R 51 to R 58 , R 61 to R 68 , R 71 to R 78 may be, for example, hydroxy group, halogen Atom, cyano group, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkyl-substituted amino group having 1 to 20 carbon atoms, acyl having 2 to 20 carbon atoms Group, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, carbon An alkylsulfonyl group having 1 to 10 carbon atoms, a haloalkyl group
  • substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, and a dialkyl-substituted amino group having 1 to 20 carbon atoms.
  • substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, and a dialkyl-substituted amino group having 1 to 20 carbon
  • substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 6 to 15 carbon atoms.
  • it is an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 31 and R 32, R 32 and R 33, R 33 and R 34, R 35 and R 36, R 36 and R 37, R 37 and R 38, R 3a and R 3b, R 41 and R 42, R 42 And R 43 , R 43 and R 44 , R 45 and R 46 , R 46 and R 47 , R 47 and R 48 , R 51 and R 52 , R 52 and R 53 , R 53 and R 54 , R 55 and R 56 , R 56 and R 57 , R 57 and R 58 , R 61 and R 62 , R 62 and R 63 , R 63 and R 64 , R 65 and R 66 , R 66 and R 67 , R 67 and R 68 , R 71 and R 72 , R 72 and R 73 , R 73 and R 74 , R 75 and R 76 , R 76 and R 77 , and R 77 and R 78 may be bonded to each other to form a cyclic structure.
  • the cyclic structure may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a condensed ring of two or more rings.
  • the hetero atom here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • Examples of cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole And a ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and a cycloheptaene ring.
  • R 31 to R 38 , R 3a , R 3b , R 41 to R 48 , R 4a , R 51 to R 58 , R 61 to R 68 , and R 71 to R 78 are each independently represented by the general formula (2) to A group represented by any one of (6) is also preferred.
  • R 3a and R 3b are preferably substituted or unsubstituted alkyl groups, and more preferably substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  • the substituent is preferably any one of R 32 to R 37 , R 3a , and R 3b in the case of the general formula (2). , R 3a and R 3b are more preferable.
  • any one of R 42 to R 47 is preferable, and in general formula (4), any one of R 52 to R 57 is preferable, and in general formula (5), If present, any one of R 62 to R 67 is preferable, and if it is general formula (6), any one of R 72 to R 77 is preferable.
  • R 1 , R 3 and R 5 are fluorine atoms, or R 1 , R 2 , R 4 and R 5 are fluorine atoms, and the remaining R Examples include compounds in which all of 1 to R 6 are groups represented by the general formula (2) or (4).
  • the molecular weight of the compound represented by the general formula (1) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (1) is intended to be formed by vapor deposition. Preferably, it is preferably 1200 or less, more preferably 1000 or less, and even more preferably 800 or less.
  • the lower limit of the molecular weight is the molecular weight of the minimum compound represented by the general formula (1).
  • the compound represented by the general formula (1) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.
  • a compound containing a plurality of structures represented by the general formula (1) in the molecule as a light emitting material.
  • a polymer obtained by previously polymerizing a polymerizable group in the structure represented by the general formula (1) and polymerizing the polymerizable group as a light emitting material Specifically, a monomer containing a polymerizable functional group is prepared in any of R 2 , R 3 , R 4 , and R 6 in the general formula (1), and this is polymerized alone or together with other monomers It is conceivable to obtain a polymer having repeating units by copolymerization and use the polymer as a light emitting material. Alternatively, it is also conceivable that dimers and trimers are obtained by reacting compounds having a structure represented by the general formula (1) and used as a luminescent material.
  • a polymer having a repeating unit including a structure represented by the general formula (1) a polymer including a structure represented by the following general formula (7) or (8) can be given.
  • Q represents a group including the structure represented by the general formula (1)
  • L 1 and L 2 represent a linking group.
  • the linking group preferably has 0 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 2 to 10 carbon atoms. And preferably has a structure represented by - linking group -X 11 -L 11.
  • X 11 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • L 11 represents a linking group, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
  • R 101 , R 102 , R 103 and R 104 each independently represent a substituent.
  • it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms.
  • An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
  • the linking group represented by L 1 and L 2 is any one of R 2 , R 3 , R 4 and R 6 having the structure of the general formula (1) constituting Q, and R 31 having the structure of the general formula (2).
  • Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.
  • a hydroxy group is introduced into any of R 2 , R 3 , R 4 and R 6 in the structure of the general formula (1). Then, it can be synthesized by reacting the following compound as a linker to introduce a polymerizable group and polymerizing the polymerizable group.
