WO2014034535A1 - 発光材料、化合物、およびそれらを用いた有機発光素子 - Google Patents
発光材料、化合物、およびそれらを用いた有機発光素子 Download PDFInfo
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- WO2014034535A1 WO2014034535A1 PCT/JP2013/072499 JP2013072499W WO2014034535A1 WO 2014034535 A1 WO2014034535 A1 WO 2014034535A1 JP 2013072499 W JP2013072499 W JP 2013072499W WO 2014034535 A1 WO2014034535 A1 WO 2014034535A1
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005495 pyridazyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Images
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Definitions
- the present invention relates to a compound useful as a light emitting material and an organic light emitting device using the compound.
- Patent Document 1 describes that a compound containing a phenazine structure represented by the following general formula is used as a host material such as an organic electroluminescence element.
- R 1 to R 8 are hydrogen atoms, alkyl groups, aryl groups, etc.
- R 9 and R 10 are defined as hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, or alkenyl groups.
- benzoxazolylphenyl group, benzothiazolylphenyl group, and indazolylphenyl group are not described as R 9 and R 10 .
- a compound containing a benzoxazolylphenyl group, a benzothiazolylphenyl group or an indazolylphenyl group a compound having the following structure is known.
- the donor site is a diphenylamino group, and there is no suggestion of making a phenazine structure, a phenoxazine structure, or a phenothiazine structure.
- Patent Document 2 describes that a compound represented by the following general formula is useful as a host material.
- R 1 and R 2 are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 13 carbon atoms
- R 11 to R 14 are hydrogen atoms.
- An atom, halogen, an alkyl group having 1 to 4 carbon atoms, or an unsubstituted aryl group having 6 to 10 carbon atoms, and any two of ⁇ , ⁇ , and ⁇ are bonded to form one bond.
- carbazole skeleton is formed, and n is 0 to 3.
- Patent Document 2 also describes a light-emitting element using a compound having the following structure as a host material as a specific compound included in the above general formula, but light emission from this compound is not observed. It is clearly stated.
- the present inventors have combined a phenazine structure, a phenoxazine structure, a phenothiazine structure, and the like with a benzoxazolylphenyl group, a benzothiazolylphenyl group, an indazolylphenyl group, and the like. Studies were carried out for the purpose of synthesizing compounds contained in molecules and evaluating their usefulness as luminescent materials. In addition, a general formula of a compound useful as a light-emitting material has been derived, and extensive studies have been conducted with the aim of generalizing the structure of an organic light-emitting device having high luminous efficiency.
- the present inventors have succeeded in synthesizing the target compound and have revealed for the first time that these compounds are useful as light emitting materials.
- 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).
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and Y represents O, S Or represents N—R 16 .
- Ar 1 represents a substituted or unsubstituted arylene group, and Ar 2 represents an aromatic ring or a heteroaromatic ring.
- R 1 to R 8 and R 11 to R 16 each independently represents a hydrogen atom or a substituent.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 may be bonded to each other to form a cyclic structure.
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 )
- Y represents O, S Or represents N—R 16 .
- Ar 2 represents an aromatic ring or a heteroaromatic ring.
- R 1 to R 8 , R 11 to R 16 and R 21 to R 24 each independently represents a hydrogen atom or a substituent.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 21 and R 22 , R 23 and R 24 are respectively They may be bonded to each other to form a cyclic structure.
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and Y represents O, S Or represents N—R 16 .
- R 1 to R 8 , R 11 to R 16 , R 21 to R 24 and R 31 to R 34 each independently represent a hydrogen atom or a substituent.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 21 and R 22 , R 23 and R 24 , R 31 And R 32 , R 32 and R 33 , and R 33 and R 34 may be bonded to each other to form a cyclic structure.
- Y is O, S or N—R 16 , and R 16 is a substituted or unsubstituted aryl group material.
- R 1 to R 8 are each independently a hydrogen atom, 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 group having 1 to 10 carbon atoms.
- a delayed phosphor comprising the luminescent material according to any one of [1] to [6].
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 )
- Y represents O, S or N—R 16 is represented.
- Ar 1 represents a substituted or unsubstituted arylene group
- Ar 2 represents an aromatic ring or a heteroaromatic ring.
- R 1 to R 8 and R 11 to R 16 each independently represent a hydrogen atom or a substituent, but when X is O, R 16 is not a phenyl group.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 may be bonded to each other to form a cyclic structure. Good.
- An organic light-emitting device having a light-emitting layer containing the light-emitting material according to any one of [1] to [6] on a substrate.
- the organic light-emitting device according to [9] which emits delayed fluorescence.
- the compound represented by the general formula (1) is useful as a light emitting material.
- the compound represented by the general formula (1) includes those that emit delayed fluorescence.
- the organic light emitting device using the compound represented by the general formula (1) as a light emitting material can realize high luminous efficiency.
- 2 is a 1 H NMR spectrum of Compound 1 synthesized in Synthesis Example 1.
- 2 is a 1 H NMR spectrum of Compound 2 synthesized in Synthesis Example 2.
- 2 is an emission spectrum of a toluene solution of compound 1 of Example 1.
- 2 is a transient decay curve of a toluene solution of Compound 1 of Example 1.
- FIG. 2 is an emission spectrum of a toluene solution of the compound 2 of Example 1.
- 2 is a transient decay curve of a toluene solution of the compound 2 of Example 1.
- 2 is an emission spectrum of a toluene solution of compound 3 of Example 1.
- FIG. 2 is a transient decay curve of a toluene solution of compound 3 of Example 1.
- FIG. 2 is a transient decay curve of a toluene solution of a comparative compound of Comparative Example 1.
- 2 is an emission spectrum of a thin film type organic photoluminescence device using Compound 1 of Example 2.
