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WO2015137136A1 - Matériau électroluminescent et élément organique électroluminescent (el) l'utilisant - Google Patents

Matériau électroluminescent et élément organique électroluminescent (el) l'utilisant Download PDF

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WO2015137136A1
WO2015137136A1 PCT/JP2015/055582 JP2015055582W WO2015137136A1 WO 2015137136 A1 WO2015137136 A1 WO 2015137136A1 JP 2015055582 W JP2015055582 W JP 2015055582W WO 2015137136 A1 WO2015137136 A1 WO 2015137136A1
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light emitting
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哲二 早野
安達　千波矢
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Kyushu University NUC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/20—Delayed fluorescence emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a light emitting material having high luminous efficiency and an organic electroluminescence (EL) element using the same.
  • the organic EL element includes at least one light emitting layer between a pair of electrodes including an anode and a cathode.
  • a voltage is applied to the organic EL element, holes from the anode and electrons from the cathode are injected into the light emitting layer. The injected holes and electrons are recombined in the light emitting layer.
  • the light-emitting layer contains a host material and a dopant material
  • recombination of holes and electrons mainly occurs in the host material, and the host material transitions from the ground state (S 0 state) to the excited state.
  • S 0 state ground state
  • T 1 state triplet lowest excited state
  • the value of the host material follows the abundance ratio between the S 1 state and the T 1 state. That is, 25% of the dopant material that has reached the excited state is in the S 1 state and 75% is in the T 1 state.
  • the fluorescent material emits fluorescence during the transition from the S 1 state to the S 0 state. Therefore, in principle, a fluorescent material, can contribute only 25% in the S 1 state into luminescence.
  • phosphorescence is light emission at the transition from the T 1 state to the S 0 state.
  • the internal quantum yield can be increased to 100%. For this reason, phosphorescent organic EL light emitting devices have been actively developed, and new dopant materials and host materials have been found.
  • an iridium complex, a platinum complex, or the like is used as the phosphorescent dopant material of the light emitting layer.
  • the host material needs to have a larger T 1 -S 0 energy gap than the dopant material, and carbazole derivatives such as 4,4′-dicarbazole biphenyl (CBP) are widely used.
  • Patent Document 1 proposes to use, as a phosphorescent host material, a bipolar compound in which a carbazolyl group as an electron withdrawing site and a heteroarylene group as an electron transporting site are bonded. It is disclosed that this phosphorescent organic EL device is excellent in external quantum yield at a low driving voltage.
  • Patent Document 2 proposes to use a bipolar compound in which a carbazolyl group and a cyano-substituted arylene group or a cyano-substituted heteroarylene group are bonded as a phosphorescent host material.
  • an organic EL element using phosphorescence can achieve high luminous efficiency.
  • most of dopant materials that emit phosphorescence with high efficiency are metal complex compounds containing noble metals such as iridium and platinum, and the material cost is extremely high. That is a problem.
  • thermally activated delayed fluorescent material has a small difference ⁇ E ST between S 1 energy and T 1 energy, a state transition from the T 1 state to the S 1 state (reverse intersystem crossing) occurs due to the thermal energy.
  • reverse intersystem crossing due to thermal energy fluorescence is emitted from the T 1 state via the S 1 state, so that an internal quantum yield of more than 25% can be achieved. It is also possible to increase to%.
  • Non-Patent Document 1 and Patent Document 3 show that a specific cyanobenzene derivative in which an electron-donating carbazolyl group is bonded to an electron-withdrawing dicyanobenzene is useful as a thermally activated delayed fluorescent material.
  • an organic EL device using 1,2,3,5-tetrakis (9-carbazolyl) -4,6-dicyanobenzene (4CzIPN) as a thermally activated delayed fluorescent material is electrically excited. It is reported that it is essentially stable below and has a durable life comparable to conventional phosphorescent organic EL devices.
  • Thermally activated thermally activated delayed fluorescent materials are attracting attention as organic EL materials with high efficiency and long durability life. As described above, heat activated delayed fluorescent material is required to be Delta] E ST is small. In general, a compound having a small ⁇ E ST tends to have a small emission quantum yield. In Non-Patent Document 1, by steric hindrance of the dicyanobenzene and the electron donating carbazolyl group electron withdrawing, to both the ⁇ -conjugated system is present non-parallel, the low Delta] E ST and high quantum yield It is described that it is compatible.
  • an object of the present invention is to provide a material useful as a light-emitting material of an organic EL element, particularly a thermally activated delayed fluorescent material, and an organic EL element using the material.
  • the present invention relates to a light emitting material comprising a compound represented by the following general formula (I).
  • m and n are each independently an integer of 1 to 3, and m + n is 2 to 4.
  • A is a substituted heteroaryl group having an electron donating property, and at least one of the substituents on the aromatic heterocyclic ring is an electron withdrawing group.
  • m is 2 or more, each A may be the same or different.
  • the light emitting material of the present invention is preferably a light emitting material that emits delayed fluorescence, and can be used for a light emitting layer of an organic EL element.
  • At least one substituent A is preferably bonded to a carbon atom adjacent to the carbon atom to which the CN group of the pyridine ring is bonded.
  • a CN group is preferably bonded to the 4-position carbon atom of the pyridine ring.
  • the chemical shift of 1 H-NMR of the hydrogen atom bonded to the pyridine ring is preferably shifted by a low magnetic field.
