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WO2019039402A1 - Composé ayant une structure cyclique d'indéobenzoazole, et élément électroluminescent organique - Google Patents

Composé ayant une structure cyclique d'indéobenzoazole, et élément électroluminescent organique Download PDF

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Publication number
WO2019039402A1
WO2019039402A1 PCT/JP2018/030545 JP2018030545W WO2019039402A1 WO 2019039402 A1 WO2019039402 A1 WO 2019039402A1 JP 2018030545 W JP2018030545 W JP 2018030545W WO 2019039402 A1 WO2019039402 A1 WO 2019039402A1
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group
substituted
atom
carbon atoms
substituent
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幸喜 加瀬
秀珍 李
雄太 平山
駿河　和行
秀一 林
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Hodogaya Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers

Definitions

  • the present invention relates to a compound and an element suitable for an organic electroluminescent element (hereinafter referred to as an organic EL element) which is a self-emission element suitable for various display devices, and more specifically, to have a benzoazole ring structure
  • the present invention relates to a compound and an organic EL device using the compound.
  • the organic EL element is a self light emitting element, it is brighter than the liquid crystal element and has excellent visibility and clear display, and therefore, active research has been conducted.
  • Eastman Kodak Company C.I. W. Tang et al. Made the organic EL device using the organic material practical by developing a laminated structure device in which various functions are shared by the respective materials. They stack phosphors capable of transporting electrons and organic substances capable of transporting holes, and inject both charges into the phosphor layer to emit light, with a voltage of 10 V or less A high luminance of 1000 cd / m 2 or more can be obtained (see, for example, Patent Document 1 and Patent Document 2).
  • Non-Patent Document 3 An element utilizing light emission by thermally activated delayed fluorescence (TADF) has also been developed.
  • TADF thermally activated delayed fluorescence
  • the light emitting layer can also be produced by doping a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence.
  • a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence.
  • the selection of the organic material in the organic EL element has a great influence on various characteristics such as the efficiency and durability of the element. (For example, refer to Non-Patent Document 2)
  • the charge injected from both electrodes is recombined in the light emitting layer to obtain light emission, it is important how efficiently both holes and electrons are transferred to the light emitting layer.
  • the electron injection property is enhanced, the mobility is increased, the hole blocking property for blocking holes injected from the anode is further enhanced, and the probability that holes and electrons recombine is improved, and further generated in the light emitting layer By trapping the excitons, high efficiency light emission can be obtained. Therefore, the role of the electron transport material is important, and there is a demand for an electron transport material having high electron injection property, high electron mobility, high hole blocking property, and high durability to holes.
  • the heat resistance and the amorphous property of the material are also important with respect to the lifetime of the element.
  • the heat generated at the time of device operation causes thermal decomposition even at low temperatures, and the materials deteriorate.
  • crystallization of a thin film occurs even for a short time, and the device is degraded. Therefore, the material to be used is required to have high heat resistance and good amorphousness.
  • a typical light emitting material tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq3) is generally used also as an electron transport material, but its electron transfer is slow, and its work function is 5.6 eV, so it is positive. The hole blocking performance is not sufficient.
  • TAZ 4-bis(triphenyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole
  • TAZ has a large work function of 6.6 eV and high hole blocking ability, it has an electron-transporting hole blocking layer laminated on the cathode side of a fluorescent light emitting layer or a phosphorescent light emitting layer prepared by vacuum deposition or coating. And contributes to high efficiency of the organic EL element (see, for example, Non-Patent Document 4).
  • Non-Patent Document 5 Low electron transportability is a major issue in TAZ, and it has been necessary to produce an organic EL device in combination with an electron transport material having higher electron transportability (see, for example, Non-Patent Document 5).
  • BCP has a large work function of 6.7 eV and high hole blocking ability, it has a low glass transition point (Tg) of 83 ° C., so the thin film lacks stability and functions sufficiently as a hole blocking layer. I can not say that.
  • An object of the present invention is an organic compound having excellent electron injection / transport performance, hole blocking ability, and excellent stability in a thin film state as a material for organic EL devices having high efficiency and high durability. It is another object of the present invention to provide a highly efficient and highly durable organic EL device using this compound.
