WO2020096326A1 - Diode électroluminescente organique - Google Patents

Diode électroluminescente organique Download PDF

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WO2020096326A1
WO2020096326A1 PCT/KR2019/014925 KR2019014925W WO2020096326A1 WO 2020096326 A1 WO2020096326 A1 WO 2020096326A1 KR 2019014925 W KR2019014925 W KR 2019014925W WO 2020096326 A1 WO2020096326 A1 WO 2020096326A1
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substituted
unsubstituted
group
light emitting
formula
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Korean (ko)
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최민우
전상영
하재승
전현수
김재은
천민승
이정하
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주식회사 엘지화학
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Priority claimed from KR1020190139626A external-priority patent/KR102264795B1/ko
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Priority to CN201980047228.7A priority Critical patent/CN112424965A/zh
Publication of WO2020096326A1 publication Critical patent/WO2020096326A1/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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking 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 suppression of an increase in progressive driving voltage.
  • the organic light emitting phenomenon refers to a phenomenon that converts 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, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.
  • the organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode.
  • the organic material layer is often formed of a multi-layered structure composed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • 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 suppression of an increase in progressive driving voltage.
  • the present invention provides the following organic light emitting device.
  • a cathode provided opposite the anode
  • a light emitting layer provided between the anode and the cathode
  • a hole transport region provided between the anode and the light emitting layer
  • It includes an electron transport region provided between the light emitting layer and the cathode,
  • a first electron blocking layer comprising a compound represented by Formula 1 below and
  • It comprises a second electron blocking layer comprising a compound represented by the formula (2):
  • L 1 to L 3 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar 1 is substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • R 1 and R 2 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 haloalkyl; Substituted or unsubstituted C 1-60 haloalkoxy; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • a and b are each an integer from 0 to 9
  • L 4 to L 6 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar 2 and Ar 3 are each independently, substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • R 3 to R 7 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 haloalkyl; Substituted or unsubstituted C 1-60 haloalkoxy; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • c is an integer from 0 to 5
  • d, e and f are each an integer from 0 to 4,
  • g is an integer from 0 to 3.
  • the organic light emitting device described above includes a first electron blocking layer and a second electron blocking layer each containing a compound having a specific structure in the hole transport region, so that an increase in progressive driving voltage is suppressed, and high luminous efficiency and low driving voltage characteristics are achieved. Can be represented.
  • 1 is an organic light emission consisting of a substrate 10, an anode 20, a second electron blocking layer 31, a first electron blocking layer 33, a light emitting layer 40, an electron transport layer 51 and a cathode 60 An example of the device is shown.
  • the substrate 10 the anode 20, the P-type carrier generation layer 35, the electron injection layer 37, the second electron blocking layer 31, the first electron blocking layer 33, the light emitting layer 40 ), Hole blocking layer (53).
  • Example 3 is a graph showing changes in driving voltage with time of the organic light emitting diodes of Example 1, Comparative Example 1 and Comparative Example 2.
  • substituted or unsubstituted refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or
  • a substituent having two or more substituents may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be straight chain or branched chain, and 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 a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. 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, styrenyl 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 an exemplary 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 is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure.
  • the fluorenyl group When the fluorenyl group is substituted, It can be back. However, it is not limited thereto.
  • heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as heterogeneous elements, and carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • heteroaryl include thiophene group, furan group, pyrrol 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 group, be
  • an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above.
  • the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group.
  • the heteroarylamine of the heteroaryl may be applied to the description of the heteroaryl described above.
  • the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group.
  • the description of the aryl group described above may be applied, except that the arylene is a divalent group.
  • the description of the heteroaryl described above may be applied, except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding.
  • the heterocycle is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that two substituents are formed by bonding.
  • the present invention provides an organic light emitting device in which a progressive driving voltage rise is suppressed by simultaneously including a first electron blocking layer and a second electron blocking layer each containing a compound having a specific structure in a hole transport region between the anode and the light emitting layer. I want to.
  • the first electron blocking layer is located in contact with the light emitting layer
  • the second electron blocking layer is located in contact with the first electron blocking layer.
  • the first electron blocking layer includes the compound represented by the formula (1), not only blocks the movement of electrons and suppresses triplet transition, but also facilitates injection and transport of holes into the light emitting layer to balance the carrier in the light emitting layer. It serves to match.
