WO2017026727A1 - Organic electroluminescent device - Google Patents
Organic electroluminescent device Download PDFInfo
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- WO2017026727A1 WO2017026727A1 PCT/KR2016/008532 KR2016008532W WO2017026727A1 WO 2017026727 A1 WO2017026727 A1 WO 2017026727A1 KR 2016008532 W KR2016008532 W KR 2016008532W WO 2017026727 A1 WO2017026727 A1 WO 2017026727A1
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- organic
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- light emitting
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- 238000000034 method Methods 0.000 claims description 13
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- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- ZXZKYYHTWHJHFT-UHFFFAOYSA-N quinoline-2,8-diol Chemical compound C1=CC(=O)NC2=C1C=CC=C2O ZXZKYYHTWHJHFT-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/72—Spiro hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the present invention relates to an organic electroluminescent device. More particularly, the present invention relates to an organic light emitting display device comprising a specific hole transport material and a specific electron blocking material.
- an organic light emitting display device is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. That is, in the organic electroluminescent device, when an electric field is applied between both electrodes, electrons are injected from the cathode, holes are injected from the anode, and they recombine in the emission layer to emit light.
- More detailed structure of the organic light emitting device is a substrate, an anode, a hole injection layer for receiving holes in the anode, a hole transport layer for transporting holes, an electron blocking layer for blocking the entry of electrons from the light emitting layer to the hole transport layer, the hole and the electron coupling It consists of a light emitting layer that emits light, a hole blocking layer that blocks the entrance of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode.
- a light emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into an electron transport layer or a hole transport layer without a separate light emitting layer.
- a single polymer generally serves as a hole transport layer, a light emitting layer, and an electron transport layer. You can also do this at the same time.
- the organic thin film layers between the two electrodes are formed by vacuum deposition or spin coating, inkjet printing, laser thermal transfer, or the like. The reason why the organic light emitting diode is manufactured in a multilayer thin film structure is to stabilize the interface between the electrode and the organic material.
- the hole and the electron transport layer have a large difference in the movement speed of holes and electrons. This is because luminous efficiency can be increased by effectively transferring electrons and electrons to the light emitting layer to balance the density of holes and electrons.
- the driving principle of the organic light emitting display device is as follows. When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole injection layer and the hole transport layer. On the other hand, electrons are injected into the light emitting layer from the cathode via the electron injection layer and the electron transport layer, and carriers are recombined in the light emitting layer to generate excitons. The excitons change from the excited state to the ground state, whereby the fluorescent molecules in the light emitting layer emit light to form an image.
- the light emitted while the excited state falls to the ground state through the singlet excited state is called “fluorescence”
- the light emitted while falling to the ground state through the triplet excited state is called “phosphorescence”.
- fluorescence the probability of singlet excited state is 25% (triple state 75%), and there is a limit of luminous efficiency, while phosphorescence is used to emit up to 75% of triplet state and 25% of singlet excited state.
- the internal quantum efficiency can be up to 100%.
- the biggest problem for the organic light emitting device is life and efficiency. As the display becomes larger, such efficiency and life problems must be solved.
- the properties of the components included in each layer of the organic thin film layer including one or more layers including a light emitting layer between the anode and the cathode have a great influence on the driving voltage, the luminous efficiency, the luminance, and the lifetime of the device. Crazy Therefore, studies on the components included in each layer of the organic thin film layer are actively conducted.
- Patent Document 1 Korean Unexamined Patent Publication No. 10-2015-0034379, Japanese Patent No. 2395088, Japanese Patent No. 3828595 and Korean Patent Publication No. 10-2013-0099098.
- An object of the present invention is to provide an organic light emitting display device in which the luminous efficiency is remarkably improved by using a specific hole transport material and a specific electron blocking material.
- the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode, the organic film comprises a light emitting layer, between the anode and the light emitting layer
- An organic electroluminescent device comprising an organic film comprising a compound represented by Formula 1 and an organic film comprising a compound represented by Formula 2 is provided:
- n are each an integer of 0 to 5;
- p, q and r are each an integer of 0 to 4.
- Ar 1 is a single bond, an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 5 to 18 nuclear atoms;
- the Ar 2 to Ar 5 are the same or group different and each is independently selected from amines with each other, C 1 ⁇ C 10 alkyl group, C 2 ⁇ C 10 alkenyl group, C 2 ⁇ C 10 alkynyl group, C 3 ⁇ C 10 of the A cycloalkyl group, a nuclear atom having 3 to 10 heterocycloalkyl groups, a C 4 to C 60 aryl group and a nuclear atom having 5 to 20 heteroaryl groups;
- R 1 to R 3 are each other the same or different, each independently represent hydrogen, deuterium (D), halogen, cyano, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 of the Alkynyl group, C 6 ⁇ C 60 Aryl group, Nucleotide 5 to 40 heteroaryl group, C 6 ⁇ C 60 Aryloxy group, C 1 ⁇ C 40 Alkyloxy group, C 6 ⁇ C 60 Aryl An amine group, a C 3 to C 40 cycloalkyl group and a nuclear atom having 3 to 40 heterocycloalkyl groups;
- L 1 to L 3 is the same as or different from each other, and is each independently a single bond, an arylene group having 6 to 40 carbon atoms, or a heteroarylene group having 5 to 40 nuclear atoms;
- the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryloxy group, alkyloxy group, arylamine group, aryl group and heteroaryl group of Ar 2 to Ar 5 and R 1 to R 3 are each independently deuterium , Halogen, cyano group, nitro group, C 1 ⁇ C 40 alkyl group, halogen, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 6 ⁇ C 60 Aryl group, heteroaryl group of 5 to 60 nuclear atoms, aryloxy group of C 6 ⁇ C 60 , alkyloxy group of C 1 ⁇ C 40 , arylamine group of C 6 ⁇ C 60 , C 3 ⁇ C 40 Cycloalkyl group of 3 to 40 heterocycloalkyl group, C 1 ⁇ C 40 alkylsilyl group, C 1 ⁇ C 40
- the compound represented by Formula 2 may be represented by the following formula (3):
- R 1 , R 2 , R 3 , Ar 4 , Ar 5 , p, q, and r are each as defined in Formula 2.
