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WO2018173598A1 - Élément électroluminescent organique - Google Patents

Élément électroluminescent organique Download PDF

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WO2018173598A1
WO2018173598A1 PCT/JP2018/006065 JP2018006065W WO2018173598A1 WO 2018173598 A1 WO2018173598 A1 WO 2018173598A1 JP 2018006065 W JP2018006065 W JP 2018006065W WO 2018173598 A1 WO2018173598 A1 WO 2018173598A1
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group
carbon atoms
aromatic
substituted
general formula
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匡志 多田
雄太 相良
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
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  • the present invention relates to an organic electroluminescent device (referred to as an organic EL device).
  • Patent Document 1 discloses an organic EL element using a TTF (Triplet-Triplet Fusion) mechanism, which is one of delayed fluorescence mechanisms.
  • TTF Triplet-Triplet Fusion
  • the TTF mechanism uses the phenomenon that singlet excitons are generated by the collision of two triplet excitons, and it is theoretically thought that the internal quantum efficiency can be increased to 40%.
  • the efficiency is lower than that of a phosphorescent organic EL element, further improvement in efficiency is required.
  • Patent Document 2 discloses an organic EL device using a thermally activated delayed fluorescence (TADF) mechanism.
  • the TADF mechanism utilizes the phenomenon that reverse intersystem crossing from triplet excitons to singlet excitons occurs in materials where the energy difference between singlet and triplet levels is small. It is thought to be increased to 100%.
  • TADF thermally activated delayed fluorescence
  • Such a delayed fluorescence type organic EL device is characterized by high luminous efficiency, but further improvement is required.
  • Patent Document 2 discloses the use of an indolocarbazole compound as a TADF material.
  • Patent Document 3 discloses a compound obtained by deuterating an indolocarbazole compound as shown below.
  • Patent Document 4 discloses the use of a deuterated indolocarbazole compound as a host material.
  • An object of the present invention is to provide a practically useful organic EL device having high efficiency and high driving stability in view of the above-described present situation.
  • the present invention relates to an organic EL device comprising one or more light emitting layers between an anode and a cathode facing each other, wherein at least one light emitting layer comprises a compound represented by the following general formula (1) by thermally activated delayed fluorescence. It is an organic EL element characterized by containing as a material.
  • Z is a condensed aromatic heterocycle represented by formula (2)
  • ring A is an aromatic hydrocarbon ring represented by formula (2a)
  • ring B is represented by (2b). It is a heterocyclic ring, and ring A and ring B are each fused with an adjacent ring at an arbitrary position.
  • Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 18 carbon atoms, or the aromatic hydrocarbon group and the aromatic heterocyclic ring.
  • a linked aromatic group constituted by connecting 2 to 8 aromatic rings of an aromatic group selected from a group.
  • Ar 2 represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 18 carbon atoms, or the aromatic hydrocarbon group and the aromatic heterocyclic group.
  • a linked aromatic group constituted by connecting 2 to 8 aromatic rings of an aromatic group selected from cyclic groups.
  • R 1 is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 44 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or A substituted or unsubstituted aromatic heterocyclic group having 3 to 18 carbon atoms.
  • n represents an integer of 1 to 2
  • a represents an integer of 0 to 4
  • b represents an integer of 0 to 2.
  • the compound represented by the general formula (1) has at least one deuterium.
  • L in the general formulas (3) to (8) is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • Ar 2 , a, b and R 1 have the same meaning as in the general formula (1).
  • L is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms.
  • Ar 3 is represented by the general formula (9), X represents CR 2 or N, and at least one X represents N.
  • R 2 is hydrogen, an aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms.
  • a linked aromatic group constituted by connecting 2 to 5 aromatic rings of an aromatic group selected from the aromatic hydrocarbon group and the aromatic heterocyclic group.
  • R 2 is a linked aromatic group
  • the linked aromatic rings may be the same or different, and may be linear or branched.