  • the polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed only of repeating units having the structure represented by the general formula (1), or other structures may be used. It may be a polymer containing repeating units.
  • the repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit not having the structure represented by the general formula (1) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene.
  • R 1 ′, R 3 ′ and R 5 ′ represent a fluorine atom, or R 1 ′, R 2 ′, R 4 ′ and R 5 ′ represent a fluorine atom, and the remaining R 1 ′ to R 6 ′ each independently represents a group represented by any one of the following general formulas (2 ′) to (6 ′).
  • L 14 ′ to L 18 ′ represent a single bond or a substituted or unsubstituted arylene group, and * represents a bonding site to the benzene ring in the general formula (1).
  • the explanation of the compound represented by formula (1) can be referred to.
  • X represents a halogen atom other than a fluorine atom, and examples include a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferable.
  • the above reaction is an application of a known reaction, and known reaction conditions can be appropriately selected and used. The details of the above reaction can be referred to the synthesis examples described below.
  • the compound represented by the general formula (1 ′) can also be synthesized by combining other known synthesis reactions.
  • the compound represented by the general formula (1) of the present invention is useful as a light emitting material of an organic light emitting device. For this reason, the compound represented by General formula (1) of this invention can be effectively used as a luminescent material for the light emitting layer of an organic light emitting element.
  • the compound represented by the general formula (1) includes a delayed fluorescent material (delayed phosphor) that emits delayed fluorescence. That is, the present invention relates to a delayed phosphor having a structure represented by the general formula (1), an invention using a compound represented by the general formula (1) as a delayed phosphor, and a general formula (1).
  • An invention of a method for emitting delayed fluorescence using the represented compound is also provided.
  • An organic light emitting device using such a compound as a light emitting material emits delayed fluorescence and has a feature of high luminous efficiency. The principle will be described below by taking an organic electroluminescence element as an example.
  • the organic electroluminescence element carriers are injected into the light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light.
  • 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used.
  • the excited triplet state has a long lifetime, energy saturation occurs due to saturation of the excited state and interaction with excitons in the excited triplet state, and in general, the quantum yield of phosphorescence is often not high.
  • delayed fluorescent materials after energy transition to an excited triplet state due to intersystem crossing, etc., are then crossed back to an excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emit fluorescence.
  • a thermally activated delayed fluorescent material by absorption of thermal energy is particularly useful.
  • excitons in the excited singlet state emit fluorescence as usual.
  • excitons in the excited triplet state absorb heat generated by the device and cross between the excited singlets to emit fluorescence.
  • the light is emitted from the excited singlet, the light is emitted at the same wavelength as the fluorescence, but the light lifetime (luminescence lifetime) generated by the reverse intersystem crossing from the excited triplet state to the excited singlet state is normal. Since the fluorescence becomes longer than the fluorescence and phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence. If such a heat-activated exciton transfer mechanism is used, the ratio of the compound in an excited singlet state, which normally generated only 25%, is increased to 25% or more by absorbing thermal energy after carrier injection. It can be raised.
  • the heat of the device will sufficiently cause intersystem crossing from the excited triplet state to the excited singlet state and emit delayed fluorescence. Efficiency can be improved dramatically.
  • the compound represented by the general formula (1) of the present invention tends to exhibit good orientation with respect to the film forming surface when it is formed as a light emitting layer.
  • the orientation of the compound with respect to the film-forming surface is excellent, there is an advantage that the traveling direction of light emitted from the compound is aligned and the light extraction efficiency from the light emitting layer is easily improved.
  • the compound represented by the general formula (1) of the present invention as a light-emitting material of a light-emitting layer, excellent organic light-emitting devices such as an organic photoluminescence device (organic PL device) and an organic electroluminescence device (organic EL device) Can be provided.
  • the compound represented by the general formula (1) of the present invention may have a function of assisting light emission of another light emitting material included in the light emitting layer as a so-called assist dopant. That is, the compound represented by the general formula (1) of the present invention contained in the light emitting layer includes the lowest excitation singlet energy level of the host material contained in the light emitting layer and the lowest excitation of other light emitting materials contained in the light emitting layer.
  • the organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate.
  • the organic electroluminescence element has a structure in which an organic layer is formed at least between an anode, a cathode, and an anode and a cathode.
  • the organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer.
  • the hole transport layer may be a hole injection / transport layer having a hole injection function
  • the electron transport layer may be an electron injection / transport layer having an electron injection function.