  • the compound represented by the above general formula (I) and the compound in which all of the electron withdrawing groups on the aromatic heterocyclic ring of the substituent A in the above general formula (I) are substituted with hydrogen atoms The 1 H-NMR chemical shift of the hydrogen atom bonded to the former pyridine ring is 0.02 ppm lower than the 1 H-NMR chemical shift of the hydrogen atom bonded to the latter pyridine ring.
  • the magnetic field is preferably shifted.
  • At least one of the electron withdrawing groups on the aromatic heterocyclic ring of the substituent A is an electron withdrawing group having a Hammet substituent constant ⁇ p of 0.1 or more. Is preferred.
  • the electron withdrawing group a cyano group, a perfluoroalkyl group, and a heteroaryl group are preferable, and among them, a cyano group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group are preferable.
  • At least one substituent A is preferably a substituted carbazolyl group.
  • the substituted carbazolyl group is represented by A1 below.
  • R 1 to R 8 are each independently a hydrogen atom or an arbitrary substituent, and at least one of R 1 to R 8 is an electron withdrawing group.
  • the 3-position substituent R 3 is preferably an electron-attracting group.
  • the 6-position substituent R 6 of the carbazole ring is preferably a hydrogen atom or an electron-attracting group, and the 1-position, 2-position, 4-position, 5-position, 7-position and 8-position substituent R 1 , R 2 , R 4 , R 5 , R 7 and R 8 are all preferably hydrogen atoms.
  • the luminescent material of the present invention is a compound having a cyano group at the 4-position of the pyridine ring and the above substituted carbazolyl group A1 at the 3-position and 5-position in the general formula (I), that is, the following general formula (II) It is preferable that it is a compound represented by this.
  • R 9 to R 24 are each independently a hydrogen atom or an arbitrary substituent, and at least one of R 9 to R 15 and at least one of R 16 to R 24 are It is an electron withdrawing group.
  • the compound represented by the general formula (II) preferably has a 1 H-NMR chemical shift of 9.12 ppm or more of hydrogen atoms bonded to the pyridine ring (2- and 6-position hydrogen atoms).
  • the present invention relates to an organic EL element using the light emitting material.
  • the organic EL device of the present invention includes a light emitting layer containing the above light emitting material between a pair of electrodes.
  • the light emitting layer includes a dopant material and a host material, and the dopant material is preferably the above light emitting material.
  • the present invention also relates to a lighting fixture and a display device including the organic EL element.
  • the luminescent material of the present invention has a high internal quantum yield and excellent luminous efficiency.
  • the emission efficiency can be dramatically increased by the emission of delayed fluorescence.
  • FIG. 1 It is a schematic cross-sectional structure showing the structure of the organic EL element which concerns on embodiment of this invention.
  • 2 is an emission spectrum of compounds 1 to 6 in a toluene solution.
  • A is a time-resolved spectrum of fluorescence of Compound 1.
  • B is a fluorescence time-resolved spectrum of Compound 4.
  • A) is a fluorescence time-resolved spectrum of a co-deposited film using Compound 1 as a dopant.
  • (B) is a fluorescence time-resolved spectrum of a co-deposited film using Compound 4 as a dopant.
  • FIG. 4 is a characteristic diagram of an organic electroluminescence device using Compound 1, wherein (A) is an emission spectrum, (B) is a graph showing voltage-current density characteristics, and (C) is a graph showing current density-external quantum efficiency characteristics. is there.
  • FIG. 3 is a characteristic diagram of an organic electroluminescence device using Compound 2, wherein (A) is an emission spectrum, (B) is a graph showing voltage-current density characteristics, and (C) is a graph showing current density-external quantum efficiency characteristics. is there.
  • FIG. 3 is a characteristic diagram of an organic electroluminescence device using Compound 2, wherein (A) is an emission spectrum, (B) is a graph showing voltage-current density characteristics, and (C) is a graph showing current density-external quantum efficiency characteristics. is there.
  • FIG. 3 is a characteristic diagram of an organic electroluminescence device using Compound 2, wherein (A) is an emission spectrum, (B) is a graph showing voltage-current density characteristics, and (C) is
  • FIG. 4 is a characteristic diagram of an organic electroluminescence device using Compound 3, wherein (A) is an emission spectrum, (B) is a graph showing voltage-current density characteristics, and (C) is a graph showing current density-external quantum efficiency characteristics. is there.
  • FIG. 4 is a characteristic diagram of an organic electroluminescence device using Compound 4, wherein (A) is an emission spectrum, (B) is a graph showing voltage-current density characteristics, and (C) is a graph showing current density-external quantum efficiency characteristics. is there.
  • FIG. 5 is a characteristic diagram of another organic electroluminescence device using Compound 4, wherein (A) shows an emission spectrum, (B) shows a graph showing voltage-current density characteristics, and (C) shows current density-external quantum efficiency characteristics. It is a graph.
  • the luminescent material of the present invention comprises a compound represented by the following general formula (I).
  • n and n are each independently an integer of 1 to 3, and m + n is 2 to 4.
  • the substituent A is a substituted heteroaryl group having an electron donating property, and at least one of the substituents on the aromatic heterocyclic ring is an electron withdrawing group.
  • m is 2 or more, each A may be the same or different.
  • the substituted heteroaryl group having an electron donating property means a heteroaryl group having at least one substituent on an electron donating aromatic heterocycle.