  • a represents an integer of 0 to 4
  • b represents an integer of 0 to 2.
  • the compounds represented by the general formulas (3) to (8) have at least one deuterium.
  • the organic EL device of the present invention can contain a host material in the light emitting layer containing the thermally activated delayed fluorescent material represented by the general formula (1).
  • the host material include a compound represented by the following general formula (10).
  • Ar 4 represents a p-valent group generated from benzene, dibenzofuran, dibenzothiophene, carbazole, carborane, triazine, or a compound in which two to three of these are connected.
  • p represents an integer of 1 or 2
  • q represents an integer of 0 to 4.
  • Ar 4 is a p-valent group derived from benzene
  • q represents an integer of 1 to 4.
  • the light emitting layer can contain at least two types of host materials represented by the general formula (10).
  • the excited triplet energy (T1) of the host material is preferably larger than the excited singlet energy (S1) of the thermally activated delayed fluorescent material represented by the general formula (1).
  • the layer represented by the general formula (10) may be contained in a layer adjacent to the light emitting layer.
  • the difference between the excited singlet energy (S1) and the excited triplet energy (T1) of the thermally activated delayed fluorescent material represented by the general formula (1) in the light emitting layer is preferably 0.2 eV or less.
  • the organic EL device of the present invention contains a specific thermally activated delayed fluorescent material in the light emitting layer, it becomes a delayed fluorescent organic EL device with high luminous efficiency and long life.
  • the organic EL device of the present invention has one or more light-emitting layers between opposed anodes and cathodes, and at least one of the light-emitting layers is a thermally activated delayed fluorescence represented by the general formula (1).
  • This organic EL device has an organic layer composed of a plurality of layers between an anode and a cathode facing each other, but at least one of the plurality of layers is a light emitting layer, and the light emitting layer contains a host material as necessary
  • a preferred host material is a compound represented by the above general formula (10).
  • Z is a condensed aromatic heterocycle represented by formula (2)
  • ring A in formula (2) is an aromatic hydrocarbon ring represented by formula (2a)
  • ring B is represented by formula (2b)
  • ring A and ring B are each fused with an adjacent ring at an arbitrary position.
  • n represents an integer of 1 to 2, preferably an integer of 1.
  • the compound represented by the general formula (1) has at least one deuterium. That is, the general formula (1) is represented by, for example, CnHmXq (where X is a heteroatom and q is an integer of 2 or more), but at least one of m H is heavy. Hydrogen D. Preferably, 10% or more, more preferably 20% or more of the m pieces of H on average are D.
  • Ar 1 is an n-valent group
  • Ar 2 is a monovalent group
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 18 carbon atoms, or the aromatic hydrocarbon group And a linked aromatic group constituted by connecting 2 to 8 aromatic rings of an aromatic group selected from the aromatic heterocyclic group.
  • it is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms, or the aromatic hydrocarbon group and the aromatic heterocyclic ring.
  • Ar 1 and Ar 2 are linked aromatic groups, the linked aromatic rings may be the same or different, and may be linear or branched.
  • the linked aromatic group as used herein refers to a group having a structure in which two or more aromatic rings of an aromatic group selected from an aromatic hydrocarbon group and an aromatic heterocyclic group are bonded by a direct bond. It is understood that the aromatic rings may be different and may be branched.
  • Ar 1 and Ar 2 include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, perylene, phenanthrene, triphenylene, corannulene, coronene, tetracene, pentacene, fluorene, benzo [a] anthracene, benzo [b] fluoranthene, benzo [a] pyrene, indeno [1,2,3-cd] pyrene, dibenzo [a, h] anthracene, picene, tetraphenylene, anthanthrene, 1,12-benzoperylene, heptacene, hexacene, Pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrol
  • Ar 1 is a group generated by taking n hydrogen atoms
  • Ar 2 is a group generated by taking one hydrogen gas.