- 2 is a transient attenuation curve of a thin film type organic photoluminescence device using Compound 1 of Example 2.
- FIG. 2 is an emission spectrum of a thin film type organic photoluminescence device using Compound 2 of Example 2.
- 3 is a transient decay curve of a thin film type organic photoluminescence device using the compound 2 of Example 2.
- 2 is an emission spectrum of a thin film type organic photoluminescence device using the compound 3 of Example 2.
- 4 is a transient attenuation curve of a thin film type organic photoluminescence device using the compound 3 of Example 2.
- 2 is an emission spectrum of an organic electroluminescence device using Compound 1 of Example 3.
- 4 is a graph showing current density-voltage characteristics of an organic electroluminescence device using Compound 1 of Example 3.
- 4 is a graph showing external quantum efficiency-current density characteristics of an organic electroluminescence device using Compound 1 of Example 3.
- 2 is an emission spectrum of an organic electroluminescence device using the compound 2 of Example 3.
- 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 having a structure represented by the following general formula (1).
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and Y represents O, S or N—R 16 is represented.
- Ar 1 represents a substituted or unsubstituted arylene group
- Ar 2 represents an aromatic ring or a heteroaromatic ring.
- R 1 to R 8 and R 11 to R 16 each independently represents a hydrogen atom or a substituent.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 may be bonded to each other to form a cyclic structure. Good.
- R 1 to R 8 in the general formula (1) each independently represents a hydrogen atom or a substituent.
- R 1 to R 8 may all be hydrogen atoms.
- those substituents may be the same or different.
- the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkyl substitution 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, a substituted or unsubstituted dialkylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, and 12 to 40 carbon atoms A substituted or unsubstituted carbazolyl group; More preferred substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms
- an unsubstituted dialkylamino group a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms It is a group.
- the alkyl group in the present specification may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, and butyl. A tert-butyl group, a pentyl group, a hexyl group and an isopropyl group.
- the aryl group may be a single ring or a fused ring, and specific examples thereof include a phenyl group and a naphthyl group.
- the alkoxy group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms.
- the two alkyl groups of the dialkylamino group may be the same or different from each other, but are preferably the same.
- the two alkyl groups of the dialkylamino group may each independently be linear, branched or cyclic, and more preferably have 1 to 6 carbon atoms.
- Specific examples include a methyl group, an ethyl group, Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.
- Two alkyl groups of the dialkylamino group may be bonded to each other to form a cyclic structure together with the nitrogen atom of the amino group.
- the aryl group that can be employed as the substituent may be a single ring or a fused ring, and specific examples thereof include a phenyl group and a naphthyl group.
- the heteroaryl group may be a monocyclic ring or a fused ring, and specific examples include a pyridyl group, a pyridazyl group, a pyrimidyl group, a triazyl group, a triazolyl group, and a benzotriazolyl group.
- These heteroaryl groups may be a group bonded through a hetero atom or a group bonded through a carbon atom constituting a heteroaryl ring.
- the two aryl groups of the diarylamino group may be monocyclic or fused, and specific examples thereof include a phenyl group and a naphthyl group. Two aryl groups of the diarylamino group may be bonded to each other to form a cyclic structure together with the nitrogen atom of the amino group.
- An example is a 9-carbazolyl group.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 in the general formula (1) are bonded to each other to form a cyclic structure. May be formed.
- the cyclic structure may be an aromatic ring or an alicyclic ring, and may contain a hetero atom.
- 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.
- X in the general formula (1) is O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and O, S, N— R 11 or C ⁇ O is preferable, and O or S is more preferable.
- R 11 each represents a hydrogen atom or a substituent, and among others a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, preferable.
- the substituted or unsubstituted alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. Even more preferably.
- the substituted or unsubstituted aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- R 1 to R 8 the description and preferred ranges of the substituents that can be taken by the above R 1 to R 8 can be referred to, but preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted And an amino group, a substituted or unsubstituted heteroaryl group, and the like.
- R 11 examples include a methyl group, an ethyl group, an n-propyl group, a phenyl group, a p-tolyl group, a diphenylaminophenyl group, a dinaphthylaminophenyl group, a triazinylphenyl group, and further a substituent ( For example, a group substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms can be given.
- X in the general formula (1) is C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 )
- R 12 to R 15 represent a hydrogen atom or a substituent.
- R 1 to R 8 can take, and a substituted or unsubstituted alkyl group is preferred.
- the substituted or unsubstituted alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. Even more preferably.
- R 12 and R 13 may be the same or different, and R 14 and R 15 may be the same or different. Preferred is the case where they are identical.
- C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ) include C (CH 3 ) 2 , C (C 2 H 5 ) 2 , C (CH 3 ) (C 2 H 5 ), C (C 3 H 7 ) 2 , Si (CH 3 ) 2 , Si (C 2 H 5 ) 2 , Si (CH 3 ) (C 2 H 5 ), Si (C 3 H 7 ) 2, etc.
- specific examples of C (R 12 ) (R 13 ) and Si (R 14 ) (R 15 ) are not limited to these.
- Y in the general formula (1) represents O, S or N—R 16, and is preferably O or S.
- R 16 represents a hydrogen atom or a substituent.
- R 11 the above description of R 11 can be referred to.
- Ar 1 in the general formula (1) represents a substituted or unsubstituted arylene group.
- the substituted or unsubstituted arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- substituent for the arylene group reference can be made to the description and preferred ranges of the substituents which can be taken by the above R 1 to R 8 , preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group. Can be mentioned.
- the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group mentioned here preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. More preferably it is.
- Ar 1 include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, and 1,3-naphthylene group.
- 1,4-phenylene group A preferred example is a 3-phenylene group.
- Ar 2 in the general formula (1) represents an aromatic ring or a heteroaromatic ring.