  • FIG. 1 A specific example of the structure of an organic electroluminescence element is shown in FIG.
  • 1 is a substrate
  • 2 is an anode
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • 5 is a light emitting layer
  • 6 is an electron transport layer
  • 7 is a cathode.
  • each member and each layer of an organic electroluminescent element are demonstrated.
  • substrate and a light emitting layer corresponds also to the board
  • the organic electroluminescence device of the present invention is preferably supported on a substrate.
  • the substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements.
  • a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
  • a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture
  • Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.
  • the light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer. , Preferably including a luminescent material and a host material. As a luminescent material, the 1 type (s) or 2 or more types chosen from the compound group of this invention represented by General formula (1) can be used. In order for the organic electroluminescence device and the organic photoluminescence device of the present invention to exhibit high luminous efficiency, it is important to confine singlet excitons and triplet excitons generated in the light emitting material in the light emitting material.
  • a host material in addition to the light emitting material in the light emitting layer.
  • the host material an organic compound having at least one of excited singlet energy and excited triplet energy higher than that of the light emitting material of the present invention can be used.
  • singlet excitons and triplet excitons generated in the light emitting material of the present invention can be confined in the molecules of the light emitting material of the present invention, and the light emission efficiency can be sufficiently extracted.
  • high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention.
  • the organic light emitting device or organic electroluminescent device of the present invention light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This emission includes both fluorescence and delayed fluorescence. However, light emission from the host material may be partly or partly emitted.
  • the amount of the compound of the present invention, which is a light emitting material is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% or more. It is preferably no greater than wt%, more preferably no greater than 20 wt%, and even more preferably no greater than 10 wt%.
  • the host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.
  • the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission, and includes a hole injection layer and an electron injection layer, Further, it may be present between the cathode and the light emitting layer or the electron transport layer.
  • the injection layer can be provided as necessary.
  • the blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer.
  • the electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer.
  • a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer.
  • the blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer.
  • the term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense.
  • the hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer.
  • the material for the hole blocking layer the material for the electron transport layer described later can be used as necessary.
  • the electron blocking layer has a function of transporting holes in a broad sense.
  • the electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .
  • the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
  • the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  • the layer when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer.
  • a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided.
  • an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided.
  • the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the compound represented by the general formula (1) may be used not only for the light emitting layer but also for layers other than the light emitting layer.
  • the compound represented by General formula (1) used for a light emitting layer and the compound represented by General formula (1) used for layers other than a light emitting layer may be same or different.
  • the compound represented by the general formula (1) may be used for the injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transporting layer, electron transporting layer, and the like. .
  • the method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.
  • the preferable material which can be used for an organic electroluminescent element is illustrated concretely.
  • the material that can be used in the present invention is not limited to the following exemplary compounds.
  • R and R 1 to R 10 in the structural formulas of the following exemplary compounds each independently represent a hydrogen atom or a substituent.
  • n represents an integer of 3 to 5.
  • the organic electroluminescent device produced by the above-described method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
  • the excited triplet energy is unstable and is converted into heat and the like, and the lifetime is short and it is immediately deactivated.
  • the excited triplet energy of a normal organic compound it can be measured by observing light emission under extremely low temperature conditions.
  • the organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, an organic light emitting device with greatly improved light emission efficiency can be obtained by containing the compound represented by the general formula (1) in the light emitting layer.
  • the organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention.
  • organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.
  • Photonics C11347), source meter (Ceethley: 2400 series), semiconductor parameter analyzer (Agilent Technology: E5273A), optical power meter measuring device (Newport: 1930C), optical spectrometer (The measurement was carried out using a spectroradiometer (manufactured by Topcon Co., Ltd .: SR-3) and a streak camera (C4334, manufactured by Hamamatsu Photonics Co., Ltd.). Further, the molecular orientation was measured using an ellipsometer ( M-2000 manufactured by JA Woollam). Construction of the optical model, fitting for minimizing the mean square error between the optical model and the actual measurement value, etc.
  • the order parameter S for evaluating the degree of orientation was defined by the following equation.
  • Mean value of the angle ⁇ is formed by the normal direction and the molecules of the substrate, which is k o, k e extinction coefficient of the molecules with the transition dipole in the horizontal direction and the normal direction respectively with respect to the substrate.
