WO2014126200A1 - 化合物、発光材料および有機発光素子 - Google Patents
化合物、発光材料および有機発光素子 Download PDFInfo
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- WO2014126200A1 WO2014126200A1 PCT/JP2014/053477 JP2014053477W WO2014126200A1 WO 2014126200 A1 WO2014126200 A1 WO 2014126200A1 JP 2014053477 W JP2014053477 W JP 2014053477W WO 2014126200 A1 WO2014126200 A1 WO 2014126200A1
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- 0 CC1=C*(C)=CCC1 Chemical compound CC1=C*(C)=CCC1 0.000 description 6
- ZAILPLDEITWEQH-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1Oc(cc1)ccc1N(C(c1c2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3)cc(C(N4C(C)(C)N[IH]c(cc5)ccc5Oc(cc5)ccc5N(C(c(c5c6)cc(C(N7C(C)=C)=O)c6C7=O)=O)C5=O)=O)c3C4=O)cc1)=O)C2=O Chemical compound CC(C)(C)c(cc1)ccc1Oc(cc1)ccc1N(C(c1c2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3)cc(C(N4C(C)(C)N[IH]c(cc5)ccc5Oc(cc5)ccc5N(C(c(c5c6)cc(C(N7C(C)=C)=O)c6C7=O)=O)C5=O)=O)c3C4=O)cc1)=O)C2=O ZAILPLDEITWEQH-UHFFFAOYSA-N 0.000 description 1
- DPYROBMRMXHROQ-UHFFFAOYSA-N Nc(c(O)c1)cc(N)c1O Chemical compound Nc(c(O)c1)cc(N)c1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N c1ccc2Oc3ccccc3Nc2c1 Chemical compound c1ccc2Oc3ccccc3Nc2c1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
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- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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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.
- 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.
- studies on organic electroluminescence devices using compounds containing a heteroaromatic ring have been found, and some proposals have been made so far.
- Patent Document 1 describes that a compound represented by the following general formula [I] or general formula [II] is used in an organic layer existing between a pair of electrodes constituting an organic electroluminescence element.
- X 1 and X 2 represent N or CH
- Y 1 and Y 2 are S, O
- NZ Z is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic ring
- R 1 to R 4 represent a hydrogen atom, halogen atom, cyano group, nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, cycloalkyl group, aryl group, complex It is defined to represent a cyclic group, an amino group, an alkylamino group, or an arylamino group.
- Patent Document 1 the compound represented by the above general formula [I] or [II] is used as a fluorescent light emitting material in the light emitting layer, or as a carrier transport material in the hole injection layer or the electron injection layer. It is described that it can be done.
- Patent Document 1 exemplifies compounds having a wide variety of structures as specific examples of the compounds represented by the above general formula [I] and general formula [II], and includes the following structures: Also exemplified is Compound A having
- Patent Document 2 describes that, in an organic electroluminescence device using a phosphorescent material, a compound included in the above general formula [I] or general formula [II] is used in an organic layer. Also in patent document 2, the compound A is described as an exemplary compound, and is used for the positive hole transport layer in the Example.
- Patent Document 1 and Patent Document 2 do not have a description that suggests a relationship between the light emission efficiency as a light emitting material and the structure of a similar compound. For this reason, it is very difficult to accurately predict what kind of property a compound having a structure similar to the compound whose effect has been confirmed in Patent Document 1 and Patent Document 2 will exhibit. Further, the compound A, whose structure is specifically shown in Patent Document 1 and Patent Document 2, has room for improvement in terms of light emission efficiency, but what structure can be used to improve light emission efficiency? Nothing is suggested in Patent Literature 1 and Patent Literature 2 regarding this point.
- the present inventors succeeded in synthesizing a compound group having a specific structure, and these compound groups have excellent properties as light emitting materials. I found out. 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 compound represented by the following general formula (1) [1] A compound represented by the following general formula (1).
- General formula (1) D-A-D [In the general formula (1), A represents the following general formulas (2) to (5): A divalent group having a structure represented by any one of the formulas (wherein a hydrogen atom in the structures of the general formulas (2) to (5) may be substituted with a substituent), Independently the following groups: Represents a group having a structure selected from: (wherein a hydrogen atom in the structure may be substituted with a substituent). ]
- a luminescent material comprising the compound according to any one of [1] to [5].