- a nitrogen atom can be preferably exemplified, and the number of hetero atoms constituting the ring skeleton is preferably 1 to 3, more preferably 1 or 2.
- Specific examples of the aromatic ring or heteroaromatic ring constituting Ar 2 include a benzene ring, a pyridine ring, and a pyridazine ring. A pyrimidine ring, a pyrazine ring, etc. can be mentioned. Another aromatic structure may be fused with the aromatic ring or heteroaromatic ring constituting Ar 2 .
- fused rings examples include aromatic rings, heteroaromatic rings, aliphatic hydrocarbon rings, and non-aromatic heterocyclic rings.
- Preferred examples of the ring skeleton atoms constituting these fused rings include carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. These fused rings are preferably 5- to 7-membered rings, more preferably 5- or 6-membered rings.
- the compound represented by the general formula (1) preferably has a structure represented by the following general formula (2).
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and Y represents O, S or N—R 16 is represented.
- Ar 2 represents an aromatic ring or a heteroaromatic ring.
- R 1 to R 8 , R 11 to R 16 and R 21 to R 24 each independently represents a hydrogen atom or a substituent.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 21 and R 22 , R 23 and R 24 are respectively They may be bonded to each other to form a cyclic structure.
- R 21 to R 24 in the general formula (2) are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
- R 21 to R 24 may all be hydrogen atoms, or all may be substituents. When two or more are substituents, they may be the same as or different from each other.
- the corresponding explanations and preferred ranges of R 1 to R 8 can be referred to.
- the compound represented by the general formula (1) has a structure represented by the following general formula (3).
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and Y represents O, S or N—R 16 is represented.
- R 1 to R 8 , R 11 to R 16 , R 21 to R 24 and R 31 to R 34 each independently represent a hydrogen atom or a substituent.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 21 and R 22 , R 23 and R 24 , R 31 And R 32 , R 32 and R 33 , and R 33 and R 34 may be bonded to each other to form a cyclic structure.
- R 31 to R 34 in the general formula (3) are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. And a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms.
- R 31 to R 34 may all be hydrogen atoms, or all may be substituents. When two or more are substituents, they may be the same as or different from each other.
- R 31 and R 32 , R 32 and R 33 , and R 33 and R 34 the corresponding explanations and preferred ranges of R 1 to R 8 can be referred to. .
- 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.
- a monomer containing a polymerizable functional group is prepared in any one of R 1 to R 8 , X, Y, Ar 1 , Ar 2 in the general formula (1), and this is polymerized alone, It is conceivable to obtain a polymer having a repeating unit by copolymerizing with other monomers and to use the polymer as a light emitting material. Alternatively, it is also possible to obtain a dimer or trimer by coupling compounds having a structure represented by the general formula (1) and use them as a light emitting material.
- Examples of the polymer having a repeating unit containing a structure represented by the general formula (1) include a polymer containing a structure represented by the following general formula (4) or (5).
- 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 bonded to any of the structures of the general formula (1) constituting Q. Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.
- repeating unit examples include structures represented by the following formulas (6) to (9).
- a polymer having a repeating unit containing these formulas (6) to (9) has a part of the structure of the general formula (1) as a hydroxy group, and this is used as a linker to react with the following compound to form a polymerizable group. And can be synthesized by 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. For example, although a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene or styrene can be mentioned, the repeating unit is not limited to the exemplified repeating unit.
- the compound represented by the following general formula (1 ′) is a novel compound.
- X represents O, S, N—R 11 , C ⁇ O, C (R 12 ) (R 13 ) or Si (R 14 ) (R 15 ), and Y represents O, S Or represents N—R 16 .
- Ar 1 represents a substituted or unsubstituted arylene group
- Ar 2 represents an aromatic ring or a heteroaromatic ring.
- R 1 to R 8 and R 11 to R 16 each independently represent a hydrogen atom or a substituent, but when X is O, R 16 is not a phenyl group.
- R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 may be bonded to each other to form a cyclic structure. Good.
- the compound represented by the general formula (1) can be synthesized by combining known reactions. For example, it can be carried out by reacting the compound represented by the general formula (11) with the compound represented by the general formula (12) according to the following scheme. This reaction itself is a known reaction, and known reaction conditions can be appropriately selected and used.
- the compound represented by the general formula (12) can be synthesized, for example, by converting a corresponding chloride into an amine and further converting into a bromide.
- 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.
- 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.
- 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 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. In FIG. 1, 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, and 7 is a cathode. Below, each member and each layer of an organic electroluminescent element are demonstrated. In addition, description of a 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.
- 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.
- 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.
- 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, thiopyran dioxide oxide 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 electroluminescence 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.
- 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. For details, see “Organic EL Display” (Ohm Co., Ltd.) ) Can be referred to.
- the organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.
- Phenoxazine 0.70 g (3.8 mmol) and 2- (4-bromophenyl) benzothiazole 0.74 g (2.5 mmol) were placed in a 100 mL two-necked flask purged with nitrogen.
- 10 mL of degassed and dehydrated toluene, 1.0 g (7.2 mmol) of potassium carbonate, 0.060 g (0.25 mmol) of palladium acetate, and 0.051 g (0.25 mmol) of tri-tert-butylphosphine were added. . This mixture was stirred at 100 ° C. for 15 hours under a nitrogen atmosphere.
- FIG. 2 shows 1 H-NMR (CDCl 3 , 500 MHz).
- FIG. 3 shows 1 H-NMR (CDCl 3 , 500 MHz).