- the compound represented by Formula 2 may be represented by the following formula (4):
- R 1 , R 2 , R 3 , Ar 4 , Ar 5 , L 3 , p, q, and r are each as defined in Formula 2.
- Alkyl as used herein means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.
- alkenyl refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
- alkynyl refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.
- Aryl in the present invention means a monovalent substituent derived from a C6 to C60 aromatic hydrocarbon combined with a single ring or two or more rings.
- a form in which two or more rings are attached to each other (pendant) or condensed may also be included.
- Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.
- Heteroaryl as used herein means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se.
- a form in which two or more rings are pendant or condensed with each other may be included, and may also include a form in which the two or more rings are condensed with an aryl group.
- heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, carbazolyl (carbazoleyl) and 2-furanyl, N-imidazolyl, 2-iso Sazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
- 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, be
- aryloxy is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms.
- R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
- alkyloxy is a monovalent substituent represented by R'O-, wherein R 'means an alkyl having 1 to 40 carbon atoms, and linear, branched or cyclic structure It may include.
- alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
- Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
- cycloalkyl is meant herein monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms.
- examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
- Heterocycloalkyl as used herein means a monovalent substituent derived from 3 to 40 non-aromatic hydrocarbons of nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S Or a hetero atom such as Se.
- heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.
- alkylsilyl means silyl substituted with alkyl having 1 to 40 carbon atoms
- arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms.
- condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
- the organic electroluminescent device of the present invention provides significantly improved driving voltage characteristics, luminous efficiency, and luminance by using a specific hole transport material and a specific electron blocking material.
- the present invention provides an organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode, wherein the organic film includes a light emitting layer, and a compound represented by the following Chemical Formula 1 between the anode and the light emitting layer: It relates to an organic electroluminescent device comprising an organic film comprising and an organic film comprising a compound represented by Formula 2 below:
- n are each an integer of 0 to 5
- p, q and r are each an integer of 0 to 4,
- Ar 1 is a single bond, an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 5 to 18 nuclear atoms,
- the Ar 2 to Ar 5 are the same or group different and each is independently selected from amines with each other, C 1 ⁇ C 10 alkyl group, C 2 ⁇ C 10 alkenyl group, C 2 ⁇ C 10 alkynyl group, C 3 ⁇ C 10 of the It is selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group of 3 to 10 nuclear atoms, an aryl group of C 4 ⁇ C 60 and a heteroaryl group of 5 to 20 nuclear atoms,
- R 1 to R 3 are each other the same or different, each independently represent hydrogen, deuterium (D), halogen, cyano, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 of the Alkynyl group, C 6 ⁇ C 60 Aryl group, Nucleotide 5 to 40 heteroaryl group, C 6 ⁇ C 60 Aryloxy group, C 1 ⁇ C 40 Alkyloxy group, C 6 ⁇ C 60 Aryl An amine group, a C 3 to C 40 cycloalkyl group and a nuclear atom having 3 to 40 heterocycloalkyl groups;
- L 1 to L 3 is the same as or different from each other, and each independently a single bond, an arylene group having 6 to 40 carbon atoms, or a heteroarylene group having 5 to 40 nuclear atoms,
- the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryloxy group, alkyloxy group, arylamine group, aryl group and heteroaryl group of Ar 2 to Ar 5 and R 1 to R 3 are each independently deuterium , Halogen, cyano group, nitro group, C 1 ⁇ C 40 alkyl group, halogen C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 6 ⁇ C 60
- the compound represented by Formula 2 may be represented by the following formula (3):
- R 1 , R 2 , R 3 , Ar 4 , Ar 5 , p, q and r are each as defined in Chemical Formula 2.
- the compound represented by Formula 2 may be represented by the following formula (4):
- R 1 , R 2 , R 3 , Ar 4 , Ar 5 , L 3 , p, q and r are each as defined in Formula 2.
- Ar 1 is a single bond or an arylene group of C 6 to C 19
- Ar 4 is an aryl group of C 4 to C 60 or a heteroaryl group of 5 to 20 nuclear atoms
- Ar 5 is an aryl group of C 4 to C 60 , but is not limited thereto.
- the compound represented by Formula 1 of the present invention may be more specifically selected from the group consisting of the following compounds, but is not limited thereto.
- the compound represented by Formula 1 of the present invention may be more preferably selected from the group consisting of the following compounds:
- the compound represented by Formula 2 of the present invention may be more specifically selected from the group consisting of the following compounds, but is not limited thereto.