  • the second electron blocking layer includes a compound represented by Chemical Formula 2, and has a triplet energy level higher than the triplet energy level of the phosphorescent material, so that the triplet exciton of the light emitting layer fails to emit light and is in the hole transport region. It serves to prevent loss. Therefore, the organic light emitting device according to the present invention can prevent the accumulation of electric charges at the interface between each layer, and thus increase in the progressive driving voltage can be suppressed, thereby exhibiting high efficiency and long life characteristics.
  • the positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth.
  • 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), and indium zinc oxide (IZO); A combination of metal and oxide 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, but are not limited thereto.
  • the cathode material is preferably 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;
  • There is a multilayer structure material such as LiF / Al or LiO 2 / Al, but is not limited thereto.
  • the organic light emitting device includes a hole transport region provided between the anode and the light emitting layer.
  • a hole transport region provided between the anode and the light emitting layer.
  • the hole transport region of the organic light emitting device of the present invention includes a first electron blocking layer and a second electron blocking layer, and preferably includes at least three layers including additional organic layers other than the first and second electron blocking layers. It consists of an organic layer.
  • the first electron blocking layer is a layer positioned in contact with the light emitting layer, and includes a compound represented by Formula 1, which is an amine-based compound in which phenanthrene having high aromaticity is substituted on both sides.
  • a compound represented by Formula 1 which is an amine-based compound in which phenanthrene having high aromaticity is substituted on both sides.
  • L 1 to L 3 are each independently a single bond, phenylene, or naphthylene.
  • L 1 and L 2 are each independently phenylene, specifically, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, and L 3 is a single bond; Or any one selected from the group consisting of:
  • Ar 1 is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, or fluorenyl,
  • dibenzofuranyl, dibenzothiophenyl and fluorenyl may each be unsubstituted or substituted with C 1-10 alkyl, or C 6-20 aryl.
  • Ar 1 is any one selected from the group consisting of:
  • X 1 is O, S, or CZ 2 Z 3 ,
  • Z 1 to Z 3 are each independently methyl or phenyl.
  • Z 1 is phenyl
  • Z 2 and Z 3 are both methyl, or both phenyl.
  • R 1 and R 2 are hydrogen, and a and b meaning the number of R 1 and R 2 are 0 or 1, respectively.
  • the compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-3:
  • L 1 to L 3 and Ar 1 is as defined in Chemical Formula 1.
  • the second electron blocking layer is a layer positioned between the anode and the first electron blocking layer, preferably, in contact with the first electron blocking layer, and includes a compound represented by Chemical Formula 2.
  • the compound represented by Chemical Formula 2 may easily transport holes to the light emitting layer including nitrogen atoms contributing to aromaticity, while electrons may not flow through the first electron blocking layer at the same time including nitrogen atoms not contributing to aromaticity. It has a stable structure. Accordingly, an increase in voltage due to interface deterioration between the first electron blocking layer and the second electron blocking layer of the organic light emitting device can be suppressed.
  • L 4 to L 6 are each independently a single bond, phenylene, or biphenylylene.
  • L 4 is a single bond, or phenylene, more preferably, a single bond, or 1,4-phenylene, and L 5 and L 6 are each independently a single bond, 1,2-phenyl Ren, 1,3-phenylene, or 1,4-phenylene or 4,4'-biphenylylene.
  • Ar 2 and Ar 3 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, carbazolyl, or spiro [acridine -9,9'-fluorene] (spiro [acridine-9,9'-fluoren]),
  • dibenzofuranyl, dibenzothiophenyl, fluorenyl and spiro [acridine-9,9'-fluorene] are each unsubstituted or substituted with C 1-10 alkyl or C 6-20 aryl. Can be substituted.
  • Ar 2 and Ar 3 are each independently any one selected from the group consisting of:
  • X 2 is O, S, or CZ 5 Z 6 ,
  • Z 4 to Z 6 are each independently methyl or phenyl.
  • Z 4 is phenyl
  • Z 5 and Z 6 are both methyl, or both phenyl.
  • R 3 to R 7 are hydrogen, and c to g, which means the number of R 3 to R 7 , are 0 or 1, respectively.
  • the compound represented by Chemical Formula 2 is represented by the following Chemical Formula 2-1:
  • L 4 to L 6 , Ar 2 and Ar 3 is as defined in Chemical Formula 1.
  • E T (EBL1) is the triplet energy of the compound represented by Formula 1,
  • E T (EBL2) is the triplet energy of the compound represented by the formula (2).