  • each R 1 is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 44 carbon atoms, It represents a substituted or unsubstituted aromatic hydrocarbon group having 3 to 18 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 18 carbon atoms.
  • it is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 22 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 3 to 12 carbon atoms, or a substituted or unsubstituted It represents an unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms. More preferably, it represents a substituted or unsubstituted aromatic hydrocarbon group having 3 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms.
  • a represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 to 1.
  • b represents an integer of 0 to 2, preferably an integer of 0 to 1.
  • R 1 examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino, diphenanthrenyl. Amino, phenyl, biphenylyl, terphenylyl, naphthyl, pyridyl, pyrimidyl, triazyl, dibenzofuranyl, dibenzothienyl, carbazolyl and the like can be mentioned.
  • L is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms, preferably a single bond, substituted or unsubstituted An unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 8 carbon atoms, more preferably a single bond, a substituted or unsubstituted phenyl group, Or a substituted or unsubstituted aromatic heterocyclic group having 3 to 6 carbon atoms.
  • L include a single bond, benzene, naphthalene, acenaphthene, acenaphthylene, azulene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan , Isoxazole, oxazole, oxadiazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, benzotriazine, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole , Benzothiadiazole, purine, pyridine,
  • Ar 3 is a group represented by the formula (9).
  • X represents CR 2 or N, and at least one X represents N.
  • R 2 is hydrogen, an aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms. Or a connected aromatic group constituted by connecting 2 to 5 aromatic rings of an aromatic group selected from the aromatic hydrocarbon group and the aromatic heterocyclic group.
  • the explanation of the linked aromatic group is the same as the case where Ar 1 and Ar 2 are linked aromatic groups.
  • substituents include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. And an alkylthio group having 1 to 10 carbon atoms and an alkylsilyl group having 3 to 30 carbon atoms.
  • a method for converting at least one hydrogen of the compound represented by the general formula (1) into deuterium is not particularly limited, but a deuterated compound is used as a reaction raw material or a precursor compound, or represented by the general formula (1). And then dehydrogenating the non-deuterium compound in the presence of a Lewis acid H / D exchange catalyst (aluminum trichloride or ethylaluminum chloride, or an acid such as CF 3 COOD or DCl). It can be prepared by treating with a solvating solvent. The degree of deuteration can be determined by NMR analysis and mass spectrometry.
  • An excellent delayed fluorescence organic EL device can be obtained by incorporating the compound represented by the general formula (1) into the light emitting layer as a TADF material.
  • the light emitting layer can contain a host material together with the TADF material, if necessary.
  • a host material By containing a host material, an excellent organic EL device is obtained.
  • the TADF material is also called a dopant.
  • the host material promotes light emission from the TADF material, which is a dopant.
  • the host material desirably has an excited triplet energy (T1) greater than the excited singlet energy (S1) of the TADF material.
  • the difference ( ⁇ E) between the excited singlet energy (S1) and the excited triplet energy (T1) is 0.2 eV or less. It becomes an excellent heat-activated delayed fluorescent material.
  • Ar 4 is a p-valent group, and is generated by removing p hydrogen from benzene, dibenzofuran, dibenzothiophene, carbazole, carborane, triazine, or a linking compound in which 2 to 3 of these are connected. It is a group.
  • the connecting compound is a compound having a structure in which rings of benzene, dibenzofuran, dibenzothiophene, carbazole, or carborane are connected by a direct bond, and a group generated by removing two hydrogens from these compounds is, for example, ⁇ It is represented by Ar-Ar-, -Ar-Ar-Ar-, or -Ar-Ar (Ar)-.
  • Ar is a ring of benzene, dibenzofuran, dibenzothiophene, carbazole, or carborane, and a plurality of Ars may be the same or different.
  • Preferred examples of the linking compound include biphenyl or terphenyl, which is a compound in which two or three benzene rings are linked.
