WO2020045954A1 - Diode électroluminescente organique - Google Patents

Diode électroluminescente organique Download PDF

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WO2020045954A1
WO2020045954A1 PCT/KR2019/010935 KR2019010935W WO2020045954A1 WO 2020045954 A1 WO2020045954 A1 WO 2020045954A1 KR 2019010935 W KR2019010935 W KR 2019010935W WO 2020045954 A1 WO2020045954 A1 WO 2020045954A1
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cyano
substituted
formula
unsubstituted
group
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PCT/KR2019/010935
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Korean (ko)
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윤정민
김공겸
천민승
구기동
김영석
이민우
오중석
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주식회사 엘지화학
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Priority claimed from KR1020190103965A external-priority patent/KR102214384B1/ko
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Priority to CN201980006391.9A priority Critical patent/CN111512458B/zh
Publication of WO2020045954A1 publication Critical patent/WO2020045954A1/fr

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    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • 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
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring

Definitions

  • the present invention relates to an organic light emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • the organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.
  • the organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode.
  • the organic layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to an organic light emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.
  • this invention provides the following organic light emitting elements.
  • a light emitting layer between the anode and the cathode A light emitting layer between the anode and the cathode
  • the maximum efficiency value (Eff max ) and the minimum efficiency value (Eff min ) at a current density of 0.1 mA / cm 2 to 10 mA / cm 2 satisfy Equation 1 below.
  • the electron transport layer includes a compound represented by the following formula (1):
  • L 1 to L 3 are each independently a single bond; Or substituted or unsubstituted C 6-60 arylene,
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • A is represented by the following formula (2) or (3),
  • W is O, S, CR 9 R 10 , or SiR 11 R 12 ,
  • T is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram
  • R 1 to R 8 are each independently hydrogen; heavy hydrogen; Or cyano, or adjacent R 6 and R 7 may combine with each other to form a spiro ring structure,
  • R 9 to R 12 are each independently hydrogen; heavy hydrogen; Cyano; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • a1 is an integer of 0 to 3
  • a2 to a6 and a8 are each independently an integer of 0 to 4,
  • a7 is an integer of 0 to 5
  • the above-described organic light emitting device uses a compound represented by Chemical Formula 1, which will be described later, as a material for the electron transport layer, and thus, the efficiency change according to the change of the current density is small, and the color change according to the driving environment is small. have.
  • the organic light emitting device may exhibit characteristics of low voltage, high efficiency, and long life.
  • FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, an electron transport layer 4, and a cathode 5. As shown in FIG.
  • an organic light emitting element is shown.
  • FIG. 3 is a graph illustrating efficiency graphs according to current densities of organic light emitting diodes of Example 16 and Comparative Example 7.
  • FIG. 3 is a graph illustrating efficiency graphs according to current densities of organic light emitting diodes of Example 16 and Comparative Example 7.
  • Means a bond connected to another substituent, and a single bond means a case where no separate atom is present in a moiety represented by L 1 to L 3 .
  • substituted or unsubstituted is deuterium; Halogen group; Cyano group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups including one or more of N, O, and S atoms, or substituted or unsubstituted with two or more
  • a substituent to which two or more substituents are linked may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent to which two phenyl groups are linked.
  • carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the ester group may be substituted with oxygen of the ester group having 1 to 25 carbon atoms, a straight chain, branched chain or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
  • the present invention is not limited thereto.
  • the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group and the like.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • the fluorenyl group is substituted, And so on.
  • the present invention is not limited thereto.
  • the heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole
  • the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above.
  • the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above.
  • the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heteroaryl.
  • the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above.
  • the description of the aryl group described above may be applied.
  • the description of the aforementioned heteroaryl may be applied except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding.
  • the heterocycle is not a monovalent group, and the description of the aforementioned heteroaryl may be applied except that two substituents are formed by bonding.