  • the difference between the triplet energy of the compound represented by Formula 1 and the triplet energy of the compound represented by Formula 2 is 0.15 eV or less, or the triplet energy of the compound represented by Formula 2 is represented by Formula 1
  • the first electron blocking layer containing the compound represented by the formula (1) does not serve to primarily block the triplet exciton of high energy that is not emitted from the light emitting layer , Since the triplet exciton exerts an electrical load on the compound represented by Chemical Formula 2, the life of the organic light emitting device may be reduced.
  • the first electron blocking layer can effectively block the exciton of the high triplet energy that is not emitted from the light emitting layer, thereby reducing the electrical load on the other organic layer close to the positive electrode. Aging can be suppressed and the life of the device can be improved.
  • the compound represented by Chemical Formula 2 of the second electron blocking layer has a triplet energy level similar to that of other organic layers close to the anode, and thus has high energy triplet excitons not filtered by the first blocking layer. Since it can be quickly moved toward the anode, a decrease in life due to non-luminous triplet excitons can be prevented.
  • This triplet energy can be calculated using a time dependent density functional theory (TD-DFT).
  • TD-DFT time dependent density functional theory
  • the calculation of the general density function uses the 'Gaussian09' package, which is a commercial calculation program developed by Gaussian, and is used as a Beke exchange and Perdew correlation-correlation functional (B3PW91) and a basis function (basis set). Use 6-31G *.
  • B3PW91 Beke exchange and Perdew correlation-correlation functional
  • Basis set basis function
  • the triplet energy can also be obtained using the following conversion formula.
  • ⁇ edge means the wavelength value of the intersection of the tangent and the horizontal axis by drawing a tangent to the rise of the short wavelength side of the phosphorescence spectrum when the phosphorescence spectrum is represented by taking the phosphorescence intensity on the vertical axis and the wavelength on the horizontal axis.
  • the organic light emitting device may further include a positive type-carrier generation layer (P-CGL) in the hole transport region.
  • P-CGL positive type-carrier generation layer
  • the 'P-type carrier generation layer' is a layer that helps more holes to move toward the emission layer by accepting electrons from the organic layer on the cathode side to generate holes, and the organic light-emitting device according to the present invention generates the P-type carrier
  • the light emitting efficiency of the device may be increased and the driving voltage may be lowered by including the layer.
  • the P-type carrier generation layer is provided between the anode and the second electron blocking layer, most preferably in contact with the anode.
  • the P-type carrier generation layer includes a p-dopant material and a hole injection material.
  • the p-dopant material refers to a material that allows the host material to have p-semiconductor properties.
  • the p-semiconductor property is a property of injecting or transporting holes at a HOMO (Highest occupied molecular orbital) energy level, that is, hole mobility. It can be defined as a property of a material that is larger than the electron mobility.
  • the p-dopant material is represented by Formula 5 or 6 below:
  • a 1 to A 3 are each independently, unsubstituted or substituted with one or more substituents each independently selected from the group consisting of cyano, halogen and C 1-10 haloalkyl, C 6-60 aryl; Or C 2-60 heteroaryl comprising any one or more heteroatoms selected from the group consisting of N, O and S,
  • a 4 to A 9 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; amides; SO 2 (C 6-60 aryl); Substituted or unsubstituted substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
  • a 1 to A 3 are each independently phenyl, naphthyl, pyridine, pyrazine, pyrimidine, quinoline, or isoquinoline,
  • a 1 to A 3 are unsubstituted or substituted with one or more cyano or halogen.
  • Chemical Formula 5 the compound represented by Chemical Formula 5 may be represented by the following Chemical Formula 5-1:
  • a 4 to A 9 are each independently, cyano; Nitro; SO 2 (C 6-10 aryl); C 6-10 aryl unsubstituted or substituted with one or more cyano or nitro; Or C 2-10 alkenyl unsubstituted or substituted with one or more cyano or nitro.
  • Chemical Formula 6 may be represented by any one of the following Chemical Formulas 6-1 to 6-6:
  • the P-type carrier generation layer contains less than 10% by weight of the p-dopant material.
  • the driving voltage may be lowered while increasing the luminous efficiency of the organic light emitting device.
  • the hole injection material generally has the ability to transport holes used in the hole injection layer, has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and electron injection of excitons generated in the light emitting layer
  • a compound that prevents migration to the layer or electron injection material and has excellent thin film formation ability can be used.
  • 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 material layer.
  • the hole injection material include: metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, perylene (perylene) ) -Based organics, anthraquinones, and polyaniline- and polythiophene-based conductive polymers, but are not limited thereto.
  • the organic light emitting device may further include a hole injection layer for injecting holes from the electrode into the hole transport region.