- Example 1 Preparation and Evaluation of Solution A toluene solution (concentration 10 ⁇ 5 mol / L) of Compound 1 synthesized in Synthesis Example 1 was prepared and irradiated with ultraviolet light at 300 K while bubbling nitrogen. As shown in FIG. 4, fluorescence having a peak wavelength of 512 nm was observed. Further, a transient decay curve shown in FIG. 5 was obtained by measuring with a small fluorescence lifetime measuring apparatus (Quantaurus-tau manufactured by Hamamatsu Photonics Co., Ltd.) before and after the nitrogen bubble. This transient decay curve shows the result of measuring the luminescence lifetime obtained by measuring the process in which the emission intensity is deactivated by applying excitation light to the compound.
- a small fluorescence lifetime measuring apparatus Quantantaurus-tau manufactured by Hamamatsu Photonics Co., Ltd.
- FIG. 8 shows an emission spectrum having a peak wavelength of 468 nm
- FIG. 9 shows a transient decay curve after a nitrogen bubble.
- a short-life component having an excitation lifetime of 0.01 ⁇ s and a long-life component of 490 ⁇ s were observed.
- the photoluminescence quantum efficiency was 14.1% before the nitrogen bubble and 21.1% after the nitrogen bubble.
- Comparative Example 1 Preparation and Evaluation of Solution
- a toluene solution of a comparative compound having the following structure was prepared.
- Example 2 Preparation and evaluation of thin film type organic photoluminescence device (thin film)
- an emission spectrum having a peak wavelength of 504 nm was obtained (FIG. 11).
- the photoluminescence quantum efficiency was 62.0% at 300K.
- the transient attenuation curve shown in FIG. 12 was obtained.
- the short life component was 0.013 ⁇ s and the long life component was 576 ⁇ s.
- an emission spectrum having a peak wavelength of 498 nm was obtained (FIG. 13), and a transient attenuation curve shown in FIG. 14 was obtained.
- the photoluminescence quantum efficiency was 65.0% at 300K.
- the short life component was 0.013 ⁇ s, and the long life component was 300 ⁇ s.
- an emission spectrum having a peak wavelength of 469 nm was obtained (FIG. 15), and a transient decay curve shown in FIG. 16 was obtained.
- the photoluminescence quantum efficiency was 35% at 300K.
- the short life component was 0.013 ⁇ s and the long life component was 462 ⁇ s.
- Example 3 Production and Evaluation of Organic Electroluminescence Element
- ITO indium tin oxide
- Lamination was performed at 0 ⁇ 10 ⁇ 4 Pa.
- ⁇ -NPD was formed on ITO to a thickness of 35 nm.
- Compound 1 and CBP were co-deposited from different vapor deposition sources to form a layer having a thickness of 15 nm as a light emitting layer. At this time, the concentration of Compound 1 was 6.0% by weight.
- TPBi is formed to a thickness of 65 nm
- further lithium fluoride (LiF) is vacuum-deposited to 0.8 nm
- aluminum (Al) is evaporated to a thickness of 80 nm to form a cathode.
- a luminescence element was obtained.
- a semiconductor parameter analyzer manufactured by Agilent Technologies: E5273A
- an optical power meter measuring device manufactured by Newport: 1930C
- an optical spectrometer manufactured by Ocean Optics: USB2000
- the organic electroluminescence device using Compound 1 as the light emitting material achieved a high external quantum efficiency of 10.29%. Assuming that an ideal organic electroluminescence device balanced using a fluorescent material having a light emission quantum efficiency of 100% is prototyped, if the light extraction efficiency is 20 to 30%, the external quantum efficiency of fluorescence emission is 5%. 7.5%. This value is generally regarded as a theoretical limit value of the external quantum efficiency of an organic electroluminescence device using a fluorescent material. The organic electroluminescence device of the present invention using Compound 1 is extremely excellent in that high external quantum efficiency exceeding the theoretical limit value is realized.
- FIG. 21 shows current density-voltage characteristics
- FIG. 22 shows current density-external quantum efficiency characteristics.
- the organic electroluminescence device using Compound 2 as the light emitting material achieved a high external quantum efficiency of 6.31%.
- the compound represented by the general formula (1) is useful as a luminescent material.
- the compound represented by General formula (1) is effectively used as a luminescent material for organic light emitting elements, such as an organic electroluminescent element.
- organic light emitting elements such as an organic electroluminescent element.
- those that emit delayed fluorescence are included, and it is also possible to provide an organic light-emitting element with high luminous efficiency. For this reason, this invention has high industrial applicability.