  • the compound represented by the general formula (I) is a compound in which an electron-withdrawing cyanopyridine moiety and an electron-donating substituted heteroaryl moiety are bonded, that is, a bipolar compound.
  • the aromatic heterocycle of the substituent A has an electron donating property, and preferably has 5 to 30 ring atoms. From the viewpoint of enhancing the electron donating property by the heteroaryl group and causing the ⁇ -conjugated system of the pyridine ring and the ⁇ -conjugated system of the aromatic heterocyclic ring of the substituent A to exist non-parallel due to steric hindrance, the aromatic heterocycle is condensed. A ring is preferred.
  • the aromatic heterocycle is preferably a nitrogen-containing condensed polycycle.
  • the electron-donating aromatic heterocycle include condensed bicyclic rings such as indole, isoindole, thienoindole, indazole, purine, quinoline, isoquinoline; carbazole, acridine, ⁇ -carboline, acridone, perimidine, phenazine, Nanthridine, phenothiazine, phenoxazine, 1,7-phenanthroline, 1,8-phenanthroline, 1,9-phenanthroline, 1,10-phenanthroline, 2,7-phenanthroline, 2,8-phenanthroline, 2,9-phenanthroline, Examples thereof include condensed tricycles such as 3,7-phenanthroline and 3,8-phenanthroline; condensed tetracycles such as kindrin and quinindrin; condensed pentacycles such as aclindoline and the like.
  • the aromatic heterocycle of the substituent A is preferably a carbazole ring, an indole ring, a thienoindole ring, an indoline ring, an acridine ring, or a phenoxazine ring, and more preferably a carbazole ring.
  • a hetero atom (for example, nitrogen) of the substituent A is preferably bonded to a carbon atom of the pyridine ring. That is, the luminescent material of the present invention is preferably composed of a compound in which the substituent A is a substituted carbazolyl group represented by the following A1 in the general formula (I).
  • R 1 to R 8 are each independently a hydrogen atom or an arbitrary substituent, and at least one of R 1 to R 8 is an electron withdrawing group.
  • the molecular structure preferably has symmetry.
  • the following structural formulas can be exemplified as combinations of positions of substituents having a symmetrical molecular structure.
  • a plurality of A may be the same or different from each other. However, in order to improve symmetry, it is preferable that both are the same.
  • a CN group is bonded to the 4-position carbon of the pyridine ring.
  • at least one substituent A is preferably bonded to a carbon atom adjacent to the carbon atom to which the CN group is bonded.
  • the bond is twisted due to steric hindrance between the aromatic heterocycle of the substituent A and the cyano group.
  • the ⁇ -conjugated system of the aromatic heterocyclic ring exists in the same plane as the ⁇ -conjugated system of the pyridine ring. Therefore, the energy difference Delta] E ST of smaller singlet lowest excitation state (S 1 state) and the lowest triplet excited state (T 1 state), reverse intersystem crossing due to thermal energy is likely to occur.
  • Examples of the compound satisfying the combination of substituents satisfying these include compounds represented by the following structural formula.
  • the plurality of A may be the same or different.
  • the compound represented by the general formula (I) preferably has two or more substituents A.
  • the structural formula (123) satisfies all the above-described conditions and is particularly preferable as the structure of the light emitting material of the present invention.
  • the substituent A has at least one electron-donating substituent on the aromatic heterocyclic ring.
  • the electron-withdrawing substituent is a substituent that lowers the electron density of the ⁇ -conjugated system of the aromatic heterocyclic ring, and may be either aliphatic or aromatic.
  • the electron-withdrawing substituent on the aromatic heterocyclic ring of the substituent A preferably has an action of reducing the electron density of the ⁇ -conjugated system of cyanopyridine to which the substituent A is bonded. Whether or not the substituent on the aromatic heterocycle of Substituent A reduces the electron density of the ⁇ -conjugated system of cyanopyridine should be judged from the 1 H-NMR chemical shift of the hydrogen atom bonded to the pyridine ring. Can do.
  • the compound represented by the general formula (I) is compared with a compound in which all of the electron withdrawing groups on the aromatic heterocyclic ring of the substituent A of the compound are substituted with hydrogen atoms
  • the 1 H-NMR chemical shift of the hydrogen atom bonded to the pyridine ring is a low magnetic field shift (the chemical shift is large).
  • R 9 to R 24 are each independently a hydrogen atom or an arbitrary substituent, at least one of R 9 to R 16 and at least one of R 17 to R 24 are It is an electron withdrawing group.
  • the chemical shift of 1 H-NMR of the hydrogen atom bonded to the 2nd and 6th carbon atoms of the pyridine ring of the compound represented by the above general formula (II) is the same as that of the compound represented by the above general formula (II).
  • the chemical shift of 1 H-NMR of the hydrogen atom bonded to the pyridine ring of the compound represented by the general formula (I) is such that all of the electron withdrawing groups on the aromatic heterocyclic ring of the substituent A of the compound are all It is preferable that the magnetic field shift is 0.02 ppm or more lower than the 1 H-NMR chemical shift of the hydrogen atom bonded to the pyridine ring of the compound substituted with a hydrogen atom, and the magnetic field shift is 0.04 ppm or more lower than the chemical shift. More preferably, a low magnetic field shift of 0.06 ppm or more is further preferable, and a low magnetic field shift of 0.07 ppm or more is particularly preferable.