- an organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode, wherein the organic film includes a light emitting layer, and is represented by the formula (1) between the anode and the light emitting layer It may include an organic film containing a compound and an organic film containing a compound represented by the formula (2).
- the organic film including the compound represented by Chemical Formula 1 is a hole transport layer
- the organic film including the compound represented by Chemical Formula 2 is an electron blocking layer, but is not limited thereto.
- the hole transport layer may further include a hole transport material known in the art, in addition to the compound represented by Formula 1, and the electron blocking layer further includes a hole transport material known in the art, in addition to the compound represented by Formula 2 Can be.
- the organic thin film layer further includes a hole injection layer, each layer included in the organic thin film layer is a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), and an emission layer (EML) Can be stacked in the order of.
- HIL hole injection layer
- HTL hole transport layer
- EBL electron blocking layer
- EML emission layer
- the organic thin film layer further includes a hole injection layer, a light emitting layer, an electron transport layer, and an electron injection layer, and each layer included in the organic thin film layer includes a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL). ), An emission layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL).
- HIL hole injection layer
- HTL hole transport layer
- EBL electron blocking layer
- EML emission layer
- ETL electron transport layer
- EIL electron injection layer
- the organic thin film layer may have a structure in which layers having various functions known in the art (not limited to organic layers) are stacked in addition to the laminated structure as described above for efficient light emission and long life of the device. .
- the organic electroluminescent device of the present invention will be described by way of example.
- the contents exemplified below do not limit the organic light emitting device of the present invention.
- a positive electrode is coated on a surface of a substrate by a conventional method to form a positive electrode.
- the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof.
- the positive electrode material indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, may be used.
- a hole injection layer is formed on the surface of the anode by vacuum thermal evaporation or spin coating of a hole injection layer (HIL) material in a conventional manner.
- hole injection layer materials include copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA), 4,4', 4" -tris (3-methylphenyl Amino) phenoxybenzene (m-MTDAPB), starburst amines 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA), 4,4', 4" -tris Examples include (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA) or IDE406 available from Idemitsu.
- a hole transport layer is formed on the surface of the hole injection layer by vacuum thermal evaporation or spin coating of a hole transport layer (HTL) material in a conventional manner.
- the hole transport layer may be formed by stacking the compound represented by Chemical Formula 1.
- the light emitting layer (EML) material on the surface of the hole transport layer by vacuum thermal evaporation or spin coating in a conventional manner to form a light emitting layer.
- EML light emitting layer
- tris (8-hydroxyquinolinolato) aluminum (Alq3), etc. may be used as the sole light emitting material or the light emitting host material among the light emitting layer materials, and in the case of blue, Balq (8-hydroxyquinolineberyllium) may be used.
- DPVBi 4,4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl) series, spiro (spiro) substance, spiro-DPVBi (spiro-4, 4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzooxazolyl) -phenol lithium salt), bis (biphenylvinyl) benzene, aluminum -Quinoline metal complexes, metal complexes of imidazole, thiazole and oxazole and the like can be used.
- An electron blocking layer is formed on the surface of the hole transport layer by vacuum thermal evaporation or spin coating of an electron blocking layer (EBL) material in a conventional manner.
- EBL electron blocking layer
- a compound represented by Chemical Formula 2 may be used as the electron blocking layer material.
- IDE102 In the case of a dopant which can be used together with a light emitting host in the light emitting layer material, IDE102, IDE105, which is available from Idemitsu as a fluorescent dopant, and tris (2-phenylpyridine) iridium (III) (Ir (ppy) as a phosphorescent dopant. 3), iridium (III) bis [(4,6-difluorophenyl) pyridinato-N, C-2 '] picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys Lett., 2001, 79, 3082-3084), platinum (II) octaethyl porphyrin (PtOEP), TBE002 (Kobiion) and the like can be used.
- FIrpic ihaya Adachi et al., Appl. Phys Lett., 2001, 79, 3082-3084
- An electron transport layer is formed on the surface of the light emitting layer by vacuum thermal evaporation or spin coating of an electron transport layer (ETL) material in a conventional manner.
- ETL electron transport layer
- the electron transport layer material used is not particularly limited, and preferably tris (8-hydroxyquinolinolato) aluminum (Alq 3) may be used.
- HBL hole blocking layer
- the hole blocking layer may be formed by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner, and the hole blocking layer material is not particularly limited, but is preferably (8-hydroxyquinolinol).
- Earth) lithium (Liq) bis (8-hydroxy-2-methylquinolinolato) -aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF and the like can be used.
- An electron injection layer is formed on the surface of the electron transport layer by vacuum thermal evaporation or spin coating of an electron injection layer (EIL) material in a conventional manner.
- EIL electron injection layer
- the material of the electron injection layer may be a material such as LiF, Liq, Li 2 O, BaO, NaCl, CsF, etc.
- the negative electrode is vacuum-deposited on the surface of the electron injection layer by a conventional method Form.
- the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used.
- indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode through which light can pass.
- the capping layer CPL may be formed on the surface of the cathode by the composition for capping layer formation of the present invention.
- the organic light emitting device may be manufactured in the order described above, that is, in the order of anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode, and vice versa.
- the electron injection layer, the electron transport layer, the light emitting layer, the electron blocking layer, the hole transport layer, the hole injection layer and the anode may be manufactured in the order.