  • the hole injection layer is provided between the P-type carrier generation layer and the second electron blocking layer, and serves to transport holes generated from the P-type carrier generation layer while injecting holes into the emission layer.
  • the hole injection layer is made of a hole injection material, and preferably, the hole injection material is the same as the hole injection material included in the P-type carrier generation layer.
  • the organic light emitting device includes a light emitting layer including a phosphorescent material.
  • the light-emitting layer includes two or more host materials, most preferably a P-type host and an N-type host material at the same time, so that an appropriate ratio of holes and electrons can be maintained in the entire light-emitting layer, and thus excitons are formed in the entire light-emitting layer.
  • the light-emitting layer includes two or more host materials, most preferably a P-type host and an N-type host material at the same time, so that an appropriate ratio of holes and electrons can be maintained in the entire light-emitting layer, and thus excitons are formed in the entire light-emitting layer.
  • the light emitting layer includes a first host material represented by Chemical Formula 3 and a second host material represented by Chemical Formula 4:
  • Ar 11 and Ar 12 are each independently substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • R 11 and R 12 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 haloalkyl; Substituted or unsubstituted C 1-60 haloalkoxy; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • h and i are each an integer from 0 to 4,
  • Y is O or S
  • Ar 13 is substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • HAr is C 2-60 heteroaryl containing one or more substituted or unsubstituted N atoms
  • R 13 and R 14 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 haloalkyl; Substituted or unsubstituted C 1-60 haloalkoxy; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • k and j are integers of 0 to 3, respectively.
  • the light emitting layer may include a compound represented by the following Chemical Formula 3-1 as a first host material, and a compound represented by the following Chemical Formula 4-1 as a second host material:
  • the light emitting layer may further include a dopant material.
  • the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound.
  • a compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like but are not limited thereto.
  • examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.
  • the light emitting layer may include an iridium complex as a dopant
  • the organic light emitting device having the above-described host material and the light emitting layer including the dopant material may exhibit a maximum wavelength ( ⁇ max ) in the emission spectrum from 500 nm to 550 nm. Therefore, the organic light emitting device is a green light emitting organic light emitting device.
  • the organic light emitting device includes an electron transport region provided between the light emitting layer and the cathode.
  • the electron transport region is a region that transports electrons from the cathode to the light emitting layer, and generally includes an electron transport layer.
  • the electron transport region includes a hole blocking layer, an electron transport layer and an electron injection layer.
  • the hole blocking layer is formed on the light emitting layer, and specifically, the hole blocking layer is provided in contact with the light emitting layer, thereby preventing excessive movement of holes and increasing the probability of hole-electron bonding, thereby improving the efficiency of the organic light emitting device. It means the floor.
  • the hole blocking layer includes a hole blocking material, an example of such a hole blocking material is a triazole derivative; Oxadiazole derivatives; Phenanthroline derivatives may be used, but are not limited thereto.
  • the electron transport layer means a layer formed between the light emitting layer and the cathode, preferably between the hole blocking layer and the electron injection layer, which will be described later, to receive electrons from the electron injection layer and transport electrons to the light emitting layer.
  • the electron transport layer includes an electron transport material, and as the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable.
  • a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer a material having high mobility for electrons is suitable.
  • the electron transport material include pyridine derivatives; Pyrimidine derivatives; Triazole derivatives; Al complex 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 according to the prior art.
  • suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.
  • the organic light emitting device may further include an electron injection layer between the electron transport layer and the cathode.
  • the electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred.
  • the material that can be used as the electron injection layer LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, tria Sol, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
  • FIG. 1 is composed of a substrate 10, an anode 20, a hole transport region 30, a light emitting layer 40, an electron transport region 50 and a cathode, and the hole transport region 30 includes a second electron blocking layer (31) and the first electron blocking layer 33 are sequentially provided, and an example of an organic light emitting device in which the electron transport layer 51 is provided in the electron transport region 50 is shown.
  • the compound represented by Formula 1 may be included in the first electron blocking layer 33 and the compound represented by Formula 2 may be included in the second electron blocking layer 31, respectively.
  • the hole transport region 30 has a P-type carrier generation layer (35)
  • the electron injection layer 37, the second electron blocking layer 31 and the first electron blocking layer 33 are sequentially provided
  • the electron transport region 50 has a hole blocking layer 53.
  • An example of an organic light emitting device in which the electron transport layer 51 and the electron injection layer 55 are sequentially provided is illustrated.