  • the organic light emitting diode according to the present invention has a current density of 0.1 in a current density-efficiency graph indicating a change in efficiency according to a current density in which the x axis is current density (mA / cm 2 ) and the y axis is efficiency (cd / A).
  • the maximum efficiency value Eff max with respect to the minimum efficiency value Eff min among the efficiency values measured in the mA / cm 2 to 10 mA / cm 2 range is 1.5 or less.
  • the efficiency is relatively constant, so that the color change according to the driving environment is small, and thus the panel failure rate may be significantly lowered.
  • the efficiency change according to the change of the current density is large, which may cause a panel failure.
  • the change in efficiency due to the change in current density is small, so that the organic light emitting diode has a low driving voltage, and may exhibit high efficiency and long life.
  • the organic light emitting device satisfying Equation 1 may be implemented using a compound having a specific structure substituted with one or more cyano groups as a material of the electron transport layer of the organic light emitting device, and will be described in detail below.
  • the anode material a material having a large work function is generally preferred to facilitate hole injection into the organic material layer.
  • the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Or a multi-layered material such as LiO 2 / Al, but is not limited thereto.
  • a hole injection layer may be further included on the anode.
  • the hole injection layer is made of a hole injection material, and has a capability of transporting holes as the hole injection material, has an effect of hole injection at the anode, excellent hole injection effect to the light emitting layer or the light emitting material, and The compound which prevents the movement to an electron injection layer or an electron injection material, and is excellent in thin film formation ability is preferable.
  • the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer.
  • the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene Organic, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer used in the present invention is a layer for receiving holes from the hole injection layer formed on the anode or the anode and transporting holes to the light emitting layer, and transporting holes from the anode or the hole injection layer with a hole transport material to the light emitting layer.
  • Suitable materials are those with high mobility for holes.
  • arylamine-based organic material examples include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively is preferably a material having good quantum efficiency with respect to fluorescence or phosphorescence.
  • Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
  • Alq 3 8-hydroxyquinoline aluminum complex
  • Carbazole series compounds Dimerized styryl compounds
  • BAlq 10-hydroxybenzo quinoline-metal compound
  • Benzoxazole, benzthiazole and benzimidazole series compounds include Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
  • PSV poly (p-phenylenevinylene)
  • the light emitting layer may include a host material and a dopant material.
  • the host material may be a condensed aromatic ring derivative or a hetero ring-containing compound.
  • the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like.
  • the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene and periplanthene having an arylamino group, and styrylamine compounds may be substituted or unsubstituted.
  • At least one arylvinyl group is substituted with the above-described arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted.
  • substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted.
  • styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like but is not limited thereto.
  • the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.
  • the organic light emitting device may include an electron transport layer between the light emitting layer and the electron injection layer.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer.
  • As an electron transporting material a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Do.
  • a compound represented by the following Chemical Formula 1 is used as a material for the electron transport layer:
  • L 1 to L 3 are each independently a single bond; Or substituted or unsubstituted C 6-60 arylene,
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • A is represented by the following formula (2) or (3),
  • W is O, S, CR 9 R 10 , or SiR 11 R 12 ,
  • T is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram
  • R 1 to R 8 are each independently hydrogen; heavy hydrogen; Or cyano, or adjacent R 6 and R 7 may combine with each other to form a spiro ring structure,
  • R 9 to R 12 are each independently hydrogen; heavy hydrogen; Cyano; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • a1 is an integer of 0 to 3
  • a2 to a6 and a8 are each independently an integer of 0 to 4,
  • a7 is an integer of 0 to 5
  • the meaning of 'at least one of L 1 to L 3 , Ar 1 , Ar 2 and A is substituted with cyano' in Formula 1 means a substituent of L 1 , a substituent of L 2 , a substituent of L 3 , and Ar 1 It means that at least one of a substituent of, a substituent of Ar 2 , and a substituent of R (R 1 to R 12 ) is a cyano group.