- HAT-CN hole injection layer
- HTL hole transport layer
- EBL electron blocking layer
- 10-Bis (2-naphthyl) anthraces (ADN) was doped with 25 nm of 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) as a dopant.
- Anthracene derivative and LiQ were mixed 1: 1 to deposit an electron transport layer (ETL) with a thickness of 30 nm, and LiQ was deposited with an electron injection layer (EIL) on a thickness of 10 nm. Thereafter, a mixture of magnesium and silver (Ag) in a 9: 1 mixture was deposited to a thickness of 15 nm, and N4, N4'-bis [4- [bis () was formed as a capping layer on the cathode.
- ETL electron transport layer
- EIL electron injection layer
- An organic electroluminescent device was manufactured by bonding a seal cap containing a hygroscopic agent with a UV curable adhesive to protect the organic electroluminescent device from O 2 or moisture in the air.
- An organic light emitting diode was manufactured according to the same method as Example 1 except for using the electron blocking material 2-2 to 2-11 instead of the compound 2-1 in Example 1.
- Example 1 the compound 1-1 was used instead of compound 1-1, and the electron blocking material was used compound 2-3, compound 2-4, and compound 2-8 instead of compound 2-1.
- An organic light emitting display device was manufactured in the same manner as in Example 1.
- An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound 1-1 and NPB instead of the compound 2-1 as the electron blocking material in Example 1.
- An organic light emitting diode was manufactured according to the same method as Example 1 except for using NPB instead of the compound 1-1 as the hole transport material in Example 8.
- the present invention relates to an organic electroluminescent device. More particularly, the present invention relates to an organic light emitting display device comprising a specific hole transport material and a specific electron blocking material.
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Abstract
The present invention relates to an organic electroluminescent device comprising a cathode, an anode and at least one layer of organic film between the cathode and the anode and, more specifically, to an organic electroluminescent device comprising, between the cathode and a light emitting layer, an organic film comprising one or more types of compounds represented by chemical formula 1 and an organic film comprising one or more types of compounds represented by chemical formula 2, thereby having high efficiency characteristics.
Description
본 발명은 유기전계발광소자에 관한 것이다. 더욱 상세하게는 특정의 정공수송물질과 특정의 전자차단물질을 포함하는 것을 특징으로 하는 유기전계발광소자에 관한 것이다.The present invention relates to an organic electroluminescent device. More particularly, the present invention relates to an organic light emitting display device comprising a specific hole transport material and a specific electron blocking material.
현재까지 평판 디스플레이의 대부분을 액정 디스플레이가 차지하고 있으나, 보다 경제적이고 성능이 뛰어나면서 액정 디스플레이와 차별화된 새로운 평판 디스플레이를 개발하려는 노력이 전세계적으로 활발히 진행되고 있다. 최근 차세대 평판 디스플레이로 각광을 받고 있는 유기전계발광소자는 액정 디스플레이에 비해 낮은 구동전압, 빠른 응답속도 및 광시야각 등의 장점을 가지고 있다.To date, the majority of flat panel displays are liquid crystal displays, but efforts are being made worldwide to develop new flat panel displays that are more economical and superior in performance. Recently, organic light emitting diodes, which have been spotlighted as next-generation flat panel displays, have advantages such as low driving voltage, fast response speed, and wide viewing angle, compared to liquid crystal displays.
일반적으로 유기전계발광소자의 가장 간단한 구조는 발광층 및 상기 층을 낀 한 쌍의 대향전극으로 구성되어 있다. 즉, 유기전계발광소자에서는 양 전극간에 전계가 인가되면, 음극으로부터 전자가 주입되고, 양극으로부터 정공이 주입되어 이들이 발광층에 있어서 재결합하여 광을 방출하는 현상을 이용한다.In general, the simplest structure of an organic light emitting display device is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. That is, in the organic electroluminescent device, when an electric field is applied between both electrodes, electrons are injected from the cathode, holes are injected from the anode, and they recombine in the emission layer to emit light.
보다 자세한 유기전계발광소자의 구조는 기판, 애노드, 애노드에서 정공을 받아들이는 정공주입층, 정공을 수송하는 정공수송층, 발광층으로부터 정공수송층으로 전자의 진입을 차단하는 전자차단층, 정공과 전자가 결합하여 빛을 내는 발광층, 발광층에서 전자수송층으로 정공의 진입을 차단하는 정공 차단층, 캐소드에서 전자를 받아들여 발광층으로 수송하는 전자수송층, 캐소드에서 전자를 받아들이는 전자주입층 및 캐소드로 구성되어 있다. 경우에 따라서 별도의 발광층 없이 전자수송층이나 정공수송층에 소량의 형광 또는 인광성 염료를 도핑하여 발광층을 구성할 수도 있으며, 고분자를 사용할 경우에는 일반적으로 하나의 고분자가 정공수송층과 발광층 및 전자수송층의 역할을 동시에 수행할 수도 있다. 두 전극 사이의 유기물 박막층들은 진공증착법 또는 스핀 코팅, 잉크젯 프린팅, 레이저 열전사법 등의 방법으로 형성된다. 이렇게 유기전계발광소자를 다층 박막 구조로 제작하는 이유는 전극과 유기물 사이의 계면 안정화를 위함이며 또한 유기물질의 경우, 정공과 전자의 이동 속도 차이가 크므로 적절한 정공수송층과 전자수송층을 사용하여 정공과 전자를 발광층으로 효과적으로 전달하여 정공과 전자의 밀도가 균형을 이루도록 하면 발광 효율을 높일 수 있기 때문이다.More detailed structure of the organic light emitting device is a substrate, an anode, a hole injection layer for receiving holes in the anode, a hole transport layer for transporting holes, an electron blocking layer for blocking the entry of electrons from the light emitting layer to the hole transport layer, the hole and the electron coupling It consists of a light emitting layer that emits light, a hole blocking layer that blocks the entrance of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode. In some cases, a light emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into an electron transport layer or a hole transport layer without a separate light emitting layer.In the case of using a polymer, a single polymer generally serves as a hole transport layer, a light emitting layer, and an electron transport layer. You can also do this at the same time. The organic thin film layers between the two electrodes are formed by vacuum deposition or spin coating, inkjet printing, laser thermal transfer, or the like. The reason why the organic light emitting diode is manufactured in a multilayer thin film structure is to stabilize the interface between the electrode and the organic material. Also, in the case of the organic material, the hole and the electron transport layer have a large difference in the movement speed of holes and electrons. This is because luminous efficiency can be increased by effectively transferring electrons and electrons to the light emitting layer to balance the density of holes and electrons.