  • Ar 4 is a p-valent group formed by taking p hydrogens from benzene, biphenyl, terphenyl, dibenzofuran, N-phenylcarbazole, carborane, or triazine.
  • p represents an integer of 1 or 2, preferably an integer of 1.
  • q represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and q is 0 when Ar 4 is a p-valent group derived from benzene. There is no.
  • the compound represented by the general formula (10) has Ar 4 and a carbazole ring.
  • the Ar 4 and carbazole ring may have a substituent as long as the function as a host is not inhibited.
  • Examples of such a substituent include a hydrocarbon group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. .
  • an organic EL device capable of delayed fluorescent emission can be obtained.
  • An organic EL device having a more excellent characteristic by including a light-emitting layer containing the thermally activated delayed fluorescent material as a dopant material and containing a host material selected from the compound represented by the general formula (10) Can be provided. Further, the characteristics can be improved by containing two or more kinds of host materials.
  • at least one kind may be a host material selected from compounds represented by the general formula (10).
  • the first host is preferably a compound represented by the general formula (10).
  • the second host may be a compound of the general formula (10) or another host material, but is preferably a compound represented by the general formula (10).
  • S1 and T1 are measured as follows.
  • a sample compound is deposited on a quartz substrate by a vacuum deposition method under a vacuum degree of 10 ⁇ 4 Pa or less to form a deposited film with a thickness of 100 nm.
  • S1 measures the emission spectrum of this deposited film, draws a tangent to the short wavelength side rise of this emission spectrum, the wavelength value ⁇ edge [nm] of the intersection of the tangent and the horizontal axis, Substitute into i) to calculate S1.
  • S1 [eV] 1239.85 / ⁇ edge (i)
  • T1 measures the phosphorescence spectrum of the above deposited film, draws a tangent line to the short wavelength rise of this phosphorescence spectrum, and calculates the wavelength value ⁇ edge [nm] of the intersection of the tangent line and the horizontal axis in the formula (ii) Substituting into to calculate T1.
  • T1 [eV] 1239.85 / ⁇ edge (ii)
  • FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represents an electron transport layer, and 7 represents a cathode.
  • the organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, or may have an electron blocking layer between the light emitting layer and the hole injection layer.
  • the exciton blocking layer can be inserted on either the cathode side or the cathode side of the light emitting layer, or both can be inserted simultaneously.
  • the organic EL device of the present invention has an anode, a light emitting layer, and a cathode as essential layers, but preferably has a hole injecting and transporting layer and an electron injecting and transporting layer in addition to the essential layers, and further has a light emitting layer and an electron injecting layer. It is preferable to have a hole blocking layer between the transport layers.
  • the hole injection / transport layer means either or both of the hole injection layer and the hole transport layer
  • the electron injection / transport layer means either or both of the electron injection layer and the electron transport layer.
  • the structure opposite to that shown in FIG. 1, that is, the cathode 7, the electron transport layer 6, the light emitting layer 5, the hole transport layer 4 and the anode 2 can be laminated in this order on the substrate 1. Addition and omission are possible.
  • the organic EL element of the present invention is preferably supported on a substrate.
  • the substrate is not particularly limited, and any substrate that has been conventionally used for an organic EL element can be used.
  • a substrate made of glass, transparent plastic, quartz, or the like can be used.
  • anode material in the organic EL element a 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.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or the pattern accuracy is not required (about 100 ⁇ m or more). May form a pattern through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the substance which can be apply
  • the transmittance be greater than 10%
  • 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.
  • the cathode material a material made of a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, or a mixture thereof is used.
  • an electron injecting metal a material made of a metal having a small work function (4 eV or less)
  • an alloy a material made of a metal having a small work function (4 eV or less)
  • an alloy referred to as an electron injecting metal
  • an alloy an electrically conductive compound, or a mixture thereof
  • Specific examples of such 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 such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc.
  • a magnesium / silver mixture, magnesium from the viewpoint of electron injectability and durability against oxidation, etc.
  • Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these cathode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance of 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 light emission luminance is improved, which is convenient.
  • a transparent or translucent cathode can be produced by forming the conductive transparent material mentioned in the description of the anode on the cathode.
  • an element in which both the anode and the cathode are transmissive can be manufactured.
  • 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 TADF material of the present invention may be used alone, or the TADF material of the present invention may be used together with a host material.
  • the TADF material of the present invention is an organic light emitting dopant material.
  • Only one kind of organic light emitting dopant material may be contained in the light emitting layer, or two or more kinds may be contained.
  • the content of the TADF material or the organic light-emitting dopant material is preferably 0.1 to 50 wt%, more preferably 1 to 30 wt% with respect to the host material. Since the organic EL device of the present invention utilizes delayed fluorescence, a dopant such as an Ir complex used in a phosphorescent organic EL device is not used.
  • the host material in the light emitting layer known host materials used in phosphorescent light emitting devices and fluorescent light emitting devices can be used, but it is preferable to use a compound represented by the general formula (10).
  • a plurality of host materials may be used in combination.
  • at least one type of host material is preferably selected from the compounds represented by the general formula (10).
  • Known host materials that can be used are compounds having a hole transporting ability, an electron transporting ability, and a high glass transition temperature, and have a S1 larger than T1 of a TADF material or a luminescent dopant material. It is preferable.
  • Such other host materials are known from a large number of patent documents, and can be selected from them.
  • Specific examples of the host material are not particularly limited, but include indole derivatives, carbazole derivatives, indolocarbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, phenylenediamine derivatives, arylamine derivatives, Various metal complexes represented by metal complexes of styryl anthracene derivatives, fluorenone derivatives, stilbene derivatives, triphenylene derivatives, carborane compounds, porphyrin compounds, phthalocyanine derivatives, 8-quinolinol derivatives and metal complexes of metal phthalocyanines, benzoxazole and benzothiazole derivatives , Poly (N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, polythiophene derivatives, polyphenylene derivative
  • each host can be deposited from different deposition sources, or multiple types of hosts can be deposited simultaneously from one deposition source by premixing before deposition to form a premix. it can.
  • 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 hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes in the light emitting layer can be improved by preventing the above.
  • a known hole blocking material can be used for the hole blocking layer, but it is preferable to use a compound represented by the general formula (10). A plurality of hole blocking materials may be used in combination.
  • the electron blocking layer has the function of a hole transport layer in a broad sense. By blocking electrons while transporting holes, the probability of recombination of electrons and holes in the light emitting layer can be improved. .
  • a known electron blocking layer material can be used, but it is preferable to use a compound represented by the general formula (10).
  • the thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • 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 between two adjacent light emitting layers in an element in which two or more light emitting layers are adjacent.
  • a known exciton blocking layer material can be used, but it is preferable to use a compound represented by the general formula (10).
  • the layer adjacent to the light emitting layer there are a hole blocking layer, an electron blocking layer, an exciton blocking layer, etc., but when these layers are not provided, a hole transport layer, an electron transport layer, etc. Become. It is preferable to use the compound represented by the general formula (10) for at least one of the two adjacent layers.
  • 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.
  • any known compound can be selected and used.
  • Examples of such hole transport materials include porphyrin derivatives, arylamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives.
  • Porphyrin derivatives, arylamine derivatives, and styryl It is preferable to use an amine derivative, and it is more preferable to use an arylamine compound.
  • 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.
  • an electron transport material (which may also serve as a hole blocking material), it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer.
  • any known compound can be selected and used.
  • polycyclic aromatic derivatives such as naphthalene, anthracene, phenanthroline, tris (8-quinolinolato) aluminum (III) Derivatives, phosphine oxide derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, bipyridine derivatives, quinoline derivatives, oxadiazole derivatives, benzimidazoles Derivatives, benzothiazole derivatives, indolocarbazole derivatives and the like.