  • L 1 to L 3 is substituted with a cyano group L 1 to L 3 represent C 6-60 arylene.
  • Equation 1 Since the compound represented by Formula 1 having such a cyano group is included in the electron transport layer, an organic light emitting device that satisfies Equation 1 may be implemented.
  • one to three of the substituents of L 1, the substituent of L 2, the substituent of L 3, the substituent of Ar 1, the substituent of Ar 2 , and the substituents of A (R 1 to R 12 ) of Formula 1 may be It can be anger.
  • one of L 1 to L 3 , Ar 1 , Ar 2 and A is substituted with cyano.
  • one or two of the substituents of L 1, the substituent of L 2, the substituent of L 3, the substituent of Ar 1, the substituent of Ar 2 , and the substituents of A (R 1 to R 12 ) of Formula 1 may be It can be anger.
  • substituted with cyano in the definition of the substituent herein means that one or more hydrogen, preferably one or two hydrogen of the hydrogen contained in the substituent is substituted with a cyano group.
  • the compound represented by Formula 1 may be represented by the following Formula 1A, 1B, or 1C:
  • L 1 to L 3 are each independently a single bond; Or C 6-20 arylene unsubstituted or substituted with cyano,
  • Ar 1 and Ar 2 are each independently C 6-20 aryl unsubstituted or substituted with methyl or cyano,
  • W is O or S
  • R 1 to R 4 are each independently hydrogen; heavy hydrogen; Or cyano,
  • L 1 to L 3 is C 6-20 arylene substituted with cyano
  • At least one of Ar 1 and Ar 2 is C 6-20 aryl substituted with cyano; or
  • At least one of R 1 to R 4 is cyano
  • L 1 to L 3 are each independently a single bond; Or C 6-20 arylene unsubstituted or substituted with cyano,
  • Ar 1 and Ar 2 are each independently C 6-20 aryl unsubstituted or substituted with methyl or cyano,
  • T is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram
  • R 5 to R 8 are each independently hydrogen; heavy hydrogen; Or cyano,
  • L 1 to L 3 is C 6-20 arylene substituted with cyano
  • At least one of Ar 1 and Ar 2 is C 6-20 aryl substituted with cyano; or
  • At least one of R 1 to R 4 is cyano
  • L 1 to L 3 are each independently a single bond; Or C 6-20 arylene unsubstituted or substituted with cyano,
  • Ar 1 and Ar 2 are each independently C 6-20 aryl unsubstituted or substituted with methyl or cyano,
  • R 5 to R 8 , R 6 ′ and R 7 ′ are each independently hydrogen; heavy hydrogen; Or cyano,
  • L 1 to L 3 is C 6-20 arylene substituted with cyano
  • At least one of Ar 1 and Ar 2 is C 6-20 aryl substituted with cyano; or
  • At least one of R 5 to R 8 , R 6 ′ and R 7 ′ is cyano.
  • C 6-20 aryl unsubstituted or substituted with methyl or cyano in the definition of a substituent means unsubstituted C 6-20 aryl; C 6-20 aryl substituted with one or more methyl; C 6-20 aryl substituted with one or more cyano; Or C 6-20 aryl substituted with one or more cyano and one or more methyl.
  • L 1 to L 3 are each independently a single bond; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylylene; Substituted or unsubstituted terphenylylene; Or substituted or unsubstituted naphthylene.
  • L 1 to L 3 are each independently a single bond; Phenylene unsubstituted or substituted with cyano; Or biphenylylene, unsubstituted or substituted with cyano.
  • L 1 to L 3 are each independently a single bond; Phenylene unsubstituted or substituted with cyano; Biphenylylene, unsubstituted or substituted with cyano; Or terphenylylene, unsubstituted or substituted with cyano.
  • Ar 1 and Ar 2 may each independently be C 6-20 aryl unsubstituted or substituted with methyl or cyano.