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Abstract
Description
その中には、フェナジン構造を含む化合物を利用した有機エレクトロルミネッセンス素子に関する研究も見受けられる。例えば特許文献1には、下記の一般式で表されるフェナジン構造を含む化合物を、有機エレクトロルミネセンス素子などのホスト材料として用いることが記載されている。下記の一般式において、R1~R8は水素原子、アルキル基、アリール基等であり、R9およびR10は水素原子、アルキル基、アリール基、ヘテロ環基またはアルケニル基であることが規定されている。しかしながら、R9およびR10として、ベンゾオキサゾリルフェニル基、ベンゾチアゾリルフェニル基、インダゾリルフェニル基は記載されていない。
[2] 前記一般式(1)で表される化合物が、下記一般式(2)で表される化合物であることを特徴とする[1]に記載の発光材料。
[3] 前記一般式(1)で表される化合物が、下記一般式(3)で表される化合物であることを特徴とする[1]に記載の発光材料。
[4] XがOまたはSであることを特徴とする[1]~[3]のいずれか1項に記載の発光材料。
[5] YがO、SまたはN-R16であって、R16が置換もしくは無置換のアリール基であることを特徴とする[1]~[4]のいずれか1項に記載の発光材料。
[6] R1~R8が、各々独立に水素原子、フッ素原子、塩素原子、シアノ基、炭素数1~10の置換もしくは無置換のアルキル基、炭素数1~10の置換もしくは無置換のアルコキシ基、炭素数1~10の置換もしくは無置換のジアルキルアミノ基、炭素数12~40の置換もしくは無置換のジアリールアミノ基、炭素数6~15の置換もしくは無置換のアリール基、または炭素数3~12の置換もしくは無置換のヘテロアリール基であることを特徴とする[1]~[5]のいずれか1項に記載の発光材料。
[7] [1]~[6]のいずれか1項に記載の発光材料からなる遅延蛍光体。
[10] 遅延蛍光を放射することを特徴とする[9]に記載の有機発光素子。
[11] 有機エレクトロルミネッセンス素子であることを特徴とする[9]または[10]に記載の有機発光素子。
一般式(1)におけるXがN-R11であるとき、R11は水素原子または置換基を表すが、なかでも置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基であることが好ましい。置換もしくは無置換のアルキル基は、炭素数1~20であることが好ましく、炭素数1~10であることがより好ましく、炭素数1~6であることがさらに好ましく、炭素数1~3であることがさらにより好ましい。置換もしくは無置換のアリール基は、炭素数6~20であることが好ましく、炭素数6~14であることがより好ましく、炭素数6~10であることがさらに好ましい。アルキル基やアリール基に対する置換基としては、上記のR1~R8がとりうる置換基の説明と好ましい範囲を参照することができるが、好ましくは置換もしくは無置換のアルキル基、置換もしくは無置換のアミノ基、置換もしくは無置換のヘテロアリール基などを挙げることができる。R11の具体例として、メチル基、エチル基、n-プロピル基、フェニル基、p-トリル基、ジフェニルアミノフェニル基、ジナフチルアミノフェニル基、トリアジニルフェニル基や、それらがさらに置換基(例えば炭素数1~6のアルキル基や炭素数6~10のアリール基)で置換された基などを挙げることができる。
一般式(1)におけるXがC(R12)(R13)またはSi(R14)(R15)であるとき、R12~R15は水素原子または置換基を表す。置換基としては、上記のR1~R8がとりうる置換基の説明と好ましい範囲を参照することができるが、好ましくは置換もしくは無置換のアルキル基である。置換もしくは無置換のアルキル基は、炭素数1~20であることが好ましく、炭素数1~10であることがより好ましく、炭素数1~6であることがさらに好ましく、炭素数1~3であることがさらにより好ましい。R12とR13は同一であっても異なっていてもよく、また、R14とR15も同一であっても異なっていてもよい。好ましいのは、同一である場合である。C(R12)(R13)またはSi(R14)(R15)の具体例として、C(CH3)2、C(C2H5)2、C(CH3)(C2H5)、C(C3H7)2、Si(CH3)2、Si(C2H5)2、Si(CH3)(C2H5)、Si(C3H7)2などを挙げることができるが、C(R12)(R13)やSi(R14)(R15)の具体例はこれらに限定されるものではない。
一般式(1)におけるYがN-R16であるとき、R16は水素原子または置換基を表す。好ましいR16については、上記のR11の説明を参照することができる。
一般式(2)におけるR21~R24としては、水素原子、炭素数1~10の置換もしくは無置換のアルキル基、または炭素数1~10の置換もしくは無置換のアルコキシ基であることが好ましく、水素原子、炭素数1~6の置換もしくは無置換のアルキル基、または炭素数1~6の置換もしくは無置換のアルコキシ基であることが好ましく、水素原子、炭素数1~3の置換もしくは無置換のアルキル基、または炭素数1~3の置換もしくは無置換のアルコキシ基であることがより好ましい。R21~R24は、すべてが水素原子であってもよいし、すべてが置換基であってもよい。2つ以上が置換基である場合は、それらは互いに同一であっても異なっていてもよい。また、R21とR22、R23とR24が互いに結合して形成しうる環状構造については、R1~R8の対応する説明と好ましい範囲を参照することができる。
一般式(3)におけるR31~R34としては、水素原子、炭素数1~10の置換もしくは無置換のアルキル基、または炭素数1~10の置換もしくは無置換のアルコキシ基であることが好ましく、水素原子、炭素数1~6の置換もしくは無置換のアルキル基、または炭素数1~6の置換もしくは無置換のアルコキシ基であることが好ましい。R31~R34は、すべてが水素原子であってもよいし、すべてが置換基であってもよい。2つ以上が置換基である場合は、それらは互いに同一であっても異なっていてもよい。また、R31とR32、R32とR33、R33とR34が互いに結合して形成しうる環状構造については、R1~R8の対応する説明と好ましい範囲を参照することができる。
一般式(1)で表される化合物は、分子量にかかわらず塗布法で成膜してもよい。塗布法を用いれば、分子量が比較的大きな化合物であっても成膜することが可能である。
例えば、一般式(1)で表される構造中にあらかじめ重合性基を存在させておいて、その重合性基を重合させることによって得られる重合体を、発光材料として用いることが考えられる。具体的には、一般式(1)のR1~R8、X、Y、Ar1、Ar2のいずれかに重合性官能基を含むモノマーを用意して、これを単独で重合させるか、他のモノマーとともに共重合させることにより、繰り返し単位を有する重合体を得て、その重合体を発光材料として用いることが考えられる。あるいは、一般式(1)で表される構造を有する化合物どうしをカップリングさせることにより、二量体や三量体を得て、それらを発光材料として用いることも考えられる。