유기전계발광소자의 구동 원리는 다음과 같다. 상기 애노드 및 캐소드 간에 전압을 인가하면 애노드로부터 주입된 정공은 정공주입층 및 정공수송층을 경유하여 발광층으로 이동된다. 한편, 전자는 캐소드로부터 전자주입층 및 전자수송층을 경유하여 발광층에 주입되고 발광층 영역에서 캐리어들이 재결합하여 엑시톤(exiton)을 생성한다. 이 엑시톤이 여기 상태에서 기저 상태로 변화되고, 이로 인하여 발광층의 형광성 분자가 발광함으로써 화상이 형성된다. 이때 여기 상태가 일중항 여기 상태를 통하여 기저 상태로 떨어지면서 발광하는 것을 "형광"이라고 하며, 삼중항 여기 상태를 통하여 기저 상태로 떨어지면서 발광하는 것을 "인광"이라고 한다. 형광의 경우, 일중항 여기 상태의 확률일 25%(삼중항 상태 75%)이며, 발광 효율의 한계가 있는 반면에 인광을 사용하면 삼중항 상태 75%와 일중항 여기 상태 25%까지 발광에 이용할 수 있으므로 이론적으로 내부양자 효율 100%까지 가능하다.The driving principle of the organic light emitting display device is as follows. When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole injection layer and the hole transport layer. On the other hand, electrons are injected into the light emitting layer from the cathode via the electron injection layer and the electron transport layer, and carriers are recombined in the light emitting layer to generate excitons. The excitons change from the excited state to the ground state, whereby the fluorescent molecules in the light emitting layer emit light to form an image. At this time, the light emitted while the excited state falls to the ground state through the singlet excited state is called "fluorescence", and the light emitted while falling to the ground state through the triplet excited state is called "phosphorescence". In the case of fluorescence, the probability of singlet excited state is 25% (triple state 75%), and there is a limit of luminous efficiency, while phosphorescence is used to emit up to 75% of triplet state and 25% of singlet excited state. Theoretically, the internal quantum efficiency can be up to 100%.
이러한 유기전계발광소자에 있어 가장 문제가 되는 것은 수명과 효율인데, 디스플레이가 대면적화되면서 이러한 효율이나 수명 문제는 반드시 해결해야 되는 상황이다. The biggest problem for the organic light emitting device is life and efficiency. As the display becomes larger, such efficiency and life problems must be solved.
유기전계발광소자에 있어서 양극과 음극 사이에 발광층을 포함하는 일층 또는 복수층으로 이루어지는 유기 박막층의 각층에 포함되는 성분들의 특성은 소자의 구동 전압, 발광 효율, 휘도, 및 소자의 수명에 큰 영향을 미친다. 따라서, 상기 유기 박막층의 각층에 포함되는 성분들에 대한 연구가 활발히 진행되고 있다. In the organic electroluminescent device, the properties of the components included in each layer of the organic thin film layer including one or more layers including a light emitting layer between the anode and the cathode have a great influence on the driving voltage, the luminous efficiency, the luminance, and the lifetime of the device. Crazy Therefore, studies on the components included in each layer of the organic thin film layer are actively conducted.
[선행기술문헌][Preceding technical literature]
(특허문헌 1) 대한민국 공개특허 제10-2015-0034379호, 일본 등록특허 제2395088호, 일본 등록특허 제3828595호 및 대한민국 공개특허 제10-2013-0099098호.(Patent Document 1) Korean Unexamined Patent Publication No. 10-2015-0034379, Japanese Patent No. 2395088, Japanese Patent No. 3828595 and Korean Patent Publication No. 10-2013-0099098.
본 발명은 특정의 정공수송물질 및 특정의 전자차단물질을 사용함으로써 발광 효율이 현저히 향상되는 유기전계발광소자를 제공하는 것을 목적으로 한다.An object of the present invention is to provide an organic light emitting display device in which the luminous efficiency is remarkably improved by using a specific hole transport material and a specific electron blocking material.