  • Ar 1 and Ar 2 are each independently phenyl unsubstituted or substituted with cyano; Biphenylyl unsubstituted or substituted with cyano; Or terphenylyl unsubstituted or substituted with cyano; Or 9,9-dimethylfluorene unsubstituted or substituted with cyano.
  • Ar 1 and Ar 2 are each independently phenyl unsubstituted or substituted with one or two cyano; Biphenylyl unsubstituted or substituted with one or two cyano; Or terphenylyl unsubstituted or substituted with one or two cyano; Or 9,9-dimethylfluorene unsubstituted or substituted with one or two cyanos.
  • W may be O or S.
  • R 1 to R 8 may be each independently hydrogen or cyano.
  • R 9 to R 12 are each independently hydrogen; heavy hydrogen; Cyano; C 6-20 aryl unsubstituted or substituted with cyano; Or C 2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of N, O and S unsubstituted or substituted with cyano.
  • R 9 to R 12 may be each independently hydrogen or cyano.
  • a1 to a8 mean the number of R 1 to R 8 , respectively.
  • two or more R 1 to R 8 may be the same as or different from each other.
  • a1 to a8 may be each independently 0 or 1.
  • a represented by Chemical Formula 3 may be represented by the following Chemical Formulas 3-1 to 3-10 according to T.
  • T When T is a benzene ring, it may be represented by the following Formula 3-1, when T is a naphthalene ring, by Formulas 3-2 to 3-4, and when T is a phenanthrene ring, by Formulas 3-5 to 3-10. have.
  • R 5 to R 8 and a5 to a8 are the same as defined in Formula 3, and * represents a position connected to L 3 of Formula 1.
  • a represented by Formula 3 may have a structure in which one compound is connected to another compound structure and one carbon when adjacent Sp 6 and R 7 combine with each other to form a spiro ring structure.
  • adjacent R 6 and R 7 in Formula 3 may combine with each other to form a spiro ring structure in which a fluorene structure and one carbon are connected to a contact point, which may be represented by the following Formula 3-11.
  • R 5 to R 8 and a5 to a8 are the same as defined in Formula 3, and R 6 ′, R 7 ′, a6 ′, and a7 ′ are each represented by R 6 , R 7 , a6, and a7.
  • * represents a position connected to L 3 of the formula (1).
  • A may be any one selected from the group consisting of Formulas 4a to 4e:
  • W is O or S
  • R 1 to R 8 are the same as defined in Formulas 2 and 3,
  • R 6 ′ and R 7 ′ refer to the description of R 6 and R 7 , respectively.
  • R 1 to R 8 , R 6 ′ and R 7 ′ may each independently be hydrogen or cyano.
  • R 1 to R 4 are hydrogen; Or one of R 1 to R 4 is cyano, the other is hydrogen,
  • R 5 to R 8 are hydrogen; Or one of R 5 to R 8 is cyano, the other is hydrogen,
  • R 5 to R 8 , R 6 ′ and R 7 ′ are hydrogen; Or one of R 5 to R 8 , R 6 ′ and R 7 ′ is cyano, and the other may be hydrogen.
  • Chemical Formula 1 may be any one selected from the group consisting of Chemical Formulas 1-1 to 1-9:
  • W is O or S
  • L 1 to L 3 , Ar 1 , Ar 2 and R 1 to R 8 are the same as defined in Chemical Formulas 1 to 3,
  • R 6 ′ and R 7 ′ refer to the description for R 6 and R 7 , respectively.
  • the compound represented by Formula 1 may be any one selected from the group consisting of:
  • the electron transport layer may further include materials known as conventional electron transport materials, specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material as used in the prior art.
  • suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.
  • the electron injection layer is a layer that injects electrons from an electrode, and has a capability of transporting electrons, an electron injection effect from a cathode, an excellent electron injection effect on a light emitting layer or a light emitting material, and a compound having excellent thin film formation ability. desirable.
  • the electron injection layer may also serve as the above-described electron transport layer.