  • the physical properties that the organic compound to be provided by the present invention should have include (1) good electron injection characteristics, (2) high electron mobility, and (3) hole blocking ability. It can be mentioned that it is excellent, (4) that the thin film state is stable, and (5) that it is excellent in heat resistance. Further, the physical characteristics that the organic EL element to be provided by the present invention should have include (1) high luminous efficiency and high power efficiency, (2) low luminous initiation voltage, and (3) practical driving The low voltage and (4) long life can be mentioned.
  • the present inventors have the ability to coordinate the nitrogen atom of the benzoazole ring having electron affinity to a metal and the excellent heat resistance. Pay attention to designing and chemically synthesizing a compound having a benzoazole ring structure, and trial manufacture of various organic EL devices using the compound, and as a result of earnestly evaluating the characteristics of the device, the present invention is completed.
  • the present invention is a compound represented by the following general formula (1) and having an indenobenzoazole ring structure.
  • a 1 to A 4 may be the same as or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a non-substituted aromatic heterocyclic group, a carbon atom having a substituted or non-substituted fused polycyclic aromatic group, or a nitrogen atom
  • Y 1 represents a hydrogen atom, a deuterium atom, a substituted or non-substituted Aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused polycyclic aromatic group, linear group having 1 to 6 carbon atoms which may have a substituent Or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear or
  • (A-1) (Wherein, the broken line is a bonding site, and R 1 and R 2 may be the same or different from each other, and may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms) Represents a group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent.
  • Ar 1 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, A substituted or unsubstituted fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, the number of carbon atoms which may have a substituent 5 to 10 cycloalkyl groups, or Represents a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and m represents an integer of 0 to 5.
  • the same Ar 1 's bound to a plurality of benzene rings may be the same as or different from each other, and the benzene ring and the substituent substituted on the benzene ring, or the substituents substituted on the same benzene ring may be a single bond And may combine with each other to form a ring via a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom)
  • the present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (1) described in [1] is represented by the following general formula (2).
  • a 5 and A 6 may be the same or different, and are hydrogen atoms, deuterium atoms or carbon atoms having a substituent, carbon atoms having a substituted or unsubstituted aromatic hydrocarbon group, substituted or no.
  • Y 2 is a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic Hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused polycyclic aromatic group, and optionally substituted linear or branched C 1 to C 6 carbon atoms
  • X is an oxygen source R 3 and R 4 may be the same as or different from each other, and may have a substituent, a linear or branched alkyl group having 1 to 6 carbon atoms, or a
  • the same Ar 2 's bound to a plurality of benzene rings may be the same or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be a single bond And may combine with each other to form a ring via a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom)
  • the present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (2) described in [2] is represented by the following general formula (3).
  • a 7 and A 8 may be identical to or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a substituted or unsubstituted aromatic heterocyclic group, or a carbon atom having a substituted or unsubstituted fused polycyclic aromatic group
  • Y 3 represents a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aromatic group
  • Ar 3 When o is an integer of 2 or more, a plurality of these are bonded to the same benzene ring Ar 3 may be identical to or different from each other, and may be a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents substituted on the same benzene ring may be a single bond, a substituted or an unsubstituted one They may be bonded to each other via a methylene group, an oxygen atom or a sulfur atom to form a ring).
  • the present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (3) described in [3] is represented by the following general formula (4).
  • Y 4 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a substituent
  • R 7 represents a linear or branched alkenyl group having 2 to 6 carbon atoms
  • X represents an oxygen atom or a sulfur atom
  • R 7 and R 8 may be the same as or different from each other
  • p represents an integer of 0 to 5. Is an integer of 2 or more If, Ar 4 which plurality bonded to the same benzene ring may be the same or different from each other. Further, a benzene ring and a benzene ring substituted substituent or substituents each other is more substituted in the same benzene ring, May be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring)
  • the present invention is a compound having an indenobenzoazole ring structure, wherein the general formula (4) described in the claim [4] is represented by the following general formula (5).
  • R 9 and R 10 may be identical to or different from each other, and may have a substituent, a linear or 1 to 6 carbon atoms, A branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched chain having 2 to 6 carbon atoms
  • Ar 6 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group
  • q is 2 or more.