  • the chemical shift of 1 H-NMR of the hydrogen atom bonded to the pyridine ring of the compound represented by the general formula (II) is preferably 9.12 ppm or more, more preferably 9.14 ppm or more, and 9.16 ppm or more. Is more preferable, and 9.17 ppm or more is particularly preferable.
  • the compound represented by the general formula (I) by having an electron-attracting substituent on the aromatic heterocyclic substituents A, S 1 energy and the T 1 energy difference Delta] E ST is small, and The emission quantum yield tends to be high. Therefore, the compound represented by the general formula (I) has a high probability of occurrence of reverse intersystem crossing from the T 1 state to the S 1 state due to thermal energy, and is useful as a light emitting material that emits delayed fluorescence.
  • the electron withdrawing site is cyanopyridine
  • the electron withdrawing moiety is substituted when the substituent A which is the electron donating site has an electron withdrawing substituent on the aromatic heterocyclic ring.
  • electron density decreases cyano pyridine moiety is sex site, it is possible to achieve both low Delta] E st and high quantum yield.
  • the electron-withdrawing substituent preferably has a Hammet substituent constant ⁇ p greater than 0, more preferably 0.1 or more, still more preferably 0.3 or more, and 0.6 or more. Are particularly preferred. If the value of Hammet's substituent constant is positive, it indicates electron withdrawing property, and the larger the value, the stronger the electron withdrawing property. Hammet's substituent constants are described in detail in Hansch, C. et. Al., Chem. Rev., 91, 165-195. (1991).
  • the electron-withdrawing substituent include a cyano group, a phenyl group, a nitro group, an acyl group, a formyl group, an acyloxy group, an acylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a halogen atom, and at least two.
  • An alkyl group substituted with the above halogen atoms (preferably a perfluoroalkyl group substituted with two or more fluorine atoms, preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms;
  • the electron withdrawing substituents those selected from the group consisting of a cyano group, a perfluoroalkyl group (in particular, a trifluoromethyl group), and a heteroaryl group are preferable.
  • the heteroaryl group preferably has a heterocyclic structure containing a nitrogen atom or a sulfur atom as a hetero atom.
  • Specific examples of the electron withdrawing heteroaryl group include an oxadiazolyl group, a benzothiadiazolyl group, a tetrazolyl group, a thiazolyl group, an imidazolyl group, and a pyridyl group.
  • heteroaryl group either a carbon atom or a hetero atom may be bonded to an aromatic heterocycle, but from the viewpoint of enhancing electron withdrawing properties, it is preferable that a carbon atom is bonded to an aromatic heterocycle.
  • heteroaryl groups those selected from the group consisting of 2-pyridyl group, 3-pyridyl group, and 4-pyridyl group are particularly preferable.
  • the electron withdrawing group is a cyano group
  • the emission wavelength tends to be shortened. Therefore, a compound in which the electron withdrawing group on the substituent A in the general formula (I) is a cyano group is useful as a blue delayed fluorescent material.
  • the electron withdrawing group is a pyridyl group, particularly when it is a 4-pyridyl group, the emission quantum yield tends to be increased. Therefore, in the general formula (I), a compound in which the electron withdrawing group on the substituent A is a pyridyl group is useful as a delayed fluorescent material with high emission efficiency.
  • the position of the electron withdrawing group on the aromatic heterocyclic ring of the substituent A is not particularly limited.
  • the bonding position of the electron withdrawing group is determined so as to reduce the electron density of the ⁇ -conjugated system of cyanopyridine to which the substituent A is bonded, depending on the type of the aromatic heterocyclic ring of the substituent A. It is done.
  • the aromatic heterocyclic ring of the substituent A is a carbazole ring, that is, when the substituent A is the A1, the electron withdrawing substituent is present at the 3-position and / or the 6-position.
  • R 3 is preferably an electron withdrawing group.
  • R 6 is preferably an electron withdrawing group or a hydrogen atom.
  • substituents on the aromatic heterocycle of the substituent A is a hydrogen atom or an arbitrary substituent.
  • substituent other than the electron withdrawing group include a hydroxy 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 group having 1 to 20 carbon atoms.
  • Alkyl substituted amino group aryl group having 6 to 40 carbon atoms, diarylamino group having 12 to 40 carbon atoms, substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms, alkenyl group having 2 to 10 carbon atoms, carbon number 2 -10 alkynyl group, 3-20 carbon trialkylsilyl group, 4-20 carbon trialkylsilylalkyl group, 5-20 carbon trialkylsilylalkenyl group, 5-20 carbon trialkylsilyl An alkynyl group etc. are mentioned.
  • the aromatic heterocyclic ring has no substituent other than the electron-withdrawing substituent (that is, has no electron-donating substituent).
  • those other than the electron withdrawing group are preferably hydrogen atoms. That is, the substituents R 1 to R 8 are preferably electron withdrawing groups or hydrogen atoms, and at least one of R 1 to R 8 is preferably an electron withdrawing group.
  • a 1 has R 3 as an electron withdrawing group
  • R 6 has a hydrogen atom or an electron withdrawing group
  • R 1 , R 2 , R 4 , R 5 , R 7 and R 8. Are preferably hydrogen atoms.
  • the substituent A1 preferably has one of the following structures.
  • Py is a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group, and a 4-pyridyl group is particularly preferable.
  • two Py may be the same or different but are preferably the same.
  • R 9 to R 24 are hydrogen atoms other than the electron withdrawing group.