  • the compound represented by Formula 1 may be included in the first electron blocking layer 33 and the compound represented by Formula 2 may be included in the second electron blocking layer 31, respectively.
  • the organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configuration.
  • a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
  • PVD physical vapor deposition
  • each layer on it it can be prepared by depositing a material that can be used as a cathode thereon.
  • an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the light emitting layer may be formed by a host and a dopant by a vacuum deposition method as well as a solution application method.
  • the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the organic light emitting device may be a front emission type, a back emission type or a double-sided emission type depending on the material used.
  • the substrate on which ITO 30 ⁇ as an anode was deposited was cut to a size of 50 mm x 50 mm x 0.5 mm, placed in distilled water in which the dispersant was dissolved, and washed with ultrasonic waves.
  • the detergent used was a product of Fischer Co., and distilled water was used for Millipore Co. As the product filter, distilled water filtered secondarily was used. After washing the ITO for 30 minutes, the ultrasonic cleaning was repeated 10 times with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.
  • Compound HIL1 and p-dopant (3 wt%) were vacuum-deposited to a thickness of 100 MPa on the positive electrode thus prepared to form a P-type carrier generation layer, and compound HIL1 was vacuum-deposited to a thickness of 1100 MPa to form a hole injection layer. .
  • a second electron blocking layer was formed by vacuum-depositing the following compound 2-1 to a thickness of 350 MPa on the hole injection layer, and the following compound 1-1 on the second electron blocking layer was vacuumed to a thickness of 150 MPa.
  • the first electron blocking layer was formed by vapor deposition.
  • the first host (GH1) and the second host (GH2) on the first electron blocking layer in a weight ratio of 6 to 4, and a dopant (GD) by vacuum deposition at 6% by weight, a light emitting layer having a thickness of 350 ⁇ Formed
  • a hole blocking layer was formed by vacuum-depositing the compound HBL1 to a thickness of 50 ⁇ ⁇ on the light emitting layer, and then vacuum-depositing the compounds ETL1 and LiQ to a thickness of 170 ⁇ and 85 ⁇ , respectively, to form an electron transport layer.
  • lithium fluoride (LiF) having a thickness of 10 ⁇ was formed into an electron injection layer, and then magnesium and silver (1: 4) were formed with a thickness of 150 ⁇ as a cathode, and CPL was deposited at 600 C to complete the device.
  • the deposition rate of the organic material in the above process was maintained at 1 ⁇ / sec.
  • vacuum deposition of each layer was performed using a cluster type 1.0E-7 vacuum deposition machine (manufactured by Selcos).
  • An organic light emitting device was used in the same manner as in the above embodiment, except that Compound HTL1 was used instead of Compound 2-1 as the second electron blocking layer material, and Compound EBL1 was used instead of Compound 1-1 as the first electron blocking layer material. It was prepared.
  • An organic light emitting device was manufactured in the same manner as in the above Example, except that Compound EBL1 was used instead of Compound 1-1 as the first electron blocking layer material.
  • the organic light emitting device of the embodiment employing the compound represented by Formula 1 and the compound represented by Formula 2 according to the present invention as a first electron blocking layer and a second electron blocking layer, respectively .
  • the organic light emitting device of Comparative Examples 1 and 2 it can be seen that not only does it exhibit excellent characteristics in terms of voltage and efficiency, but also has a significantly lower increase in the progressive driving voltage.
  • substrate 20 anode
  • first electron blocking layer 35 P-type carrier generation layer

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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 qui comprend une région de transport de trous contenant un composant ayant une structure spécifique, de manière à obtenir une faible tension d'attaque ainsi qu'un rendement lumineux élevé, et à éliminer l'augmentation de la tension d'attaque progressive.
PCT/KR2019/014925 2018-11-06 2019-11-05 Diode électroluminescente organique WO2020096326A1 (fr)

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WO2021070965A1 (fr) * 2019-10-11 2021-04-15 出光興産株式会社 Composé, matériau pour éléments électroluminescents organiques, élément électroluminescent organique et dispositif électronique
CN113861042A (zh) * 2020-06-30 2021-12-31 北京鼎材科技有限公司 一种化合物及其应用
CN114141971A (zh) * 2020-09-04 2022-03-04 江苏三月科技股份有限公司 一种包含菲基三芳胺类化合物的有机电致发光装置及其应用
WO2023027173A1 (fr) * 2021-08-27 2023-03-02 出光興産株式会社 Composé, matériau d'élément électroluminescent organique, élément électroluminescent organique et dispositif électronique

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