  • a plurality of Ar 6 bonded to the same benzene ring may be the same or different from each other, and a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents on the same benzene ring
  • the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 7 and Ar 8 are a hydrogen atom or a deuterium atom. Except)
  • the present invention is a compound having an indenobenzoazole ring structure, wherein the general formula (5) described in [5] is represented by the following general formula (6).
  • R 11 and R 12 may be the same as or different from each other, and have a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent
  • a substituent Represents an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent
  • Ar 9 represents deuterium Atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensation
  • Polycyclic aromatic group linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent
  • Have a group or a substituent R 10 represents
  • a plurality of benzene rings may be attached to the same benzene ring Ar 9 which is bonded individually may be the same as or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be a single bond, or may be substituted or absent They may be bonded to each other via a substituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 10 and Ar 11 are other than a hydrogen atom or a deuterium atom.
  • the present invention provides an organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween, wherein the indenobenzoazole according to any one of the above [1] to [6].
  • a compound having a ring structure is used as a constituent material of at least one organic layer.
  • the present invention is the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is an electron transport layer.
  • the present invention is also the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is a hole blocking layer.
  • the present invention is the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is a light emitting layer.
  • the present invention is the organic EL device according to the above [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is an electron injection layer.
  • a carbon atom having a substituent a “carbon atom having a substituted aromatic hydrocarbon group” represented by A 1 to A 6 in the general formulas (1) to (6), a “substituted aromatic heterocyclic group”
  • Specific examples of the "substituent" of the "carbon atom having” or the “carbon atom having a substituted fused polycyclic aromatic group” include a deuterium atom, a cyano group, a nitro group; a fluorine atom, a chlorine atom, a bromine atom and an iodine Halogen atoms such as atoms; silyl groups such as trimethylsilyl group and triphenylsilyl group; linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; methyloxy group, ethyloxy group And C 1 -C 6 linear or branched alkyloxy group such as propyloxy group; alkenyl
  • Substituted or unsubstituted aromatic hydrocarbon group represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted As the “aromatic hydrocarbon group”, the “aromatic heterocyclic group” or the “fused polycyclic aromatic group” in the substituted fused polycyclic aromatic group, there can be mentioned A in the general formulas (1) to (6) 1 are represented by a 6 "aromatic hydrocarbon group", “aromatic heterocyclic group” or can be given the same as those shown with respect to the "condensed polycyclic aromatic group", also a mode which can be taken , I can mention the same thing.
  • Substituted aromatic hydrocarbon group represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted aromatic heterocyclic group”, “substituted fused polycyclic aromatic group”, “substituted A linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a "cycloalkyl group having a carbon number of 5 to 10 which may have a substituent," or Examples of the “substituent” of “optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms” include A 1 to A in the general formulas (1) to (6). The same thing as what was shown regarding "substituent" represented by 6 can be mentioned, and the aspect which can take can mention the same thing.
  • Substituted or unsubstituted aromatic hydrocarbon group “substituted or unsubstituted aromatic heterocyclic group” represented by Ar 1 to Ar 11 in the general formulas (1) to (6), or “substituted or unsubstituted As the “aromatic hydrocarbon group”, the “aromatic heterocyclic group” or the “fused polycyclic aromatic group” in the substituted fused polycyclic aromatic group, there can be mentioned A in the general formulas (1) to (6) 1 are represented by a 6 "aromatic hydrocarbon group", “aromatic heterocyclic group” or can be given the same as those shown with respect to the "condensed polycyclic aromatic group", also a mode which can be taken , I can mention the same thing.
  • Substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group”, “substituted fused polycyclic aromatic group”, “substituted” represented by Ar 1 to Ar 11 in the general formulas (1) to (6)
  • a linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a "cycloalkyl group having a carbon number of 5 to 10 which may have a substituent," or Examples of the “substituent” of “optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms” include A 1 to A in the general formulas (1) to (6).
  • the same thing as what was shown regarding "substituent" represented by 6 can be mentioned, and the aspect which can take can mention the same thing.
  • substituents include the same ones as described for “substituents” represented by A 1 to A 6 in the general formulas (1) to (6), and the possible embodiments are also as follows: I can mention the same thing.
  • the compound having an indenobenzoazole ring structure represented by the general formula (1) which is suitably used for the organic EL device of the present invention, is a compound of an electron injection layer, an electron transport layer or a hole blocking layer of an organic EL device. It can be used as a constituent material. It is a compound having high electron mobility and a preferable material of the electron injection layer or the electron transport layer.