- a delayed phosphor having a structure represented by the general formula (1).
- An organic light emitting device comprising a light emitting layer containing the light emitting material according to [6] on a substrate.
- the organic light-emitting device according to [8] which emits delayed fluorescence.
- the organic light-emitting device according to [8] or [9] which is an organic electroluminescence device.
- 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.
- 1 is a 1 H NMR spectrum of Compound 1.
- 2 is a mass spectrum of Compound 1.
- 1 is a 1 H NMR spectrum of Compound 3.
- 3 is a mass spectrum of Compound 3.
- 1 is a 1 H NMR spectrum of Compound 4.
- 4 is a mass spectrum of Compound 4.
- 2 is an emission spectrum of an organic photoluminescence device using Compound 1.
- 2 is a transient decay curve of an organic photoluminescence device using Compound 1.
- 2 is an emission spectrum of an organic photoluminescence device using Compound 3.
- 4 is a transient decay curve of an organic photoluminescence device using Compound 3.
- 2 is an emission spectrum of an organic photoluminescence device using Compound 4.
- 4 is a transient decay curve of an organic photoluminescence device using Compound 4.
- 2 is an emission spectrum of an organic electroluminescence device using Compound 1.
- 2 is a graph showing current density-external quantum efficiency characteristics of an organic electroluminescence device using Compound 1.
- 2 is an emission spectrum of an organic electroluminescence device using Compound 3.
- 5 is a graph showing current density-external quantum efficiency characteristics of an organic electroluminescence device using Compound 3.
- 2 is an emission spectrum of an organic electroluminescence device using Compound 4.
- 6 is a graph showing current density-external quantum efficiency characteristics of an organic electroluminescence device using Compound 4.
- 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.
- A represents a divalent group having a structure represented by any of the following general formulas (2) to (5).
- the hydrogen atom present in the above structure may be substituted with a substituent.
- the number of substituents is not particularly limited, and the substituents may not be present. When two or more substituents are present, these substituents may be the same as or different from each other.
- substituents examples include a hydroxy group, a halogen atom, 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, an aryl group having 6 to 40 carbon atoms, and a carbon number.
- Examples thereof include 20 trialkylsilylalkyl groups, 5 to 20 trialkylsilylalkenyl groups, and 5 to 20 trialkylsilylalkynyl groups.
- those that can be substituted with a substituent may be further substituted.
- substituents are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted groups having 3 to 40 carbon atoms. Or it is an unsubstituted heteroaryl group.
- Further preferred substituents are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 15 carbon atoms, 3 to 12 substituted or unsubstituted heteroaryl groups.
- the alkyl group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and tert-butyl. Group, pentyl group, hexyl group and isopropyl group.
- the alkoxy group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group. A group, a pentyloxy group, a hexyloxy group, and an isopropyloxy group.
- the aryl group that can be employed as the substituent may be a single ring or a condensed ring, and specific examples thereof include a phenyl group and a naphthyl group.
- the heteroaryl group may be a single ring or a condensed ring, and specific examples thereof 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 bonding position of D bonded to the rightmost benzene ring in the general formulas (2) to (5) may be any of the ortho, meta, and para positions. Further, the bonding position of D bonded to the leftmost benzene ring in the general formulas (2) to (5) may be any of the ortho, meta, and para positions. Preferred is the meta or para position, and most preferred is the para position.
- a in the general formula (1) is preferably a group having a structure represented by any of the following general formulas (6) to (9).
- R 1 to R 10 each independently represents a hydrogen atom or a substituent.
- R 1 to R 10 may all be hydrogen atoms. Moreover, when two or more are substituents, those substituents may be the same or different.
- R 1 to R 10 can take, reference can be made to the explanation and preferred ranges of the substituents that A can take in the general formula (1).
- 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 , and R 7 and R 8 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.
- Preferable examples of the structures represented by the general formulas (6) to (9) include structures in which R 1 to R 10 are all hydrogen atoms.
- a line-symmetric structure in which R 1 and R 8 , R 2 and R 7 , R 3 and R 6 , R 4 and R 5 , and R 9 and R 10 are the same can also be given.
- Two Ds in the general formula (1) each independently represent a group having a structure selected from the following group.
- the hydrogen atom present in the structure described in the above group may be substituted with a substituent.