상기 목적을 달성하기 위하여, 본 발명은 양극, 음극, 및 상기 양극과 음극 사이에 적어도 한 층 이상의 유기막을 포함하는 유기 전계 발광소자로서, 상기 유기막은 발광층을 포함하며, 상기 양극과 발광층 사이에 하기 화학식 1로 표시되는 화합물을 포함하는 유기막 및 하기 화학식 2로 표시되는 화합물을 포함하는 유기막을 포함하는 유기전계발광소자를 제공한다:In order to achieve the above object, the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode, the organic film comprises a light emitting layer, between the anode and the light emitting layer An organic electroluminescent device comprising an organic film comprising a compound represented by Formula 1 and an organic film comprising a compound represented by Formula 2 is provided:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서, here,
m 및 n은 각각 0 내지 5의 정수이며;m and n are each an integer of 0 to 5;
p, q 및 r은 각각 0 내지 4의 정수이며;p, q and r are each an integer of 0 to 4;
Ar1은 단일결합, C6~C18의 아릴렌기 또는 핵원자수 5 내지 18개의 헤테로아릴렌기이며;Ar 1 is a single bond, an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 5 to 18 nuclear atoms;
Ar2 내지 Ar5는 서로 동일하거나 상이하고, 각각 독립적으로 아민기, C1~C10의 알킬기, C2~C10의 알케닐기, C2~C10의 알키닐기, C3~C10의 시클로알킬기, 핵원자수 3 내지 10개의 헤테로시클로알킬기, C4~C60의 아릴기 및 핵원자수 5 내지 20개의 헤테로아릴기로 이루어진 군으로부터 선택되며;The Ar 2 to Ar 5 are the same or group different and each is independently selected from amines with each other, C 1 ~ C 10 alkyl group, C 2 ~ C 10 alkenyl group, C 2 ~ C 10 alkynyl group, C 3 ~ C 10 of the A cycloalkyl group, a nuclear atom having 3 to 10 heterocycloalkyl groups, a C 4 to C 60 aryl group and a nuclear atom having 5 to 20 heteroaryl groups;
R1 내지 R3은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소(D), 할로겐, 시아노, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 40개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40개의 헤테로시클로알킬기로 이루어진 군으로부터 선택되며;R 1 to R 3 are each other the same or different, each independently represent hydrogen, deuterium (D), halogen, cyano, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of the Alkynyl group, C 6 ~ C 60 Aryl group, Nucleotide 5 to 40 heteroaryl group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryl An amine group, a C 3 to C 40 cycloalkyl group and a nuclear atom having 3 to 40 heterocycloalkyl groups;
L1 내지 L3는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합, C6~C40의 아릴렌기 또는 핵원자수 5 내지 40개의 헤테로아릴렌기이며; L 1 to L 3 is the same as or different from each other, and is each independently a single bond, an arylene group having 6 to 40 carbon atoms, or a heteroarylene group having 5 to 40 nuclear atoms;
상기 Ar2 내지 Ar5 및 R1 내지 R3의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴옥시기,알킬옥시기, 아릴아민기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, 할로겐, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다.The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryloxy group, alkyloxy group, arylamine group, aryl group and heteroaryl group of Ar 2 to Ar 5 and R 1 to R 3 are each independently deuterium , Halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, halogen, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 60 Aryl group, heteroaryl group of 5 to 60 nuclear atoms, aryloxy group of C 6 ~ C 60 , alkyloxy group of C 1 ~ C 40 , arylamine group of C 6 ~ C 60 , C 3 ~ C 40 Cycloalkyl group of 3 to 40 heterocycloalkyl group, C 1 ~ C 40 alkylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 an aryl phosphine group, C 6 ~ C 60 mono or diaryl phosphine of blood group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ one or more substituents selected from aryl silyl group consisting of C 60 When substituted with or unsubstituted with a plurality of substituents, they may be the same or different from each other.
본 발명의 바람직한 한 구현예에 따르면, 상기 화학식 2로 표시되는 화합물은 하기 화학식 3으로 표시되는 것일 수 있다:According to one preferred embodiment of the present invention, the compound represented by Formula 2 may be represented by the following formula (3):
[화학식 3][Formula 3]
상기 화학식 3에서 R1, R2, R3, Ar4, Ar5, p, q 및 r 각각은 상기 화학식 2에서 정의한 바와 같다. In Formula 3, R 1 , R 2 , R 3 , Ar 4 , Ar 5 , p, q, and r are each as defined in Formula 2.
본 발명의 바람직한 한 구현예에 따르면, 상기 화학식 2로 표시되는 화합물은 하기 화학식 4로 표시되는 것일 수 있다:According to one preferred embodiment of the present invention, the compound represented by Formula 2 may be represented by the following formula (4):
[화학식 4][Formula 4]
상기 화학식 4에서 R1, R2, R3, Ar4, Ar5, L3, p, q 및 r 각각은 상기 화학식 2에서 정의한 바와 같다. In Formula 4, R 1 , R 2 , R 3 , Ar 4 , Ar 5 , L 3 , p, q, and r are each as defined in Formula 2.
본 발명에서 "알킬"은 탄소수 1 내지 40개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있으나, 이에 한정되지는 않는다."Alkyl" as used herein means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.
본 발명에서 "알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkenyl" refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
본 발명에서 "알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.
본 발명에서 "아릴"은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60개의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등을 들 수 있으나, 이에 한정되지는 않는다."Aryl" in the present invention means a monovalent substituent derived from a C6 to C60 aromatic hydrocarbon combined with a single ring or two or more rings. In addition, a form in which two or more rings are attached to each other (pendant) or condensed may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.