  • the organic EL device of the present invention uses a material for an organic EL device which is excellent in electron injection / transport performance, thin film stability and durability, it can be seen from the electron transport layer as compared with the conventional organic EL device.
  • the electron transport efficiency to the light emitting layer is improved, the light emission efficiency is improved, the driving voltage is lowered, and the durability of the organic EL element can be improved. It has become possible to realize organic EL devices with high efficiency, low drive voltage, and long life.
  • the organic EL device of the present invention efficiently injects electrons from the electron transport layer to the light emitting layer by selecting a compound having a specific indenobenzoazole ring structure capable of effectively expressing the role of electron injection / transport
  • a compound having a specific indenobenzoazole ring structure capable of effectively expressing the role of electron injection / transport
  • the luminous efficiency, the driving voltage, and the durability of the conventional organic EL element can be improved.
  • FIG. 2 shows the structures of Exemplary Compound 1 to Exemplary Compound 15 of the present invention.
  • FIG. 2 shows the structures of Exemplary Compound 16 to Exemplary Compound 30 of the present invention.
  • FIG. 16 shows the structures of Exemplary Compound 31 to Exemplary Compound 45 of the present invention.
  • FIG. 17 shows the structures of Exemplary Compound 46 to Exemplary Compound 60 of the present invention.
  • FIG. 17 shows the structures of Exemplary Compound 61 to Exemplary Compound 74 of the present invention.
  • FIG. 31 shows the structures of Exemplary Compound 75 to Exemplary Compound 89 of the present invention.
  • FIG. 16 shows structures of Exemplary Compound 90 to Exemplary Compound 107 of the present invention.
  • FIG. 16 shows structures of Exemplary Compound 108 to Exemplary Compound 122 of the present invention.
  • FIG. 16 shows the structures of Exemplary Compound 123 to Exemplary Compound 137 of the present invention.
  • FIG. 16 shows the structures of Exemplary Compound 138 to Exemplary Compound 152 of the present invention.
  • FIG. 16 shows the structures of Exemplary Compound 153 to Exemplary Compound 167 of the present invention.
  • FIG. 16 shows structures of Exemplary Compound 168 to Exemplary Compound 176 of the present invention. It is the figure which showed the organic EL element structure of Examples 6-8 and Comparative Examples 1-3.
  • the compounds having a benzoazole ring structure of the present invention are novel compounds. These compounds can be synthesized, for example, according to methods known per se as follows (see, for example, Patent Documents 5 and 6, Non-patent Documents 6 and 7).
  • Purification of the compound having an indenobenzoazole ring structure represented by the general formulas (1) to (6) is purification by column chromatography, adsorption purification with silica gel, activated carbon, activated clay or the like, recrystallization or crystallization method with a solvent , Sublimation purification method and the like. Identification of the compounds was performed by NMR analysis. Melting point, glass transition point (Tg) and work function were measured as physical property values. The melting point is an index of vapor deposition property, the glass transition point (Tg) is an index of stability of the thin film state, and the work function is an index of hole transporting property or hole blocking property.
  • the melting point and the glass transition point (Tg) were measured with a powder using a high sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS).
  • the work function was obtained by preparing a thin film of 100 nm on an ITO substrate and using an ionization potential measurement device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).
  • the structure of the organic EL device of the present invention comprises, in order on the substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, and hole transport.
  • Those having an electron blocking layer between the layer and the light emitting layer and those having a hole blocking layer between the light emitting layer and the electron transport layer can be mentioned.
  • a structure which combines a hole injection layer and a hole transport layer a structure which combines an electron injection layer and an electron transport layer It can also be done.
  • an electrode material having a large work function such as ITO or gold is used.
  • a hole injection layer of the organic EL device of the present invention in addition to a porphyrin compound represented by copper phthalocyanine, a starburst type triphenylamine derivative, having two or more triphenylamine structures or carbazolyl structures in the molecule,
  • an acceptor heterocyclic compound such as hexacyanoazatriphenylene or a coated polymer material may be used. it can.