一般式(4)および(5)において、R101、R102、R103およびR104は、各々独立に置換基を表す。好ましくは、炭素数1~6の置換もしくは無置換のアルキル基、炭素数1~6の置換もしくは無置換のアルコキシ基、ハロゲン原子であり、より好ましくは炭素数1~3の無置換のアルキル基、炭素数1~3の無置換のアルコキシ基、フッ素原子、塩素原子であり、さらに好ましくは炭素数1~3の無置換のアルキル基、炭素数1~3の無置換のアルコキシ基である。
L1およびL2で表される連結基は、Qを構成する一般式(1)の構造のいずれかに結合する。1つのQに対して連結基が2つ以上連結して架橋構造や網目構造を形成していてもよい。
一般式(1)で表される化合物は、既知の反応を組み合わせることによって合成することができる。例えば、以下のスキームにしたがって一般式(11)で表される化合物と一般式(12)で表される化合物を反応させることにより行うことができる。この反応自体は公知の反応であり、公知の反応条件を適宜選択して用いることができる。また、一般式(12)で表される化合物は、例えば、対応する塩化物をアミンに変換し、さらに臭化物へと変換することにより合成することが可能である。
本発明の一般式(1)で表される化合物は、有機発光素子の発光材料として有用である。このため、本発明の一般式(1)で表される化合物は、有機発光素子の発光層に発光材料として効果的に用いることができる。一般式(1)で表される化合物の中には、遅延蛍光を放射する遅延蛍光材料(遅延蛍光体)が含まれている。そのような化合物を発光材料として用いた有機発光素子は、遅延蛍光を放射し、発光効率が高いという特徴を有する。その原理を、有機エレクトロルミネッセンス素子を例にとって説明すると以下のようになる。
以下において、有機エレクトロルミネッセンス素子の各部材および各層について説明する。なお、基板と発光層の説明は有機フォトルミネッセンス素子の基板と発光層にも該当する。
本発明の有機エレクトロルミネッセンス素子は、基板に支持されていることが好ましい。この基板については、特に制限はなく、従来から有機エレクトロルミネッセンス素子に慣用されているものであればよく、例えば、ガラス、透明プラスチック、石英、シリコンなどからなるものを用いることができる。
有機エレクトロルミネッセンス素子における陽極としては、仕事関数の大きい(4eV以上)金属、合金、電気伝導性化合物およびこれらの混合物を電極材料とするものが好ましく用いられる。このような電極材料の具体例としてはAu等の金属、CuI、インジウムチンオキシド(ITO)、SnO2、ZnO等の導電性透明材料が挙げられる。また、IDIXO(In2O3-ZnO)等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極材料を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、あるいはパターン精度をあまり必要としない場合は(100μm以上程度)、上記電極材料の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。あるいは、有機導電性化合物のように塗布可能な材料を用いる場合には、印刷方式、コーティング方式等湿式成膜法を用いることもできる。この陽極より発光を取り出す場合には、透過率を10%より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω/□以下が好ましい。さらに膜厚は材料にもよるが、通常10~1000nm、好ましくは10~200nmの範囲で選ばれる。
一方、陰極としては、仕事関数の小さい(4eV以下)金属(電子注入性金属と称する)、合金、電気伝導性化合物およびこれらの混合物を電極材料とするものが用いられる。このような電極材料の具体例としては、ナトリウム、ナトリウム-カリウム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、インジウム、リチウム/アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性および酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、リチウム/アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極材料を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω/□以下が好ましく、膜厚は通常10nm~5μm、好ましくは50~200nmの範囲で選ばれる。なお、発光した光を透過させるため、有機エレクトロルミネッセンス素子の陽極または陰極のいずれか一方が、透明または半透明であれば発光輝度が向上し好都合である。
また、陽極の説明で挙げた導電性透明材料を陰極に用いることで、透明または半透明の陰極を作製することができ、これを応用することで陽極と陰極の両方が透過性を有する素子を作製することができる。
発光層は、陽極および陰極のそれぞれから注入された正孔および電子が再結合することにより励起子が生成した後、発光する層であり、発光材料を単独で発光層に使用しても良いが、好ましくは発光材料とホスト材料を含む。発光材料としては、一般式(1)で表される本発明の化合物群から選ばれる1種または2種以上を用いることができる。本発明の有機エレクトロルミネッセンス素子および有機フォトルミネッセンス素子が高い発光効率を発現するためには、発光材料に生成した一重項励起子および三重項励起子を、発光材料中に閉じ込めることが重要である。従って、発光層中に発光材料に加えてホスト材料を用いることが好ましい。ホスト材料としては、励起一重項エネルギー、励起三重項エネルギーの少なくとも何れか一方が本発明の発光材料よりも高い値を有する有機化合物を用いることができる。その結果、本発明の発光材料に生成した一重項励起子および三重項励起子を、本発明の発光材料の分子中に閉じ込めることが可能となり、その発光効率を十分に引き出すことが可能となる。もっとも、一重項励起子および三重項励起子を十分に閉じ込めることができなくても、高い発光効率を得ることが可能な場合もあるため、高い発光効率を実現しうるホスト材料であれば特に制約なく本発明に用いることができる。本発明の有機発光素子または有機エレクトロルミネッセンス素子において、発光は発光層に含まれる本発明の発光材料から生じる。この発光は蛍光発光および遅延蛍光発光の両方を含む。但し、発光の一部或いは部分的にホスト材料からの発光があってもかまわない。