본 발명에서 "헤테로아릴"은 핵원자수 5 내지 40개의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 나아가 아릴기와의 축합된 형태도 포함될 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(카바졸yl)과 같은 폴리사이클릭 고리 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있으나, 이에 한정되지는 않는다."Heteroaryl" as used herein means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may be included, and may also include a form in which the two or more rings are condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, carbazolyl (carbazoleyl) and 2-furanyl, N-imidazolyl, 2-iso Sazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
본 발명에서 "아릴옥시"는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 6 내지 60개의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
본 발명에서 "알킬옥시"는 R'O-로 표시되는 1가의 치환기로, 상기 R'는 탄소수 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R 'means an alkyl having 1 to 40 carbon atoms, and linear, branched or cyclic structure It may include. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서 "아릴아민"은 탄소수 6 내지 60개의 아릴로 치환된 아민을 의미한다."Arylamine" in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
본 발명에서 "시클로알킬"은 탄소수 3 내지 40개의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있으나, 이에 한정되지는 않는다.By "cycloalkyl" is meant herein monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
본 발명에서 "헤테로시클로알킬"은 핵원자수 3 내지 40개의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등을 들 수 있으나, 이에 한정되지는 않는다."Heterocycloalkyl" as used herein means a monovalent substituent derived from 3 to 40 non-aromatic hydrocarbons of nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S Or a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.
본 발명에서 "알킬실릴"은 탄소수 1 내지 40개의 알킬로 치환된 실릴이고, "아릴실릴"은 탄소수 6 내지 60개의 아릴로 치환된 실릴을 의미한다.In the present invention, "alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 6 to 60 carbon atoms.
본 발명에서 "축합고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.As used herein, the term “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
본 발명의 유기전계발광소자는 특정의 정공수송물질 및 특정의 전자차단물질을 사용함으로써 크게 개선된 구동 전압 특성, 발광 효율, 및 휘도를 제공한다. The organic electroluminescent device of the present invention provides significantly improved driving voltage characteristics, luminous efficiency, and luminance by using a specific hole transport material and a specific electron blocking material.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 양극, 음극, 및 상기 양극과 음극 사이에 적어도 한 층 이상의 유기막을 포함하는 유기 전계 발광소자로서, 상기 유기막은 발광층을 포함하며, 상기 양극과 발광층 사이에 하기 화학식 1로 표시되는 화합물을 포함하는 유기막 및 하기 화학식 2로 표시되는 화합물을 포함하는 유기막을 포함하는 유기전계발광소자에 관한 것이다:The present invention provides an organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode, wherein the organic film includes a light emitting layer, and a compound represented by the following Chemical Formula 1 between the anode and the light emitting layer: It relates to an organic electroluminescent device comprising an organic film comprising and an organic film comprising a compound represented by Formula 2 below:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서, here,
m 및 n은 각각 0 내지 5의 정수이며,m and n are each an integer of 0 to 5,
p, q 및 r은 각각 0 내지 4의 정수이며,p, q and r are each an integer of 0 to 4,
Ar1은 단일결합, C6~C18의 아릴렌기 또는 핵원자수 5 내지 18개의 헤테로아릴렌기이며,Ar 1 is a single bond, an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 5 to 18 nuclear atoms,
Ar2 내지 Ar5는 서로 동일하거나 상이하고, 각각 독립적으로 아민기, C1~C10의 알킬기, C2~C10의 알케닐기, C2~C10의 알키닐기, C3~C10의 시클로알킬기, 핵원자수 3 내지 10개의 헤테로시클로알킬기, C4~C60의 아릴기 및 핵원자수 5 내지 20개의 헤테로아릴기로 이루어진 군으로부터 선택되며,The Ar 2 to Ar 5 are the same or group different and each is independently selected from amines with each other, C 1 ~ C 10 alkyl group, C 2 ~ C 10 alkenyl group, C 2 ~ C 10 alkynyl group, C 3 ~ C 10 of the It is selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group of 3 to 10 nuclear atoms, an aryl group of C 4 ~ C 60 and a heteroaryl group of 5 to 20 nuclear atoms,
R1 내지 R3은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소(D), 할로겐, 시아노, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 40개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40개의 헤테로시클로알킬기로 이루어진 군으로부터 선택되며;R 1 to R 3 are each other the same or different, each independently represent hydrogen, deuterium (D), halogen, cyano, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of the Alkynyl group, C 6 ~ C 60 Aryl group, Nucleotide 5 to 40 heteroaryl group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryl An amine group, a C 3 to C 40 cycloalkyl group and a nuclear atom having 3 to 40 heterocycloalkyl groups;
L1 내지 L3는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합, C6~C40의 아릴렌기 또는 핵원자수 5 내지 40개의 헤테로아릴렌기이며,L 1 to L 3 is the same as or different from each other, and each independently a single bond, an arylene group having 6 to 40 carbon atoms, or a heteroarylene group having 5 to 40 nuclear atoms,
상기 Ar2 내지 Ar5 및 R1 내지 R3의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴옥시기,알킬옥시기, 아릴아민기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, 할로겐C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다.The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryloxy group, alkyloxy group, arylamine group, aryl group and heteroaryl group of Ar 2 to Ar 5 and R 1 to R 3 are each independently deuterium , Halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, halogen C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 60 An aryl group, a heteroaryl group of 5 to 60 nuclear atoms, an aryloxy group of C 6 to C 60 , an alkyloxy group of C 1 to C 40 , an arylamine group of C 6 to C 60 , and a C 3 to C 40 group Cycloalkyl group, 3 to 40 heterocycloalkyl group, C 1 ~ C 40 alkylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 an aryl phosphine group, C 6 ~ C 60 mono or diaryl phosphine of blood group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ one or more substituents selected from the group consisting of aryl silyl group of C 60 If substituted or unsubstituted and the ring, is substituted with plural substituents, they may be the same or different from each other.