  • These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
  • NPD N, N'-diphenyl-N, N'-di (m-tolyl) -benzidine
  • NPD N, N'-diphenyl-N Benzidine derivatives such as N, N'-di ( ⁇ -naphthyl) -benzidine (hereinafter abbreviated as NPD), N, N, N ', N'-tetrabiphenylyl benzidine, 1,1-bis [(di-4) -Tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), a molecule having two or more triphenylamine structures or carbazolyl structures in the molecule, each of which is a single bond or a divalent group having no hetero atom
  • TAPC 1,1-bis [(di-4) -Tolylamino) phenyl] cyclohexane
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PSS poly (styrene sulfonate)
  • a material in which trisbromophenylamine hexachloroantimony, a radialene derivative is further P-doped to a material usually used in the layer, A high molecular compound having a structure of a benzidine derivative such as TPD in its partial structure can be used.
  • TCTA 4,4 ′, 4 ′ ′-tri (N-carbazolyl) triphenylamine
  • TCTA 9,9-bis [4- (carbazole-) 9-yl) phenyl] fluorene
  • mCP 1,3-bis (carbazol-9-yl) benzene
  • Ad 2,2-bis (4-carbazol-9-ylphenyl) adamantane
  • triphenylsilyl groups represented by 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene.
  • compounds having electron blocking activity such as compounds having a triarylamine structure.
  • these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials.
  • a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
  • the light emitting layer of the organic EL device of the present invention in addition to the metal complex of quinolinol derivative including Alq 3 in addition to the compound having the indenobenzoazole ring structure of the present invention, various metal complexes, anthracene derivative, bisstyryl Benzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives and the like can be used.
  • the light emitting layer may be composed of a host material and a dopant material. Anthracene derivative is preferably used as the host material, but the light emission including the compound having an indenobenzoazole ring structure of the present invention.
  • a heterocyclic compound having an indole ring as a partial structure of a condensed ring a heterocyclic compound having a carbazole ring as a partial structure of a condensed ring, a carbazole derivative, a thiazole derivative, a benzimidazole derivative, a polydialkyl fluorene derivative, etc.
  • a dopant material quinacridone, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives and the like can be used.
  • these may be formed separately, they may be used as a single layer formed by mixing with other materials, layers formed separately by the above plural materials, and by the above plural materials
  • a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed.
  • a phosphorescence material as a light emitting material.
  • a phosphorescence light emitter a phosphorescence light emitter of metal complex such as iridium and platinum can be used.
  • a green phosphor such as Ir (ppy) 3
  • a blue phosphor such as FIrpic or FIr 6
  • a red phosphor such as Btp 2 Ir (acac), or the like may be used as the host material.
  • CBP 4,4'-di (N-carbazolyl) biphenyl
  • carbazole derivatives such as TCTA and mCP
  • CBP 4,4'-di (N-carbazolyl) biphenyl
  • carbazole derivatives such as TCTA and mCP
  • UGH2 triphenylsilyl
  • a -1H-benzimidazole) hereinafter abbreviated as TPBI
  • TPBI -1H-benzimidazole
  • Non-Patent Document 3 a material that emits delayed fluorescence such as PICCB, such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as a light-emitting material.
  • PICCB a material that emits delayed fluorescence
  • CC2TA a material that emits delayed fluorescence
  • PXZ-TRZ a material that emits delayed fluorescence
  • 4CzIPN a material that emits delayed fluorescence
  • These materials can be thin film-formed by a known method such as a spin coating method or an inkjet method in addition to the vapor deposition method.
  • phenanthroline derivatives such as vasocuproin (hereinafter abbreviated as BCP) and metals of quinolinol derivatives such as BAlq
  • BCP vasocuproin
  • metals of quinolinol derivatives such as BAlq
  • various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and other compounds having a hole blocking function can be used. These materials may double as the material of the electron transport layer. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials.
  • a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
  • metal complexes of quinolinol derivatives including Alq 3 and BAlq, various metal complexes, and triazole derivatives as an electron transport layer of the organic EL device of the present invention Triazine derivatives, oxadiazole derivatives, pyridine derivatives, benzimidazole derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, silole derivatives and the like can be used.
  • these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials.
  • a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed.