  • R 11 and R 19 are preferably electron withdrawing groups, and R 14 and R 22 are preferably hydrogen atoms or electron withdrawing groups.
  • R 11 and R 19 are electron withdrawing groups, R 14 and R 22 are hydrogen atoms or electron withdrawing groups, and R 9 , R 10 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 23 , R 24 are all preferably hydrogen atoms.
  • the compound represented by the general formula (II) is preferably any one of the following compounds.
  • Py is a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group, and a 4-pyridyl group is particularly preferable.
  • two Py may be the same or different but are preferably the same.
  • the organic EL element includes an organic layer between a pair of electrodes including an anode and a cathode, and at least one of the organic layers is a light emitting layer.
  • the light emitting material of the present invention is useful as a light emitting material for an organic EL device and can be effectively used as a material for a light emitting layer.
  • the compound represented by the general formula (I) includes a delayed fluorescent material (delayed phosphor) that emits delayed fluorescence.
  • An organic EL element using a delayed fluorescent material as a light emitting material emits delayed fluorescent light and has high luminous efficiency according to the principle described below.
  • the delayed fluorescent material a transition from a triplet excited state to a singlet excited state (reverse intersystem crossing) occurs due to triplet-triplet annihilation or absorption of thermal energy, and the singlet excited state changes to the ground state. Fluorescence is emitted during the transition. Thus, the fluorescence generated via the inverse intersystem crossing is delayed fluorescence.
  • a “thermally activated delayed fluorescent material” that causes crossing of inverse terms by absorption of thermal energy is particularly useful.
  • excitons in a singlet excited state emit fluorescence as usual.
  • excitons in the triplet excited state absorb thermal energy emitted from the device, and are excited into a singlet excited state (crossing between inverse terms) to emit fluorescence.
  • Fluorescence generated via reverse intersystem crossing is light emission from singlet excitation, and thus light emission at the same wavelength as light emission from excitons excited directly from the ground state to the singlet excitation state.
  • the lifetime of the fluorescence (light emission lifetime) generated via the crossing between inverse terms is longer than that of normal fluorescence or phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence.
  • thermally activated exciton transfer mechanism By using such a thermally activated exciton transfer mechanism, it is possible to increase the ratio of singlet excited states, which normally generate only 25%, to 25% or more by absorbing thermal energy after carrier injection. It becomes.
  • a compound that emits strong fluorescence and delayed fluorescence even at a low temperature of less than 100 ° C. the reverse intersystem crossing from the triplet excited state to the singlet excited state is sufficiently generated by the heat of the device to emit delayed fluorescence. Therefore, the light emission efficiency can be dramatically improved.
  • FIG. 1 is a schematic cross-sectional view illustrating a configuration of an organic EL element according to an embodiment.
  • This element includes an anode 2 and a cathode 4 on a substrate 1 and an organic layer 3 between the pair of electrodes. At least one of the organic layers 3 has a light emitting layer.
  • the organic layer 3 may be composed of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer.
  • the organic layer other than the light emitting layer examples 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.
  • the organic layer 3 has a hole injection layer 31 and a hole transport layer 32 on the anode 2 side of the light emitting layer 33, and an electron transport layer 34 and an electron injection on the cathode 4 side of the light emitting layer 33. It has a layer 35.
  • the organic EL element of this invention should just have a light emitting layer between a pair of electrodes, and is not limited to the structure shown in FIG. Below, each member and each layer of an organic EL element are demonstrated.
  • the organic EL element preferably has a pair of electrodes 2 and 4 and an organic layer 3 on the substrate 1.
  • the material of the substrate is not particularly limited, and is appropriately selected from, for example, a transparent substrate such as glass, a silicon substrate, a flexible film substrate, and the like.
  • the substrate preferably has a transmittance in the visible light region of 80% or more and 90% or more from the viewpoint of increasing light extraction efficiency. Further preferred.
  • the material of the anode is not particularly limited, but metals, alloys, metal oxide electrically conductive compounds and mixtures thereof having a high work function (for example, 4 eV or more) are preferably used.
  • Specific examples of the material of the anode include a metal thin film such as Au, and metal oxides such as indium / tin oxide (ITO), indium / zinc oxide (IZO), zinc oxide, and tin oxide.
  • ITO or IZO which is a highly transparent metal oxide, is preferably used from the viewpoint of improving the extraction efficiency of light generated from the light emitting layer and ease of patterning.
  • dopants such as aluminum, gallium, silicon, boron, and niobium, may be contained as needed.
  • the material of the anode is not particularly limited, but metals, alloys, metal oxides, electrically conductive compounds and mixtures thereof having a small work function (for example, 4 eV or less) are preferably used.
  • the metal having a small work function include Li for an alkali metal and Mg and Ca for an alkaline earth metal.
  • a simple metal made of rare earth metal or the like, or an alloy such as Al, In, or Ag with these metals can also be used.
  • a metal complex compound containing at least one selected from the group consisting of alkaline earth metal ions and alkali metal ions is used as the organic layer in contact with the cathode.
  • a metal capable of reducing metal ions in the complex compound to a metal in a vacuum, such as Al, Zr, Ti, Si, or an alloy containing these metals, as the cathode.
  • either the anode or the cathode is preferably light transmissive, and specifically, the transmittance in the visible light region is preferably 70% or more. % Or more is more preferable, and it is further more preferable that it is 90% or more.
  • the transmittance in the visible light region is preferably 70% or more. % Or more is more preferable, and it is further more preferable that it is 90% or more.