- a hydrogen atom bonded to a ring skeleton constituent atom may be substituted with a substituent.
- the number of substituents is not particularly limited, and the substituents may not be present. When two or more substituents are present, these substituents may be the same as or different from each other.
- Examples of the substituent that can substitute a hydrogen atom present in the structure described in the above group include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
- alkylthio group having 1 to 20 carbon atoms an alkyl-substituted amino group having 1 to 20 carbon atoms, an aryl-substituted amino group having 12 to 40 carbon atoms, an acyl group having 2 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, Heteroaryl group having 3 to 40 carbon atoms, substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxycarbonyl having 2 to 10 carbon atoms Group, alkylsulfonyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, amide group, alkylamide group having 2 to 10 carbon atoms, tria having 3 to 20 carbon atoms Kirushiriru group, trialkylsilyl group having 4-20 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 hydrogen atoms bonded to adjacent ring skeleton atoms present in the structure described in the above group 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.
- D in the general formula (1) is preferably a group having a structure represented by any of the following general formulas (10) to (12).
- R 11 to R 18 and R 21 to R 25 each independently represent a hydrogen atom or a substituent.
- R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 21 and R 22 , R 22 and R 23 , R 23 And R 24 , and R 24 and R 25 may be bonded to each other to form a cyclic structure.
- the two Ds in the general formula (1) may be the same or different, but preferably have the same structure. It is also preferred that A in the general formula (1) has a symmetric structure, two Ds are the same, and the whole molecule has a symmetric structure.
- Ordinary luminescent materials have an AD structure in which A acting as an acceptor and D acting as a donor are combined.
- the compound represented by the general formula (1) has a structure of DAD, and two D acting as donors are bonded to A acting as an acceptor. .
- DAD double dioxide
- the function as a donor is canceled out, and there is a risk that the molecule does not function effectively as a light emitting material.
- a combination of A and D in the general formula (1) can be arbitrarily selected.
- A is a group having a structure represented by the general formula (6), and D is represented by the general formula (11).
- a compound which is a group having a structure A is a group having a structure represented by the general formula (7), and D is a group having a structure represented by the general formula (11)
- A is a general formula A group having a structure represented by (8), wherein D is a group having a structure represented by the general formula (11), and A is a group having a structure represented by the general formula (9)
- D is a compound having a structure represented by the general formula (11),
- A is a group having a structure represented by the general formula (6), and D is represented by the general formula (10).
- a compound having a structure represented by formula (6), wherein A is a group having a structure represented by formula (6), and D is represented by formula (12) That like compound is a group having the structure, and the like are preferable
- 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 repeating unit is prepared by preparing a monomer containing a polymerizable functional group in either A or D of the general formula (1) and polymerizing the monomer alone or copolymerizing with another monomer. It is conceivable to obtain a polymer having the above and use the polymer as a light emitting material.
- 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 the structure represented by the general formula (1) a polymer including a structure represented by the following general formula (13) or (14) 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 A or D in the structure of the general formula (1) constituting Q, R 1 to R 10 in the structures of the general formulas (6) to (9), the general formula ( It can be bonded to any one of R 11 to R 18 and R 21 to R 28 of the structures 10) to (12). 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 either A or D of the structure of the general formula (1), and the following compounds are used as linkers: It can be synthesized by reacting to introduce a polymerizable group and polymerizing the polymerizable group.
- the polymer containing a structure represented by the general formula (1) in the molecule may be a polymer consisting only of a repeating unit 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.
- the compound represented by the general formula (1) can be synthesized by combining known reactions. For example, it can be synthesized according to the following scheme.
- D and A in the above formula the corresponding description in the general formula (1) can be referred to.
- X in the above formula represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom and an iodine atom are preferable.
- A is a group having a structure represented by the general formula (6)
- D is a group having a structure represented by the general formula (11).
- the compound can be synthesized according to the following scheme.
- R 1 to R 18 in the above formula the corresponding descriptions in the general formula (6) and the general formula (11) can be referred to.
- X in the above formula represents a halogen atom.
- the reactions in the above two schemes apply known reactions, 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 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.
- 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, R ′, and R 1 to R 10 each independently represent a hydrogen atom or a substituent.
- 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.
- 2,5-diaminobenzene-1,4-dithiol dihydrochloride (2.0 g, 8.2 mmol) and 4-bromobenzoic acid (3.8 g, 18.8 mmol) were charged into a 100 ml two-necked flask.