  • 1,4-dibromo-2,3,5,6-tetrafluorobenzene (0.240 g, 0.78 mmol)
  • 2- (4- (9H-phenoxazin-9-yl) phenyl-1-yl) -4 , 4,5,5-tetramethyl-1,3,2-dioxaborolane (0.05 g, 0.13 mmol), tetrahydrofuran (17 ml), Pd (PPh 3 ) 4 (0.08 g, 0.07 mmol)
  • 2M K 2 CO 3 aq 5 mL was placed in a 50 ml three-necked flask and degassed. The degassed solution was heated to 66 ° C.
  • 1,4-dibromo-2,3,5,6-tetrafluorobenzene (0.308 g, 1 mmol), 2- (4- (9H-10,10-dimethylacridin-9-yl) phenyl-1-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.10 g, 0.2 mmol), tetrahydrofuran (50 ml), Pd (PPh 3 ) 4 (0.20 g, 0.17 mmol), 2M K 2 CO 3 aq (12 mL) was placed in a 200 ml three-necked flask and degassed. The degassed solution was heated to 66 ° C.
  • 1,3,5-tribromo-2,4,6-trifluorobenzene (0.738 g, 2 mmol), 2- ⁇ 4- (9H-carbazolyl-9-yl) phenyl-1-yl ⁇ -4,4 5,5-tetramethyl-1,3,2-dioxaborolane (0.52 g, 1.4 mmol), tetrahydrofuran (55 ml), tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 : 0.30 g,. 26 mmol), and 2M K 2 CO 3 aq (15 mL) were placed in a 200 ml three-necked flask and degassed.
  • the degassed solution was heated to 66 ° C. under a nitrogen stream, and further 1,4- ⁇ 4- (9H-carbazolyl-9-yl) phenyl-1-yl ⁇ -4,4,5,5-tetra
  • a solution of methyl-1,3,2-dioxaborolane (1.70 g, 4.6 mmol) in 20 ml of tetrahydrofuran was added dropwise over 12 hours, and the mixture was stirred for 6 days while maintaining the temperature at 66 ° C. After returning this reaction solution to room temperature, tetrahydrofuran was removed from the reaction solution using an evaporator to obtain a precipitate. The precipitate was collected by filtration, washed with water, and dried in vacuo.
  • Comparative Synthesis Example 2 Synthesis of Comparative Compound 2 Except for using 1,4-dibromo-2,3,5,6-tetrafluorobenzene instead of 1,3,5-tribromo-2,4,6-trifluorobenzene was synthesized in the same manner as in the synthesis step of Comparative Compound 1 in Comparative Synthesis Example 1.
  • Example 1 Preparation and Evaluation of Solution Using Compound 1
  • a toluene solution of Compound 1 was prepared in a glove box under an Ar atmosphere. An emission spectrum by 337 nm excitation light was measured. The measured emission spectrum is shown in FIG.
  • the maximum emission wavelength of the toluene solution of Compound 1 was 505 nm, and the photoluminescence quantum efficiency was 17.2% in air and 45.4% after deaeration.
  • the transient decay curve was measured about the toluene solution of the compound 1, the light emission lifetime (tau) in the air was 8.22 ns.
  • the emission lifetime ⁇ 1 of immediate fluorescence is 19.6 ns
  • the emission lifetime ⁇ 2 of delayed fluorescence is 8 .52 ⁇ s.
  • Example 2 Production and Evaluation of Organic Photoluminescence Device Using Compound 2
  • a toluene solution of Compound 2 was prepared by changing the point where Compound 2 was used instead of Compound 1. Further, a thin film of Compound 2 having a thickness of 50 nm was formed on a quartz substrate by a vacuum vapor deposition method under a vacuum degree of 4.0 ⁇ 10 ⁇ 4 Pa or less to obtain an organic photoluminescence device. Separately, Compound 2 and mCP are deposited on a quartz substrate by a vacuum deposition method under a vacuum degree of 4.0 ⁇ 10 ⁇ 4 Pa or less from different deposition sources, and the concentration of Compound 2 is 6.0 weight.
  • % Thin film was formed with a thickness of 50 nm to obtain an organic photoluminescence device.
  • Compound 2 and DPEPO are vapor-deposited from a different vapor deposition source on a quartz substrate by a vacuum vapor deposition method under a vacuum degree of 4.0 ⁇ 10 ⁇ 4 Pa or less.
  • a thin film of 0% by weight was formed with a thickness of 50 nm to obtain an organic photoluminescence device.
  • the orientation angle of the molecule relative to the film-forming surface of Compound 2 was 16.0 °.
  • the absorption emission spectrum of the toluene solution is shown in FIG.