ホスト材料を用いる場合、発光材料である本発明の化合物が発光層中に含有される量は0.1重量%以上であることが好ましく、1重量%以上であることがより好ましく、また、50重量%以下であることが好ましく、20重量%以下であることがより好ましく、10重量%以下であることがさらに好ましい。
発光層におけるホスト材料としては、正孔輸送能、電子輸送能を有し、かつ発光の長波長化を防ぎ、なおかつ高いガラス転移温度を有する有機化合物であることが好ましい。
注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、正孔注入層と電子注入層があり、陽極と発光層または正孔輸送層の間、および陰極と発光層または電子輸送層との間に存在させてもよい。注入層は必要に応じて設けることができる。
阻止層は、発光層中に存在する電荷(電子もしくは正孔)および/または励起子の発光層外への拡散を阻止することができる層である。電子阻止層は、発光層および正孔輸送層の間に配置されることができ、電子が正孔輸送層の方に向かって発光層を通過することを阻止する。同様に、正孔阻止層は発光層および電子輸送層の間に配置されることができ、正孔が電子輸送層の方に向かって発光層を通過することを阻止する。阻止層はまた、励起子が発光層の外側に拡散することを阻止するために用いることができる。すなわち電子阻止層、正孔阻止層はそれぞれ励起子阻止層としての機能も兼ね備えることができる。本明細書でいう電子阻止層または励起子阻止層は、一つの層で電子阻止層および励起子阻止層の機能を有する層を含む意味で使用される。
正孔阻止層とは広い意味では電子輸送層の機能を有する。正孔阻止層は電子を輸送しつつ、正孔が電子輸送層へ到達することを阻止する役割があり、これにより発光層中での電子と正孔の再結合確率を向上させることができる。正孔阻止層の材料としては、後述する電子輸送層の材料を必要に応じて用いることができる。
電子阻止層とは、広い意味では正孔を輸送する機能を有する。電子阻止層は正孔を輸送しつつ、電子が正孔輸送層へ到達することを阻止する役割があり、これにより発光層中での電子と正孔が再結合する確率を向上させることができる。
励起子阻止層とは、発光層内で正孔と電子が再結合することにより生じた励起子が電荷輸送層に拡散することを阻止するための層であり、本層の挿入により励起子を効率的に発光層内に閉じ込めることが可能となり、素子の発光効率を向上させることができる。励起子阻止層は発光層に隣接して陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。すなわち、励起子阻止層を陽極側に有する場合、正孔輸送層と発光層の間に、発光層に隣接して該層を挿入することができ、陰極側に挿入する場合、発光層と陰極との間に、発光層に隣接して該層を挿入することができる。また、陽極と、発光層の陽極側に隣接する励起子阻止層との間には、正孔注入層や電子阻止層などを有することができ、陰極と、発光層の陰極側に隣接する励起子阻止層との間には、電子注入層、電子輸送層、正孔阻止層などを有することができる。阻止層を配置する場合、阻止層として用いる材料の励起一重項エネルギーおよび励起三重項エネルギーの少なくともいずれか一方は、発光材料の励起一重項エネルギーおよび励起三重項エネルギーよりも高いことが好ましい。
正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、正孔輸送層は単層または複数層設けることができる。
正孔輸送材料としては、正孔の注入または輸送、電子の障壁性のいずれかを有するものであり、有機物、無機物のいずれであってもよい。使用できる公知の正孔輸送材料としては例えば、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、カルバゾール誘導体、インドロカルバゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体およびピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、また導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられるが、ポルフィリン化合物、芳香族第3級アミン化合物およびスチリルアミン化合物を用いることが好ましく、芳香族第3級アミン化合物を用いることがより好ましい。
電子輸送層とは電子を輸送する機能を有する材料からなり、電子輸送層は単層または複数層設けることができる。
電子輸送材料(正孔阻止材料を兼ねる場合もある)としては、陰極より注入された電子を発光層に伝達する機能を有していればよい。使用できる電子輸送層としては例えば、ニトロ置換フルオレン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド、フレオレニリデンメタン誘導体、アントラキノジメタンおよびアントロン誘導体、オキサジアゾール誘導体等が挙げられる。さらに、上記オキサジアゾール誘導体において、オキサジアゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子吸引基として知られているキノキサリン環を有するキノキサリン誘導体も、電子輸送材料として用いることができる。さらにこれらの材料を高分子鎖に導入した、またはこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。
一方、りん光については、本発明の化合物のような通常の有機化合物では、励起三重項エネルギーは不安定で熱等に変換され、寿命が短く直ちに失活するため、室温では殆ど観測できない。通常の有機化合物の励起三重項エネルギーを測定するためには、極低温の条件での発光を観測することにより測定可能である。
合成例1で合成した化合物1のトルエン溶液(濃度10-5mol/L)を調製して、窒素をバブリングしながら300Kで紫外光を照射したところ、図4に示すようにピーク波長が512nmの蛍光が観測された。また、窒素バブル前後に小型蛍光寿命測定装置(浜松ホトニクス(株)製Quantaurus-tau)による測定を行って、図5に示す過渡減衰曲線を得た。この過渡減衰曲線は、化合物に励起光を当てて発光強度が失活してゆく過程を測定した発光寿命測定結果を示すものである。通常の一成分の発光(蛍光もしくはリン光)では発光強度は単一指数関数的に減衰する。これは、グラフの縦軸がセミlog である場合には、直線的に減衰することを意味している。図5に示す化合物1の過渡減衰曲線では、観測初期にこのような直線的成分(蛍光)が観測されているが、数μ秒以降には直線性から外れる成分が現れている。これは遅延成分の発光であり、初期の成分と加算される信号は、長時間側に裾をひくゆるい曲線になる。このように発光寿命を測定することによって、化合物1は蛍光成分のほかに遅延成分を含む発光体であることが確認された。すなわち、化合物1のトルエン溶液において、励起寿命が0.013μsの短寿命成分と、39μsの長寿命成分が観測された。化合物1のトルエン溶液中でのフォトルミネッセンス量子効率を絶対PL量子収率測定装置(浜松ホトニクス(株)製Quantaurus-QY)により300Kで測定したところ、窒素バブル前が16.0%であり、窒素バブル後が33.4%であった。