  • an organic EL element capable of extracting light from both the anode side and the cathode side 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 the anode and the cathode, respectively.
  • the organic EL device of the present invention contains one or more light-emitting materials composed of the compound represented by the general formula (I) in the light-emitting layer.
  • the organic EL device of the present invention may be one in which the above light emitting material is used alone in the light emitting layer, but the light emitting layer contains a dopant material and a host material, and the above light emitting material is used as the dopant material. Is preferred.
  • the light-emitting layer includes a dopant material and a host material
  • dopant material singlet excitons and triplet excitons generated from the light-emitting material (dopant material) can be confined in the light-emitting material, and thus the light emission efficiency tends to be increased. There is.
  • the organic EL device of the present invention light is emitted from the dopant material contained in the light emitting layer.
  • This emission includes both fluorescence emission and delayed fluorescence emission.
  • part of the light emission may be light emission from the host material.
  • the content of the dopant material in the light emitting layer is preferably 0.1 to 49% by weight, more preferably 0.5 to 40% by weight, and 1 to 30% by weight. Is more preferable.
  • the content of the host material in the light emitting layer is preferably 51 to 99.9% by weight, more preferably 60 to 99.5% by weight, and even more preferably 70 to 99% by weight.
  • the host material is preferably a compound that exhibits good film formability and ensures good dispersibility of the dopant material.
  • the host material preferably has at least one of singlet excitation energy and triplet excitation energy higher than that of the dopant material. Since the excitation energy of the host material is higher than the excitation energy of the dopant material, singlet and triplet excitons generated by the dopant can be confined in the molecule of the dopant material, increasing the luminous efficiency. Can do.
  • the energy transfer of the dopant material occurs actively from the singlet exciton of the host material.
  • the singlet excitation energy of the host material is preferably larger than the singlet excitation energy of the dopant material.
  • the difference between the singlet excitation energies of both is preferably 1 eV or less, and more preferably 0.5 eV or less.
  • the host material preferably has both hole transport performance and electron transport performance, and preferably has a small difference between the hole transport performance and the electron transport performance.
  • the ratio of hole mobility to electron mobility which is an index of transport performance, is preferably in the range of 0.002 to 500.
  • the host material include carbazole compounds, arylsilane compounds, phosphorus oxide compounds, oxadiazole compounds, quinolinol metal complexes, and the like.
  • the carbazole compound include N, N′-dicarbazolyl-4-4′-biphenyl (CBP) and N, N-dicarbazolyl-3,5-benzene (mCP).
  • mCP N, N-dicarbazolyl-3,5-benzene
  • An example of the arylsilane compound is p-bis (triphenylsilyl) benzene (UGH2).
  • Examples of phosphorus oxide compounds include 4,4′-bis (diphenylphosphoryl) -1,1′-biphenyl (PO1) and bis (2- (diphenylphosphino) phenyl) ether oxide (DPEPO). Can be mentioned.
  • the host material one kind of material may be used alone, or two or more kinds of materials may be used in combination.
  • the organic layer 3 preferably has a hole injection layer 31 and a hole transport layer 32 on the anode 2 side of the light emitting layer 33.
  • the hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic.
  • the hole transport material is preferably a compound that is easily radical cationized.
  • a compound that is easily radical cationized for example, an arylamine compound, an imidazole compound, an oxadiazole compound, an oxazole compound, a triazole compound, a chalcone compound, a styrylanthracene compound, or a stilbene compound.
  • arylamine compounds are suitable as hole transport materials because they have high hole mobility in addition to being easily radical cationized.
  • hole transport materials containing an arylamine compound triarylamine derivatives such as 4,4'-bis [N- (2-naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD) are preferable.
  • the organic layer 3 preferably has an electron injection layer 35 and an electron transport layer 34 on the cathode 4 side of the light emitting layer 33.
  • the electron transport material has either electron injection or transport or hole barrier properties, and may be either organic or inorganic.
  • the electron transport material is preferably a compound that easily undergoes radical anion, for example, a nitro-substituted fluorene derivative, a diphenylquinone derivative, a thiopyran dioxide derivative, a carbodiimide, a fluorenylidenemethane derivative, an anthraquinodimethane and anthrone derivative, an oxadiazole derivative And thiadiazole derivatives, phenanthroline derivatives, quinoline derivatives, quinoxaline derivatives and the like.
  • the electron transport material examples include 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), tris [(8-hydroxyquinolinato)] aluminum (III) (Alq 3 ), 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) and the like.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • Alq 3 tris [(8-hydroxyquinolinato)] aluminum
  • TPBi 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene
  • Alq 3 is preferably used from the viewpoint of versatility.
  • a blocking layer may be provided for the purpose of blocking diffusion of holes, electrons, or excitons existing in the light emitting layer to the outside of the light emitting layer.
  • the electron blocking layer is disposed between the light emitting layer and the hole transport layer, and blocks electrons from passing through the light emitting layer and diffusing to the hole transport side layer side.
  • the hole blocking layer is disposed between the light emitting layer and the electron transport layer, and prevents holes from passing through the light emitting layer and diffusing to the electron transport side layer side.
  • the same material as that of the above-described electron transport layer can be used.
  • the electron blocking layer the same material as the hole transport layer described above can be used.
  • 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 or hole transport layer. By providing the exciton blocking layer, excitons can be efficiently confined in the light emitting layer, and the light emission efficiency of the device can be improved.