  • An absorption spectrum of an organic photoluminescence device having a thin film of only Compound 2 is shown in FIG. 4, and an emission spectrum is shown in FIG.
  • An emission spectrum of an organic photoluminescence device having a thin film of Compound 2 and mCP is shown in FIG.
  • An emission spectrum of an organic photoluminescence device having a thin film of Compound 2 and DPEPO is shown in FIG. 7, and a fluorescence spectrum and a phosphorescence spectrum are shown in FIG.
  • the maximum emission wavelength was 457 nm
  • the photoluminescence quantum efficiency was 11.5% in air, and 18% after deaeration.
  • the photoluminescence quantum efficiency of the organic photoluminescence device is 31.1% for a device having a thin film of compound 2 only, 30% for a device having a thin film of compound 2 and mCP, and 48% of a device having a thin film of compound 2 and DPEPO. Met.
  • the difference ⁇ Est between the energy in the excited singlet state and the energy in the excited triplet state obtained from the fluorescence spectrum and the phosphorescence spectrum was 0.351 eV.
  • transient decay curves show the results of luminescence lifetime measurement in which the process in which the emission intensity is deactivated by applying excitation light to the compound is measured.
  • the light emission intensity decays in a single exponential manner. This means that if the vertical axis of the graph is semi-log, it will decay linearly.
  • Comparative Example 1 Preparation and Evaluation of Organic Photoluminescence Device Using Comparative Compound 1
  • a dichloromethane solution of Comparative Compound 1 and a thin film only of Comparative Compound 1 were used.
  • An organic photoluminescence device having the above was produced.
  • the emission wavelength peak of the degassed dichloromethane solution was 363 nm, and the emission quantum yield was 48%.
  • the light emission lifetime ⁇ was 4.795 ns, and no delay component was observed.
  • the neat thin film had an emission wavelength peak of 381 nm and an emission quantum yield of 30%.
  • the light emission lifetime was 4.993 ns, and no delay component was observed.
  • Comparative Example 2 Production and Evaluation of Organic Photoluminescence Device Using Comparative Compound 2
  • a dichloromethane solution of Comparative Compound 2 and a thin film only of Comparative Compound 2 were prepared.
  • An organic photoluminescence element having the same was produced.
  • the emission wavelength peak of the degassed dichloromethane solution was 447 nm, and the emission quantum yield was 92%.
  • the emission lifetime ⁇ was 2.133 ns, and no delay component was observed.
  • the neat thin film had an emission wavelength peak of 429 nm and an emission quantum yield of 30%. The emission lifetime was 1.296 ns, and no delay component was observed.
  • Example 3 Production and evaluation of organic electroluminescence device using compound 2 Each thin film was formed by vacuum deposition on a glass substrate on which an anode made of indium tin oxide (ITO) having a thickness of 100 nm was formed. And a degree of vacuum of 4 ⁇ 10 ⁇ 4 Pa. First, ⁇ -NPD was formed to a thickness of 40 nm on ITO. Next, Compound 2 and DPEPO were co-evaporated from different vapor deposition sources to form a layer having a thickness of 30 nm to form a light emitting layer. At this time, the concentration of Compound 2 was 6.0% by weight.
  • ITO indium tin oxide
  • DPEPO is formed to a thickness of 5 nm
  • TPBi is formed to a thickness of 30 nm
  • lithium fluoride (LiF) is vacuum-deposited to 0.5 nm
  • aluminum (Al) is then evaporated to a thickness of 100 nm.
  • a cathode was formed, and an organic electroluminescence element was obtained.
  • the emission spectrum of the manufactured organic electroluminescence device is shown in FIG. 11, the voltage-current density characteristic is shown in FIG. 12, and the current density-external quantum efficiency characteristic is shown in FIG.
  • the organic electroluminescence device using Compound 2 as the light emitting material achieved a high external quantum efficiency of 8.3%.
  • the compound of the present invention is useful as a luminescent material. For this reason, the compound of this invention is effectively used as a luminescent material for organic light emitting elements, such as an organic electroluminescent element. Since the compounds of the present invention include those that emit delayed fluorescence, it is also possible to provide an organic light-emitting device with high luminous efficiency. For this reason, this invention has high industrial applicability.

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Abstract

　Composé de formule générale (1), utile comme matériau électroluminescent. Dans ladite formule, R1, R3, et R5 représentent des atomes de fluor, ou bien R1, R2, R4 et R5 représentent des atomes de fluor. Les éléments restants, R1-R6, représentent des groupes de formule générale (2).
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