同様にして、化合物1のかわりに合成例2で合成した化合物2を用いてトルエン溶液の作製と評価を行った。図6にピーク波長が503nmの発光スペクトルを示し、図7に窒素バブル後の過渡減衰曲線を示す。励起寿命が0.012μsの短寿命成分と、140μsの長寿命成分が観測された。フォトルミネッセンス量子効率は、窒素バブル前が17.5%であり、窒素バブル後が24.7%であった。
同様にして、化合物3を用いてトルエン溶液の作製と評価を行った。図8にピーク波長が468nmの発光スペクトルを示し、図9に窒素バブル後の過渡減衰曲線を示す。励起寿命が0.01μsの短寿命成分と、490μsの長寿命成分が観測された。フォトルミネッセンス量子効率は、窒素バブル前が14.1%であり、窒素バブル後が21.1%であった。
実施例1と同様にして、下記の構造を有する比較化合物のトルエン溶液を作成した。窒素バブリング前後の過渡減衰曲線は、図10に示すように重なっていた。窒素バブリング後に明確な遅延蛍光が確認できなかったため、比較化合物は遅延蛍光体ではないことが確認された。
シリコン基板上に真空蒸着法にて、真空度5.0×10-4Paの条件にて化合物1とCBPとを異なる蒸着源から蒸着し、化合物1の濃度が6.0重量%である薄膜を0.3nm/秒にて100nmの厚さで形成して薄膜型有機フォトルミネッセンス素子とした。実施例1と同じ測定装置を用いて測定したところ、ピーク波長が504nmの発光スペクトルを得た(図11)。フォトルミネッセンス量子効率は300Kで62.0%であった。実施例1と同じ測定装置を用いて励起子の寿命を測定したところ、図12に示す過渡減衰曲線を得た。短寿命成分は0.013μsであり、長寿命成分は576μsであった。
同様にして、化合物2を用いて薄膜を形成して評価したところ、ピーク波長が498nmの発光スペクトルを得て(図13)、図14に示す過渡減衰曲線を得た。フォトルミネッセンス量子効率は300Kで65.0%であった。短寿命成分は0.013μsであり、長寿命成分は300μsであった。
同様にして、化合物3を用いて薄膜を形成して評価したところ、ピーク波長が469nmの発光スペクトルを得て(図15)、図16に示す過渡減衰曲線を得た。フォトルミネッセンス量子効率は300Kで35%であった。短寿命成分は0.013μsであり、長寿命成分は462μsであった。
膜厚100nmのインジウム・スズ酸化物(ITO)からなる陽極が形成されたガラス基板上に、各薄膜を真空蒸着法にて、真空度5.0×10-4Paで積層した。まず、ITO上にα-NPDを35nmの厚さに形成した。次に、化合物1とCBPを異なる蒸着源から共蒸着し、15nmの厚さの層を形成して発光層とした。この時、化合物1の濃度は6.0重量%とした。次に、TPBiを65nmの厚さに形成し、さらにフッ化リチウム(LiF)を0.8nm真空蒸着し、次いでアルミニウム(Al)を80nmの厚さに蒸着することにより陰極を形成し、有機エレクトロルミネッセンス素子とした。
製造した有機エレクトロルミネッセンス素子を、半導体パラメータ・アナライザ(アジレント・テクノロジー社製:E5273A)、光パワーメータ測定装置(ニューポート社製:1930C)、および光学分光器(オーシャンオプティクス社製:USB2000)を用いて測定したところ、図17に示すようにピーク波長が508nmの発光が認められた。電流密度-電圧特性を図18に示し、電流密度-外部量子効率特性を図19に示す。化合物1を発光材料として用いた有機エレクトロルミネッセンス素子は10.29%の高い外部量子効率を達成した。仮に発光量子効率が100%の蛍光材料を用いてバランスの取れた理想的な有機エレクトロルミネッセンス素子を試作したとすると、光取り出し効率が20~30%であれば、蛍光発光の外部量子効率は5~7.5%となる。この値が一般に、蛍光材料を用いた有機エレクトロルミネッセンス素子の外部量子効率の理論限界値とされている。化合物1を用いた本発明の有機エレクトロルミネッセンス素子は、理論限界値を超える高い外部量子効率を実現している点で極めて優れている。
同様にして、化合物2を用いて有機エレクトロルミネッセンス素子を作製して評価したところ、図20に示すようにピーク波長が504nmの発光が認められた。電流密度-電圧特性を図21に示し、電流密度-外部量子効率特性を図22に示す。化合物2を発光材料として用いた有機エレクトロルミネッセンス素子は6.31%の高い外部量子効率を達成した。
2 陽極
3 正孔注入層
4 正孔輸送層
5 発光層
6 電子輸送層
7 陰極
Claims (11)
- XがOまたはSであることを特徴とする請求項1~3のいずれか1項に記載の発光材料。
- YがO、SまたはN-R16であって、R16が置換もしくは無置換のアリール基であることを特徴とする請求項1~4のいずれか1項に記載の発光材料。
- R1~R8が、各々独立に水素原子、フッ素原子、塩素原子、シアノ基、炭素数1~10の置換もしくは無置換のアルキル基、炭素数1~10の置換もしくは無置換のアルコキシ基、炭素数1~10の置換もしくは無置換のジアルキルアミノ基、炭素数12~40の置換もしくは無置換のジアリールアミノ基、炭素数6~15の置換もしくは無置換のアリール基、または炭素数3~12の置換もしくは無置換のヘテロアリール基であることを特徴とする請求項1~5のいずれか1項に記載の発光材料。
- 請求項1~6のいずれか1項に記載の発光材料からなる遅延蛍光体。
- 請求項1~6のいずれか1項に記載の発光材料を含む発光層を基板上に有することを特徴とする有機発光素子。
- 遅延蛍光を放射することを特徴とする請求項9に記載の有機発光素子。
- 有機エレクトロルミネッセンス素子であることを特徴とする請求項9または10に記載の有機発光素子。
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Also Published As
Publication number | Publication date |
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JPWO2014034535A1 (ja) | 2016-08-08 |
TW201416411A (zh) | 2014-05-01 |
US20150239880A1 (en) | 2015-08-27 |
KR20150050570A (ko) | 2015-05-08 |
JP6225111B2 (ja) | 2017-11-01 |
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