- 30 ml of polyphosphoric acid was added and heated and stirred at 100 ° C. for 30 hours. After the reaction, heating was stopped and the reaction solution was cooled to room temperature, and then the reaction product was put into a mixed solution of 300 ml of water and 300 ml of chloroform.
- FIG. 2 shows a 1 H-NMR spectrum (CDCl 3 , 500 MHz), and FIG. 3 shows a mass spectrum.
- a 100 ml two-necked flask was charged with 1.5 g (7.0 mmol) of 4,6-diaminohydroquinone dihydrochloride, 3.3 g (16.4 mmol) of 4-bromobenzoic acid, and 30 ml of polyphosphoric acid, and heated at 100 ° C. for 72 hours. , Stirred. After stopping the heating and cooling to room temperature, the reaction product was put into a mixed solution of 300 ml of water and 300 ml of chloroform, and then the organic phase and the aqueous phase were separated with a separatory funnel. After the organic phase was dried and concentrated, 100 ml of methanol was added to precipitate a solid content.
- FIG. 4 shows a 1 H-NMR spectrum (CDCl 3 , 500 MHz), and FIG. 5 shows a mass spectrum.
- a 100 ml two-necked flask was charged with 1.5 g (7.0 mmol) of 44,6-diaminoresorcinol dihydrochloride, 3.3 g (16.4 mmol) of 4-bromobenzoic acid, and 20 ml of polyphosphoric acid. Heated and stirred. After stopping the heating and cooling to room temperature, the reaction product was put into a mixed solution of 300 ml of water and 300 ml of chloroform, and then the organic phase and the aqueous phase were separated with a separatory funnel. After the organic phase was dried and concentrated, 100 ml of methanol was added to precipitate a solid content.
- FIG. 6 shows a 1 H-NMR spectrum (CDCl 3 , 500 MHz), and FIG. 7 shows a mass spectrum.
- Example 1 Preparation and evaluation of organic photoluminescence device (thin film) A thin film in which Compound 1 and CBP are deposited from different deposition sources on a silicon substrate by a vacuum deposition method under a vacuum degree of 5.0 ⁇ 10 ⁇ 4 Pa, and the concentration of Compound 1 is 6.0% by weight. was formed at a thickness of 100 nm at 0.3 nm / second to obtain an organic photoluminescence device.
- An organic photoluminescence device was produced in the same manner using Compound 3 instead of Compound 1.
- An emission spectrum by 330 nm excitation light is shown in FIG. 10, and a transient decay curve is shown in FIG.
- the photoluminescence quantum efficiency was measured at 300K, it was 21% in the air and 60% in a nitrogen atmosphere.
- An organic photoluminescence device was produced in the same manner using Compound 4 instead of Compound 1.
- the emission spectrum by 330 nm excitation light is shown in FIG. 12, and the transient decay curve is shown in FIG.
- the photoluminescence quantum efficiency was measured at 300 K, it was 84% in the air and 98% in a nitrogen atmosphere.
- Example 2 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 measurement 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 13.5%. Since the photoluminescence quantum efficiency using Compound 1 as the light-emitting material was 78%, the singlet exciton generation probability is calculated as 87% (calculated assuming that the light extraction efficiency is 20% and the recombination probability is 100%). . 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 (13.5%) exceeding the theoretical limit value is realized.
- An organic electroluminescence device was produced by the same method using Compound 3 instead of Compound 1 and mCBP instead of CBP.
- the emission spectrum is shown in FIG. 16, and the current density-external quantum efficiency characteristic is shown in FIG.
- the organic electroluminescence device using Compound 3 as the light emitting material achieved a high external quantum efficiency of 13.3%. Since the photoluminescence quantum efficiency using Compound 3 as the light-emitting material was 81%, the singlet exciton generation probability is calculated as 82% (calculated assuming that the light extraction efficiency is 20% and the recombination probability is 100%). .
- An organic electroluminescence device was produced by the same method using Compound 4 instead of Compound 1 and mCBP instead of CBP.
- the emission spectrum is shown in FIG. 18, and the current density-external quantum efficiency characteristic is shown in FIG.