  • the electron injection material include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinomimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, Perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like, derivatives thereof, metal complex compounds and nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
  • FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, an electron transport layer 4, and a cathode 5. As shown in FIG. In such a structure, the compound represented by Formula 1 may be included in the electron transport layer.
  • the compound represented by Formula 1 may be included in the electron transport layer.
  • the electron transport layer and the electron injection layer may be provided as one layer such as an electron injection and transport layer.
  • the organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configuration. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. After forming the above-described respective layers, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • PVD physical vapor deposition
  • the light emitting layer may be formed of a host and a dopant not only by vacuum deposition but also by solution coating.
  • the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double side emission type according to a material used.
  • Compound 7 was prepared in the same manner as in Preparation Example 1, except that Compound A6 was used instead of Compound A1 and Compound B6 was used instead of Compound B1.
  • Compound 8 was prepared in the same manner as in Preparation Example 1, except that Compound B7 was used instead of Compound B1 in Preparation Example 1.
  • Compound 9 was prepared in the same manner as in Preparation Example 1, except that Compound A7 was used instead of Compound A1 and Compound B8 was used instead of Compound B1.
  • Compound 10 was prepared in the same manner as in Preparation Example 1, except that Compound A4 was used instead of Compound A1 and Compound B9 was used instead of Compound B1.
  • Compound 11 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 and Compound B10 was used instead of Compound B1.
  • Compound 12 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 and Compound B11 was used instead of Compound B1.
  • Compound 13 was prepared in the same manner as in Preparation Example 1, except that Compound A5 was used instead of Compound A1 and Compound B9 was used instead of Compound B1.
  • Compound 14 was prepared in the same manner as in Preparation Example 1, except that Compound A8 was used instead of Compound A1 and Compound B12 was used instead of Compound B1.
  • Compound 15 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 and Compound B13 was used instead of Compound B1.
  • Compound 16 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 and Compound B14 was used instead of Compound B1 in Preparation Example 1.
  • Compound 17 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 and Compound B12 was used instead of Compound B1.
  • a glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) at a thickness of 1000 ⁇ was placed in distilled water in which a dispersant was dissolved, and washed with ultrasonic waves. Fischer Co. was used for the detergent, and Millipore Co. Secondary filtered distilled water was used as a filter of the product. After ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.
  • ITO Indium Tin Oxide
  • Hexonitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.
  • a hole transport layer was formed by vacuum depositing HT1 (400 kPa), a material for transporting holes, thereon.
  • the host H1 and the dopant D1 compound were vacuum deposited to a thickness of 300 kPa to form a light emitting layer.
  • Compound 1 and LiQ (Lithium Quinolate) prepared in Preparation Example 1 were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron transport layer having a thickness of 350 Pa.
  • the organic light emitting device was manufactured by sequentially depositing lithium fluoride (LiF) and aluminum having a thickness of 2,000 ⁇ on the electron transport layer to form a electron injection layer and a cathode.
  • LiF lithium fluoride
  • aluminum having a thickness of 2,000 ⁇ on the electron transport layer to form a electron injection layer and a cathode.
  • the deposition rate of the organic material was maintained at 0.4 ⁇ 0.7 ⁇ / sec
  • the lithium fluoride of the cathode was maintained at 0.3 ⁇ / sec
  • the deposition rate of aluminum was 2 ⁇ / sec
  • the vacuum degree during deposition was 2 x 10 -7
  • the organic light emitting device was manufactured by maintaining ⁇ 5 ⁇ 10 ⁇ 6 torr.
  • Example 1 The compound used in Example 1 is as follows.
  • An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compounds shown in Table 1 below instead of compound 1 as the electron transport layer material in Example 1.
  • the compound used in the comparative example is summarized as follows.
  • the organic light emitting device using the compound represented by Formula 1 as the material of the electron transport layer unlike the organic light emitting device of the comparative example, the value of Eff max / Eff min is 1.5 or less Able to know.