  • the exciton blocking layer can be disposed on either the anode side or the cathode side of the light emitting layer, or may be disposed on both.
  • As the blocking layer a material in which at least one of singlet excitation energy and triplet excitation energy is higher than the singlet excitation energy and triplet excitation energy of the light-emitting dopant material is preferably used.
  • the method for forming the electrodes and the organic layer is not particularly limited, and dry processes such as sputtering, CVD, and vacuum deposition, and wet processes such as spin coating and various printing methods are appropriately employed.
  • the light emitting layer containing the host material and the dopant material can be formed, for example, by co-evaporating the host material and the dopant material. At this time, the host material and the dopant material may be mixed in advance.
  • the organic EL device of the present invention may be one using a compound represented by the above general formula (I) in addition to the light emitting layer.
  • the compound represented by the general formula (1) is used in a layer other than the light emitting layer, the same compound may be used in the light emitting layer and the layer other than the light emitting layer, or different compounds may be used.
  • part or all of the element is sealed with sealing glass or a metal cap under an inert gas atmosphere, or a protective layer such as an ultraviolet curable resin is used.
  • a coating is preferred.
  • the organic EL device of the present invention emits light by applying an electric field between the anode and the cathode. At this time, if light is emitted by singlet excitation energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In the case of light emission by triplet excitation energy, the 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 dopant material of the light emitting layer causes crossing of inverse terms due to thermal energy.
  • the exciton transitioned to the singlet excited state due to the crossing between inverse terms emits thermally activated delayed fluorescence. Therefore, the organic EL device of the present invention can exhibit a high internal quantum yield and can be an energy-saving light source with low power consumption.
  • the organic EL element of the present invention can be effectively applied to lighting fixtures and display devices.
  • the display device include a liquid crystal display device using an organic EL element as a lighting device (backlight), an organic EL display device using an organic EL element as a display panel, and the like.
  • organic EL display device reference can be made to “Organic EL Display” by Shizushi Tokito, Chiba Yasada, Hideyuki Murata (Ohm), and the like.
  • the organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a mixture.
  • the obtained mixture was purified by silica gel chromatography to obtain 0.53 g (yield 56%) of the target product as a yellow solid.
  • the obtained compound was further purified by sublimation and used as a luminescent material.
  • the obtained compound was confirmed to be Compound 1 by 1 H-NMR.
  • the obtained compound was confirmed to be Compound 2 by 1 H-NMR.
  • the obtained compound was confirmed to be compound 3 by 1 H-NMR.
  • the obtained compound was confirmed to be compound 4 by 1 H-NMR.
  • the obtained compound was confirmed to be compound 5 by 1 H-NMR.
  • the obtained compound was confirmed to be compound 6 by 1 H-NMR.
  • Example 1 Evaluation of emission characteristics in toluene solution
  • toluene solutions of the compounds 1 to 6 obtained in Synthesis Examples 1 to 6 were prepared, and nitrogen was bubbled for about 30 minutes, and then the fluorescence spectrum was measured at 300K.
  • the emission spectra of the compounds 1 to 6 in the toluene solution are shown in FIG. In FIG. 2, the emission intensity is normalized by the intensity value at the peak wavelength.
  • FIGS. 3 (A) and 3 (B) The time-resolved spectra of the fluorescence of compound 1 and compound 4 are shown in FIGS. 3 (A) and 3 (B), respectively.
  • exciton quenching energy transfer from the triplet excited state of the luminescent material to the oxygen molecule
  • delayed fluorescence shortens the life ( For example, see Endo, A. et al., Appl. Phys. Lett., 98, 83302 (2011)).
  • the time-resolved spectrum was measured without bubbling nitrogen into the solution, the lifetime ⁇ 2 was shortened in all of the compounds 1 to 6 (see “no bubbling” in FIGS. 3A and 3B). From these results, it was confirmed that Compounds 1 to 6 are materials that emit delayed fluorescence.
  • Emission peak wavelength, internal quantum yield, lifetime of fluorescent component ( ⁇ 1 ), and lifetime of delayed fluorescent component ( ⁇ 2 ) in toluene solutions of compounds 1-6 are substituted at the 3-position of the carbazolyl group of each compound
  • the 1 H-NMR chemical shifts of the groups and the hydrogen atoms at the 2nd and 6th positions of the pyridine ring are shown in Table 1.
  • Compound 1 having a cyano group that is an electron-attracting substituent on the carbazole ring of the electron-donating moiety is higher than Compound 5 having no substituent on the carbazole ring.
  • the emission peak wavelength is blue-shifted, suggesting that it is useful as a blue delayed fluorescent material.
  • compounds 2 to 4 having a pyridyl group on the carbazole ring have higher internal quantum yield than compound 5 and are useful as delayed fluorescent materials with high emission efficiency.
  • Compound 6 having an electron-donating methoxy group on the carbazole ring has a significantly red-shifted emission peak wavelength and a low internal quantum yield as compared with Compound 5.
  • Example 2 Formation and evaluation of vacuum-deposited film containing host material
  • As the host material bis (2- (diphenylphosphino) phenyl) ether oxide (DPEPO) was used.
  • DPEPO bis (2- (diphenylphosphino) phenyl) ether oxide
  • mCP N-dicarbazolyl-3,5-benzene
  • the fluorescence spectrum, internal quantum yield, and fluorescence lifetime were measured. In measuring the internal quantum yield, the measurement was performed in a nitrogen atmosphere while flowing nitrogen into the measuring apparatus. The measurement results are shown in Table 2.