  • the method for forming each layer when producing the organic EL device of the present invention is not particularly limited, and may be produced by either a dry process or a wet process.
  • Synthesis Examples 2-8 Compounds 115, 119, 125, 131, 142, 150, or 158 are deuterated in the same manner as in Synthesis Example 1, so that each deuterated compound 115D, 119D, 125D, 131D, 142D, 150D , Or 158D, respectively.
  • the S1 and T1 of the deuterated product and the compound 104 before being deuterated were measured. Furthermore, S1 and T1 of the compounds 215, 217, 238, 243, and mCP were measured. The measurement method and calculation method are the same as those described above.
  • Experimental example 1 The fluorescence lifetime of compound 104D was measured.
  • a compound 104D and a compound 217 are deposited from different deposition sources on a quartz substrate by a vacuum deposition method under a vacuum degree of 10 ⁇ 4 Pa or less, and a co-deposited film having a concentration of 15% by weight of the compound 104D is formed to 100 nm Formed in thickness.
  • the emission spectrum of this thin film was measured, and light emission having a peak at 483 nm was confirmed.
  • the emission lifetime was measured with a small fluorescence lifetime measuring apparatus (Quantaurus-tau manufactured by Hamamatsu Photonics Co., Ltd.) under a nitrogen atmosphere.
  • a fluorescence with an excitation lifetime of 12 ns and a delayed fluorescence of 13 ⁇ s were observed, and it was confirmed that the compound 104D was a compound exhibiting delayed fluorescence.
  • the fluorescence lifetime was measured in the same manner as described above. As a result, delayed fluorescence was observed, and it was confirmed that the material showed delayed fluorescence emission. .
  • the fluorescence lifetime was measured in the same manner, and delayed fluorescence was observed. It was confirmed that there was.
  • Example 1 Each thin film was laminated at a vacuum degree of 4.0 ⁇ 10 ⁇ 5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 70 nm was formed.
  • HAT-CN was formed to a thickness of 10 nm as a hole injection layer on ITO, and then HT-1 was formed as a hole transport layer to a thickness of 25 nm.
  • a compound (217) was formed to a thickness of 5 nm as an electron blocking layer. Then, the compound (217) as a host and the compound (104D) as a dopant were co-deposited from different vapor deposition sources to form a light emitting layer with a thickness of 30 nm.
  • the compound (238) was formed to a thickness of 5 nm as a hole blocking layer.
  • ET-1 was formed to a thickness of 40 nm as an electron transport layer.
  • lithium fluoride (LiF) was formed to a thickness of 1 nm as an electron injection layer on the electron transport layer.
  • aluminum (Al) was formed as a cathode to a thickness of 70 nm on the electron injection layer, and an organic EL device was produced.
  • Examples 2 to 11 and Comparative Examples 1 to 8 An organic EL device was produced in the same manner as in Example 1 except that the dopant and host were changed to the compounds shown in Table 2.
  • Examples 12 and 13 An organic EL device was produced in the same manner as in Example 1 except that the electron blocking layer, the host, and the hole blocking layer were changed to the compounds shown in Table 2.
  • Example 14 Each thin film was laminated at a vacuum degree of 4.0 ⁇ 10 ⁇ 5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 70 nm was formed.
  • HAT-CN was formed to a thickness of 10 nm on ITO as a hole injection layer
  • HT-1 was formed to a thickness of 25 nm as a hole transport layer.
  • a compound (217) was formed to a thickness of 5 nm as an electron blocking layer.
  • the compound (217) as a host, the compound (238) as a second host, and the compound (104D) as a dopant were co-deposited from different vapor deposition sources to form a light emitting layer with a thickness of 30 nm.
  • the co-evaporation was performed under the vapor deposition conditions where the concentration of the compound (104D) was 15 wt% and the weight ratio of the host to the second host was 50:50.
  • the compound (238) was formed to a thickness of 5 nm as a hole blocking layer.