- the organic electroluminescence device using Compound 4 as the light emitting material achieved a high external quantum efficiency of 16.4%. Since the photoluminescence quantum efficiency using Compound 4 as a light-emitting material was 98%, the singlet exciton generation probability is calculated as 84% (calculated assuming that the light extraction efficiency is 20% and the recombination probability is 100%). .
- 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
Description
一般式(1)
D-A-D
[一般式(1)において、Aは下記一般式(2)~(5):
[4] 一般式(1)のDが下記一般式(10)~(12)のいずれかで表される構造を有することを特徴とする[1]~[3]のいずれか1項に記載の化合物。
[5] Dが一般式(11)で表される構造を有することを特徴とする[4]に記載の化合物。
[7] 上記一般式(1)で表される構造を有する遅延蛍光体。
[8] [6]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。
[9] 遅延蛍光を放射することを特徴とする[8]に記載の有機発光素子。
[10] 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[8]または[9]に記載の有機発光素子。
本発明の化合物は、下記一般式(1)で表される構造を有することを特徴とする。
一般式(1)
D-A-D
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AかD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反応させることにより、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(13)および(14)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AかD、一般式(6)~(9)の構造のR1~R10、一般式(10)~(12)の構造のR11~R18、R21~R28のいずれかに結合することができる。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合成することが可能である。
一般式(1)で表される化合物のうち、例えばAが一般式(6)で表される構造を有する基であって、Dが一般式(11)で表される構造を有する基である化合物は以下のスキームにより合成することが可能である。
上記の2つのスキームにおける反応は、公知の反応を応用したものであり、公知の反応条件を適宜選択して用いることができる。上記の反応の詳細については、後述の合成例を参考にすることができる。また、一般式(1)で表される化合物は、その他の公知の合成反応を組み合わせることによっても合成することができる。
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。すなわち本発明は、一般式(1)で表される構造を有する遅延蛍光体の発明と、一般式(1)で表される化合物を遅延蛍光体として使用する発明と、一般式(1)で表される化合物を用いて遅延蛍光を発光させる方法の発明も提供する。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。
有機フォトルミネッセンス素子は、基板上に少なくとも発光層を形成した構造を有する。また、有機エレクトロルミネッセンス素子は、少なくとも陽極、陰極、および陽極と陰極の間に有機層を形成した構造を有する。有機層は、少なくとも発光層を含むものであり、発光層のみからなるものであってもよいし、発光層の他に1層以上の有機層を有するものであってもよい。そのような他の有機層として、正孔輸送層、正孔注入層、電子阻止層、正孔阻止層、電子注入層、電子輸送層、励起子阻止層などを挙げることができる。正孔輸送層は正孔注入機能を有した正孔注入輸送層でもよく、電子輸送層は電子注入機能を有した電子注入輸送層でもよい。具体的な有機エレクトロルミネッセンス素子の構造例を図1に示す。図1において、1は基板、2は陽極、3は正孔注入層、4は正孔輸送層、5は発光層、6は電子輸送層、7は陰極を表わす。
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。
得られたジブロモ体の一部0.71g(1.4mmol)とフェノキサジン0.65g(3.5mmol)、炭酸カリウム0.59g(4.3mmol)を窒素置換した50ml二口フラスコに投入した。この反応器中へ酢酸パラジウム0.032g(0.14mmol)とトリーtert―ブチルホスフィン0.029g(0.14mmol)を高純度窒素ガスで脱気処理した脱水トルエン10mlに溶解した混合液を滴下し、窒素雰囲気下80℃で24時間加熱、攪拌した。反応終了後、この反応物に水300mlとクロロホルム300mlを入れ、有機相と水相を分離した。有機相を濃縮したのち、メタノールを100ml加えて10分間超音波照射して固形分を析出させた。析出固形物を吸引濾過して乾燥させた後に、得られた粉末を370℃で昇華精製して化合物1の黄色粉末0.12gを得た(収率12%)。図2に1H-NMRスペクトル(CDCl3,500MHz)、図3にマススペクトルを示す。
得られたジブロモ体の一部0.70g(1.5mmol)とフェノキサジン0.60g(3.3mmol)、炭酸カリウム1.23g(9.9mmol)を窒素置換した200ml二口フラスコに入れた。この反応器へ酢酸パラジウム0.033g(0.15mmol)、トリーtert―ブチルホスフィン0.030g(0.15mmol)を高純度窒素ガスで脱気処理した脱水トルエン50mlに溶解して滴下して窒素雰囲気下80℃で48時間加熱、攪拌した。