  • These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
  • alkali metal salts such as lithium fluoride and cesium fluoride
  • alkaline earth metal salts such as magnesium fluoride
  • Metal complexes of quinolinol derivatives such as lithium quinolinol
  • metal oxides such as aluminum oxide, or metals such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), cesium (Cs), etc.
  • Yb ytterbium
  • Sm samarium
  • Ca calcium
  • Cs cesium
  • a material generally used in the layer may be further N-doped with a metal such as cesium.
  • an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as an electrode material.
  • the melting point and the glass transition point of the indenobenzoazole compound represented by the general formula (1) were measured by a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS). Melting point glass transition point Compound of Example 1 269 ° C. 136 ° C. The compound of Example 2 256 ° C 127 ° C Compound of Example 3 353 ° C 178 ° C
  • the compound having an indenobenzoazole ring structure represented by the general formula (1) has a glass transition point of 100 ° C. or more, which indicates that the thin film state is stable.
  • the compound having an indenobenzoazole ring structure represented by the general formula (1) has a work function larger than the work function 5.5 eV of general hole transport materials such as NPD and TPD, and a large hole Has a blocking ability.
  • the organic EL device has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a hole blocking layer on an ITO electrode previously formed as a transparent anode 2 on a glass substrate 1.
  • the layer 6, the electron transport layer 7, the electron injection layer 8, and the cathode (aluminum electrode) 9 were sequentially deposited and manufactured.
  • the glass substrate 1 on which ITO having a film thickness of 50 nm was formed was subjected to ultrasonic cleaning for 20 minutes in isopropyl alcohol and then dried for 10 minutes on a hot plate heated to 200 ° C. Thereafter, UV ozone treatment was carried out for 15 minutes, and then the ITO-attached glass substrate was mounted in a vacuum deposition machine, and the pressure was reduced to 0.001 Pa or less.
  • a compound (HTM-1) of the following structural formula was formed as a hole transport layer 4 to have a film thickness of 60 nm.
  • Binary vapor deposition was performed at a vapor deposition rate to form a film thickness of 20 nm.
  • Lithium fluoride was formed as the electron injection layer 8 to a film thickness of 1 nm on the hole blocking and electron transporting layers 6 and 7. Finally, aluminum was deposited 100 nm to form a cathode 9. The characteristics of the produced organic EL device were measured at room temperature in the air. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
  • Example 6 the compound (Compound-4) of Example 2 is used instead of the compound (Compound-105) of Example 1 of the present invention as the material of the hole blocking layer / electron transport layer 6 and 7 and the deposition rate ratio
  • the characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
  • the device life was measured using the organic EL devices produced in Examples 6 to 8 and Comparative Examples 1 to 3, and the results are shown in Table 1.
  • the device life is equivalent to 95% when the light emission luminance is 1900 cd / m 2 (when the initial luminance is 100% when constant current driving is performed with the light emission luminance at the start of light emission (initial luminance) 2000 cd / m 2 : The time to decay to 95%) was measured.
  • the driving voltage when a current having a current density of 10 mA / cm 2 is applied is 3.81 of the organic EL elements of Comparative Examples 1 to 3 using the compounds ETM-2 to 4 of the above structural formula.
  • the voltage was lowered to 3.37 to 3.60 V with respect to ⁇ 4.05 V.
  • the luminous efficiency is improved to 8.58 to 8.87 cd / A for the organic EL devices of Examples 6 to 8 as compared with 7.40 to 7.68 cd / A for the organic EL devices of Comparative Examples 1 to 3.
  • the organic EL devices of Examples 6 to 8 are as large as 7.48 to 8.14 lm / W, compared with 5.96 to 6.30 lm / W of the organic EL devices of Comparative Examples 1 to 3. Improved.
  • the organic EL elements of Examples 6 to 8 greatly extend the life to 129 to 149 hours, compared with 35 to 55 hours for the organic EL elements of Comparative Examples 1 to 3. There is.
  • the organic EL device of the present invention is superior to the devices using the compounds ETM-2 to 4 of the above structural formula in luminous efficiency and power efficiency, and can realize an organic EL device having a long life. all right.
  • the compound having a specific indenobenzoazole ring structure of the present invention is excellent as a compound for an organic EL device because it has good electron injection characteristics, excellent hole blocking ability, and stable thin film state. There is.