  • ET-1 was formed to a thickness of 40 nm as an electron transport layer.
  • lithium fluoride (LiF) was formed to a thickness of 1 nm as an electron injection layer on the electron transport layer.
  • aluminum (Al) was formed as a cathode to a thickness of 70 nm on the electron injection layer, and an organic EL device was produced.
  • Table 2 shows compounds used as a dopant, a host, a second host, a hole blocking layer, and an electron blocking layer.
  • Table 3 shows the maximum emission wavelength, external quantum efficiency, and lifetime of the emission spectrum of the produced organic EL device.
  • the maximum light emission wavelength and external quantum efficiency are values when the drive current density is 2.5 mA / cm 2 , and are initial characteristics.
  • the lifetime was measured as the time required for the luminance to decay to 95% of the initial luminance at an initial luminance of 500 cd / m 2 .
  • the organic EL device using the deuterated TADF material represented by the general formula (1) as the luminescent dopant is superior to the case where the non-deuterated TADF material is used as the luminescent dopant. It can be seen that it has a long life characteristic. This is thought to be due to the fact that the bond-dissociation energy increased due to the deuteration of carbon-hydrogen bonds to carbon-deuterium bonds, and the deterioration of the TADF material due to carbon-hydrogen bond cleavage was suppressed. It is done.
  • the organic EL element of the present invention is a delayed fluorescence type organic EL element having a high light emission efficiency and a long lifetime, and is practically useful as a display element or a light source element for a display such as a mobile phone.

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un élément électroluminescent organique de type à fluorescence retardée activé thermiquement ayant une efficacité lumineuse élevée et une longue durée de vie. Un élément électroluminescent organique comprend des couches électroluminescentes disposées entre une anode et une cathode qui se font face, au moins l'une des couches électroluminescentes contenant un composé d'indolocarbazole qui sert de matériau de fluorescence retardée activé thermiquement ou à la fois du composé d'indolocarbazole et d'un matériau hôte, le composé d'indolocarbazole est représenté par la formule générale (1), Z dans la formule représente un cycle indolocarbazole représenté par la formule (2), et au moins l'un des atomes d'hydrogène dans le composé indolocarbazole est substitué par un atome de deutérium.
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WO2021182775A1 (fr) 2020-03-11 2021-09-16 주식회사 엘지화학 Dispositif électroluminescent organique
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WO2021066370A1 (fr) 2019-10-02 2021-04-08 LG Display Co.,Ltd. Diode électroluminescente organique et dispositif électroluminescent organique la comportant
KR20210045244A (ko) * 2019-10-16 2021-04-26 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
KR102578741B1 (ko) * 2019-10-16 2023-09-13 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
KR20210046439A (ko) * 2019-10-18 2021-04-28 엘지디스플레이 주식회사 유기발광다이오드 및 유기발광장치
CN112687812B (zh) * 2019-10-18 2024-05-07 乐金显示有限公司 有机发光二极管和包括该有机发光二极管的有机发光装置
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CN114830366A (zh) * 2019-12-25 2022-07-29 日铁化学材料株式会社 有机电场发光元件
EP4083033A4 (fr) * 2019-12-25 2024-01-17 NIPPON STEEL Chemical & Material Co., Ltd. Élément électroluminescent organique
WO2021131766A1 (fr) * 2019-12-25 2021-07-01 日鉄ケミカル＆マテリアル株式会社 Élément électroluminescent organique
JP7554209B2 (ja) 2019-12-25 2024-09-19 日鉄ケミカル＆マテリアル株式会社 有機電界発光素子
JPWO2021131766A1 (fr) * 2019-12-25 2021-07-01
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WO2021182775A1 (fr) 2020-03-11 2021-09-16 주식회사 엘지화학 Dispositif électroluminescent organique
WO2024016249A1 (fr) * 2022-07-21 2024-01-25 北京大学深圳研究生院 Matériau hôte organique et dispositif électroluminescent

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