  • FIGS. 4A and 4B show fluorescence time-resolved spectra of samples using Compound 1 and Compound 4 as dopant materials, respectively.
  • the co-deposited film using Compound 4 having a 4-pyridyl group as an electron-attracting substituent as a dopant showed an extremely high quantum yield of 99.0%.
  • the co-deposited film using Compound 1 having a cyano group as an electron-donating substituent as a dopant has a short emission wavelength of 459 nm and a high internal quantum yield of 76.4%. It can be seen that this is useful as a blue delayed fluorescent material with high luminous efficiency.
  • Example 3 Production and evaluation of organic electroluminescence device using compound 1
  • ITO indium tin oxide
  • ⁇ -NPD was formed on ITO to a thickness of 40 nm
  • mCP was formed thereon to a thickness of 10 nm.
  • Compound 1 and DPEPO were co-evaporated from different vapor deposition sources to form a 20 nm thick layer as a light emitting layer. At this time, the concentration of Compound 1 was 10% by weight.
  • FIG. 5 (A) shows the emission spectrum of the manufactured organic electroluminescence device measured at a current density of 100 mA / cm 2
  • FIG. 5 (B) shows the voltage-current density characteristics, and the current density-external quantum efficiency characteristics. Is shown in FIG.
  • the organic electroluminescence device using Compound 1 as a light emitting material achieved a high external quantum efficiency of 8.6% at a current density of 0.01 mA / cm 2 .
  • Example 4 Production and evaluation of organic electroluminescence device using compound 2
  • a light emitting layer having a thickness of 20 nm was formed by co-evaporating Compound 2 and mCP from different evaporation sources.
  • An organic electroluminescence device was manufactured. When the light emitting layer was formed, the concentration of Compound 2 was 10% by weight.
  • the organic electroluminescent device produced, 1mA / cm 2, 10mA / cm 2, 100mA / cm the emission spectrum measured at a current density of 2 shown in FIG. 6 (A), the voltage - current density characteristics Figure 6 (B)
  • the current density vs. external quantum efficiency characteristics are shown in FIG.
  • the organic electroluminescence device using Compound 2 as the light emitting material achieved a high external quantum efficiency of 9.7% at a current density of 0.01 mA / cm 2 .
  • Example 5 Production and evaluation of organic electroluminescence device using compound 3
  • a luminescent layer using Compound 1 and DPEPO instead of forming a luminescent layer with a thickness of 20 nm by co-evaporating Compound 3 and PPF from different evaporation sources, and forming DPEPO on the luminescent layer
  • an organic electroluminescence device was manufactured in the same manner as in Example 3 except that PPF was formed to a thickness of 10 nm.
  • the concentration of Compound 3 was 10% by weight.
  • the organic electroluminescent device produced, 1mA / cm 2, 10mA / cm 2, 100mA / cm the emission spectrum measured at a current density of 2 shown in FIG.
  • Example 6 Production and evaluation of organic electroluminescence device using compound 4
  • a light emitting layer having a thickness of 20 nm was formed by co-evaporating Compound 4 and mCP from different vapor deposition sources.
  • An organic electroluminescence device was manufactured.
  • the concentration of Compound 4 was 10% by weight.
  • the organic electroluminescent device produced, 1mA / cm 2, 10mA / cm 2, 100mA / cm the emission spectrum measured at a current density of 2 shown in FIG. 8 (A), the voltage - current density characteristics Figure 8 (B)
  • FIG. 8C shows the current density-external quantum efficiency characteristics.
  • the organic electroluminescence device using Compound 4 as the light emitting material achieved a very high external quantum efficiency of 15.7% at a current density of 0.1 mA / cm 2 .
  • Example 7 Production and evaluation of other organic electroluminescence device using compound 4
  • DPEPO is formed on the light-emitting layer.
  • an organic electroluminescence device was manufactured in the same manner as in Example 3 except that PPF was formed to a thickness of 10 nm.
  • the concentration of Compound 4 was 10% by weight.
  • the organic electroluminescent device produced, 1mA / cm 2, 10mA / cm 2, 100mA / cm the emission spectrum measured at a current density of 2 shown in FIG. 9 (A), the voltage - current density characteristics to Figure 9 (B)
  • the current density vs. external quantum efficiency characteristics are shown in FIG.
  • Other organic electroluminescent devices using Compound 4 as the light emitting material achieved a very high external quantum efficiency of 18.2% at a current density of 0.01 mA / cm 2 .

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Abstract

L'invention concerne l'utilisation d'un composé représenté par la formule générale (I) dans une couche électroluminescente d'un élément organique électroluminescent (EL), permettant d'augmenter l'efficacité lumineuse. Dans la formule générale (I), m et n sont chacun un nombre entier compris entre 1 et 3 et la valeur de m + n est de 2 à 4. A est un groupe hétéroaryle substitué ayant des propriétés de donneur d'électrons, et au moins un groupe substituant sur un noyau aromatique hétérocyclique est un groupe attracteur d'électrons. Les groupes cyano, les groupes perfluoroalkyle, les groupes hétéroaryle, et analogues, sont préférables en tant que groupes substituants attracteurs d'électrons sur le noyau aromatique hétérocyclique, et parmi ces derniers, les groupes cyano et les groupes pyridyle sont préférés.
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