  • the organic light emitting device using the compound represented by Chemical Formula 1 as a material of the electron transport layer exhibits excellent characteristics in terms of driving voltage, luminous efficiency, and lifetime as compared with the organic light emitting device of Comparative Example.
  • the organic light emitting device employing the compound represented by Chemical Formula 1 as an electron transporting layer material has a small change in efficiency and a small change in color depending on the driving environment, even though the current density increases, compared to the organic light emitting device of the comparative example. It is believed that the service life is improved. Therefore, considering that the luminous efficiency and lifetime characteristics of the organic light emitting device generally have a trade-off relationship with each other, the organic light emitting device employing the compound of the present invention has significantly improved device characteristics compared to the comparative device. It can be seen that.
  • substrate 2 anode

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une diode électroluminescente organique comprenant : une anode; une cathode; une couche électroluminescente disposée entre l'anode et la cathode; et une couche de transport d'électrons disposée entre la cathode et la couche électroluminescente, la couche de transport d'électrons comprenant un composé représenté par la formule chimique 1, la diode électroluminescente organique présentant un rapport de valeur d'efficacité maximale (Effmax) à une valeur d'efficacité minimale (Effmin) inférieur ou égal à 1,5 à une densité de courant de 0,1 mA/cm2 à 10 mA/cm2 dans un diagramme de densité de courant/efficacité de celle-ci.
PCT/KR2019/010935 2018-08-28 2019-08-27 Diode électroluminescente organique WO2020045954A1 (fr)

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KR20180101609 2018-08-28
KR10-2018-0101609 2018-08-28
KR1020190103965A KR102214384B1 (ko) 2018-08-28 2019-08-23 유기 발광 소자
KR10-2019-0103965 2019-08-23

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KR101593368B1 (ko) * 2015-04-22 2016-02-11 주식회사 엘지화학 헤테로환 화합물 및 이를 포함하는 유기 발광 소자
KR20170071399A (ko) * 2015-12-15 2017-06-23 주식회사 두산 유기 화합물 및 이를 포함하는 유기 전계 발광 소자
WO2017171376A1 (fr) * 2016-03-28 2017-10-05 주식회사 엘지화학 Composé et élément électronique organique le comprenant
KR101784606B1 (ko) * 2015-04-27 2017-11-06 주식회사 엘지화학 이중스피로형 화합물 및 이를 포함하는 유기 발광 소자
KR20170126691A (ko) * 2016-05-10 2017-11-20 주식회사 엘지화학 신규한 화합물 및 이를 포함하는 유기 발광 소자
WO2018182259A1 (fr) * 2017-03-30 2018-10-04 주식회사 엘지화학 Elément électroluminescent organique
WO2019004790A1 (fr) * 2017-06-30 2019-01-03 주식회사 엘지화학 Composé hétérocyclique et élément électroluminescent organique le contenant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101593368B1 (ko) * 2015-04-22 2016-02-11 주식회사 엘지화학 헤테로환 화합물 및 이를 포함하는 유기 발광 소자
KR101784606B1 (ko) * 2015-04-27 2017-11-06 주식회사 엘지화학 이중스피로형 화합물 및 이를 포함하는 유기 발광 소자
KR20170071399A (ko) * 2015-12-15 2017-06-23 주식회사 두산 유기 화합물 및 이를 포함하는 유기 전계 발광 소자
WO2017171376A1 (fr) * 2016-03-28 2017-10-05 주식회사 엘지화학 Composé et élément électronique organique le comprenant
KR20170126691A (ko) * 2016-05-10 2017-11-20 주식회사 엘지화학 신규한 화합물 및 이를 포함하는 유기 발광 소자
WO2018182259A1 (fr) * 2017-03-30 2018-10-04 주식회사 엘지화학 Elément électroluminescent organique
WO2019004790A1 (fr) * 2017-06-30 2019-01-03 주식회사 엘지화학 Composé hétérocyclique et élément électroluminescent organique le contenant

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