反応終了後、この反応物を水300ml、クロロホルム300mlの混合溶液を入れて分液ロートで有機相と水相を分離した。有機相を濃縮、乾固した後にメタノールを100ml加えて10分間超音波処理して固形分を析出させた。析出した固形分を濾過、乾燥させ、得られた粉末を350℃で昇華精製して化合物3の0.57gを黄色針状結晶として得た(収率57%)。図4に1H-NMRスペクトル(CDCl3,500MHz)、図5にマススペクトルを示す。
得られたジブロモ体の一部0.70g(1.5mmol)とフェノキサジン0.60g(3.3mmol)、炭酸カリウム1.23g(9.9mmol)を窒素置換した200ml二口フラスコに入れた。この反応器へ酢酸パラジウム0.033g(0.15mmol)、トリーtert―ブチルホスフィン0.030g(0.15mmol)を高純度窒素ガスで脱気処理した脱水トルエン50mlに溶解して滴下して窒素雰囲気下80℃で48時間加熱、攪拌した。
反応終了後、この反応物を水300ml、クロロホルム300mlの混合溶液を入れて分液ロートで有機相と水相を分離した。有機相を濃縮、乾固した後にメタノールを100ml加えて10分間超音波処理して固形分を析出させた。析出した固形分を濾過、乾燥させ、得られた粉末を350℃で昇華精製して化合物4の0.28gを黄色針状結晶として得た(収率28%)。図6に1H-NMRスペクトル(CDCl3,500MHz)、図7にマススペクトルを示す。
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の厚さで形成して有機フォトルミネッセンス素子とした。
作製した有機フォトルミネッセンス素子について、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)、光学分光器(オーシャンオプティクス社製:USB2000)およびストリークカメラ(浜松ホトニクス(株)製C4334型)を用いて測定を行った。330nm励起光による発光スペクトルを図8に示し、過渡減衰曲線を図9に示す。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。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。
フォトルミネッセンス量子効率を300Kで測定したところ、大気中で60%、窒素雰囲気下で78%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。発光スペクトルを図14に示し、電流密度-外部量子効率特性を図15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13.5%の高い外部量子効率を達成した。化合物1を発光材料として用いたフォトルミネッセンス量子効率が78%であったことから、1重項励起子生成確率は87%と計算される(光取り出し効率20%、再結合確率100%として計算)。
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(13.5%)を実現している点で極めて優れている。
6-31G))を用いて計算した結果を表1に示す。この結果、化合物Aは、実施例の化合物に比べて大きな■EST値を持つことから、発光能力が低いことは明らかである。
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 (10)
- 一般式(1)の2つのDが同一の構造を有することを特徴とする請求項1または2に記載の化合物。
- Dが一般式(11)で表される構造を有することを特徴とする請求項4に記載の化合物。
- 請求項1~5のいずれか1項に記載の化合物からなる発光材料。
- 請求項6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8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8または9に記載の有機発光素子。
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CN201480008866.5A CN105073756B (zh) | 2013-02-18 | 2014-02-14 | 化合物、发光材料及有机发光元件 |
KR1020157025871A KR102167463B1 (ko) | 2013-02-18 | 2014-02-14 | 화합물, 발광 재료 및 유기 발광 소자 |
US14/768,507 US9793492B2 (en) | 2013-02-18 | 2014-02-14 | Compound, light emitter, and organic light emitting device |
JP2015500308A JP6262711B2 (ja) | 2013-02-18 | 2014-02-14 | 化合物、発光材料および有機発光素子 |
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JP (1) | JP6262711B2 (ja) |
KR (1) | KR102167463B1 (ja) |
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Also Published As
Publication number | Publication date |
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KR102167463B1 (ko) | 2020-10-19 |
TWI641612B (zh) | 2018-11-21 |
TW201439097A (zh) | 2014-10-16 |
US9793492B2 (en) | 2017-10-17 |
JP6262711B2 (ja) | 2018-01-17 |
JPWO2014126200A1 (ja) | 2017-02-02 |
CN105073756A (zh) | 2015-11-18 |
US20160005978A1 (en) | 2016-01-07 |
KR20150120489A (ko) | 2015-10-27 |
CN105073756B (zh) | 2018-01-02 |
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