  • By manufacturing an organic EL element using the compound high efficiency can be obtained, driving voltage can be reduced, and durability can be improved. For example, it has become possible to expand to home appliances and lighting applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir, en tant que matériau pour un élément électroluminescent organique ayant un rendement élevé et une durabilité élevée, un composé organique ayant d'excellentes performances d'injection et de transport d'électrons, une capacité à bloquer des trous positifs, et d'excellentes caractéristiques hautement stables dans une forme de couche mince. Le problème décrit par la présente invention concerne en outre, la fourniture d'un élément électroluminescent organique ayant une efficacité élevée et une durabilité élevée à l'aide du composé. La solution selon l'invention porte sur une structure cyclique d'indéobenzoazole représentée par la formule générale (1). (Dans la formule, A1-A4 peuvent être identiques ou différents et représentent chacun un atome de carbone ayant un atome d'hydrogène, un atome de deutérium ou un substituant, un atome de carbone ayant un groupe hydrocarboné aromatique substitué ou non substitué, un atome de carbone ayant un groupe hétérocyclique aromatique substitué ou non substitué, un atome de carbone ayant un groupe aromatique polycyclique condensé substitué ou non substitué, ou un atome d'azote, Y1 représente un atome d'hydrogène, un atome de deutérium, un groupe hydrocarboné aromatique substitué ou non substitué, un groupe hétérocyclique aromatique substitué ou non substitué, un groupe aromatique polycyclique condensé substitué ou non substitué, un groupe alkyle à chaîne linéaire ou ramifiée éventuellement substitué ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle éventuellement substitué ayant de 5 à 10 atomes de carbone, ou un groupe alcényle à chaîne linéaire ou ramifiée éventuellement substitué ayant 2 à 6 atomes de carbone, et X représente un atome d'oxygène ou un atome de soufre, à condition qu'un site entre des atomes de carbone adjacents de A1-A4 soit représenté par la formule structurale (A-1)).
PCT/JP2018/030545 2017-08-23 2018-08-17 Composé ayant une structure cyclique d'indéobenzoazole, et élément électroluminescent organique Ceased WO2019039402A1 (fr)

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US20140319473A1 (en) * 2013-04-25 2014-10-30 Samsung Display Co., Ltd. Heterocyclic compound and organic light emitting device comprising the same
WO2015111943A1 (fr) * 2014-01-23 2015-07-30 주식회사 두산 Composé organique et dispositif électroluminescent organique le contenant
US20150349266A1 (en) * 2014-06-03 2015-12-03 Samsung Display Co., Ltd. Organic light-emitting device
WO2017111439A1 (fr) * 2015-12-22 2017-06-29 주식회사 두산 Composé organique et dispositif électroluminescent organique comprenant ledit composé
CN107266385A (zh) * 2017-06-26 2017-10-20 上海道亦化工科技有限公司 一种芴类有机电致发光化合物及其有机电致发光器件
CN107382992A (zh) * 2017-08-09 2017-11-24 上海道亦化工科技有限公司 一种咔唑类有机电致发光化合物及其有机电致发光器件
CN107501201A (zh) * 2017-08-09 2017-12-22 上海道亦化工科技有限公司 一种螺唑类有机电致发光化合物及其有机电致发光器件

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140319473A1 (en) * 2013-04-25 2014-10-30 Samsung Display Co., Ltd. Heterocyclic compound and organic light emitting device comprising the same
WO2015111943A1 (fr) * 2014-01-23 2015-07-30 주식회사 두산 Composé organique et dispositif électroluminescent organique le contenant
US20150349266A1 (en) * 2014-06-03 2015-12-03 Samsung Display Co., Ltd. Organic light-emitting device
WO2017111439A1 (fr) * 2015-12-22 2017-06-29 주식회사 두산 Composé organique et dispositif électroluminescent organique comprenant ledit composé
CN107266385A (zh) * 2017-06-26 2017-10-20 上海道亦化工科技有限公司 一种芴类有机电致发光化合物及其有机电致发光器件
CN107382992A (zh) * 2017-08-09 2017-11-24 上海道亦化工科技有限公司 一种咔唑类有机电致发光化合物及其有机电致发光器件
CN107501201A (zh) * 2017-08-09 2017-12-22 上海道亦化工科技有限公司 一种螺唑类有机电致发光化合物及其有机电致发光器件

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