본 발명의 바람직한 한 구현 예에 따르면, 상기 화학식 2로 표시되는 화합물은 하기 화학식 3으로 표시되는 것일 수 있다:According to one preferred embodiment of the present invention, the compound represented by Formula 2 may be represented by the following formula (3):
[화학식 3][Formula 3]
여기서, R1, R2, R3, Ar4, Ar5, p, q 및 r 각각은 상기 화학식 2에서 정의한 바와 같다. Here, R 1 , R 2 , R 3 , Ar 4 , Ar 5 , p, q and r are each as defined in Chemical Formula 2.
본 발명의 바람직한 한 구현 예에 따르면, 상기 화학식 2로 표시되는 화합물은 하기 화학식 4로 표시되는 것일 수 있다:According to one preferred embodiment of the present invention, the compound represented by Formula 2 may be represented by the following formula (4):
[화학식 4] [Formula 4]
여기서, R1, R2, R3, Ar4, Ar5, L3, p, q 및 r 각각은 상기 화학식 2에서 정의한 바와 같다.Here, R 1 , R 2 , R 3 , Ar 4 , Ar 5 , L 3 , p, q and r are each as defined in Formula 2.
본 발명의 바람직한 한 구현 예에 따르면, 상기 Ar1은 단일 결합 또는 C6~C19의 아릴렌기이며, 상기 Ar4는 C4~C60의 아릴기 또는 핵원자수 5 내지 20개의 헤테로아릴기이며, 상기 Ar5는 C4~C60의 아릴기이지만, 예시에 국한되는 것은 아니다. According to one preferred embodiment of the present invention, Ar 1 is a single bond or an arylene group of C 6 to C 19 , and Ar 4 is an aryl group of C 4 to C 60 or a heteroaryl group of 5 to 20 nuclear atoms. Ar 5 is an aryl group of C 4 to C 60 , but is not limited thereto.
본 발명의 바람직한 한 구현 예에 따르면, 본 발명의 화학식 1로 표시되는 화합물은 보다 구체적으로 아래의 화합물로 이루어진 군에서 선택될 수 있으나, 이에 한정되는 것은 아니다.According to one preferred embodiment of the present invention, the compound represented by Formula 1 of the present invention may be more specifically selected from the group consisting of the following compounds, but is not limited thereto.
본 발명의 상기 화학식 1로 표시되는 화합물은 보다 바람직하게 하기 화합물로 이루어진 군에서 선택될 수 있다:The compound represented by Formula 1 of the present invention may be more preferably selected from the group consisting of the following compounds:
본 발명의 바람직한 한 구현 예에 따르면, 본 발명의 화학식 2로 표시되는 화합물은 보다 구체적으로 아래의 화합물로 이루어진 군에서 선택될 수 있으나, 이에 한정되는 것은 아니다.According to one preferred embodiment of the present invention, the compound represented by Formula 2 of the present invention may be more specifically selected from the group consisting of the following compounds, but is not limited thereto.
본 발명에 있어서, 양극, 음극, 및 상기 양극과 음극 사이에 적어도 한 층 이상의 유기막을 포함하는 유기 전계 발광소자로서, 상기 유기막은 발광층을 포함하며, 상기 양극과 발광층 사이에 하기 화학식 1로 표시되는 화합물을 포함하는 유기막 및 하기 화학식 2로 표시되는 화합물을 포함하는 유기막을 포함할 수 있다. 구체적으로, 상기 화학식 1로 표시되는 화합물을 포함하는 유기막은 정공수송층이며, 상기 화학식 2로 표시되는 화합물을 포함하는 유기막은 전자차단층이지만, 예시에 국한되는 것은 아니다. In the present invention, an organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode, wherein the organic film includes a light emitting layer, and is represented by the formula (1) between the anode and the light emitting layer It may include an organic film containing a compound and an organic film containing a compound represented by the formula (2). Specifically, the organic film including the compound represented by Chemical Formula 1 is a hole transport layer, and the organic film including the compound represented by Chemical Formula 2 is an electron blocking layer, but is not limited thereto.
상기 정공수송층에는 상기 화학식 1로 표시되는 화합물 외에 이 분야에 공지된 정공수송물질이 더 포함될 수 있으며, 상기 전자차단층에는 상기 화학식 2로 표시되는 화합물 외에 이 분야에 공지된 정공수송물질이 더 포함될 수 있다.The hole transport layer may further include a hole transport material known in the art, in addition to the compound represented by Formula 1, and the electron blocking layer further includes a hole transport material known in the art, in addition to the compound represented by Formula 2 Can be.
본 발명에 있어서, 상기 유기 박막층은 정공주입층을 더 포함하며, 유기 박막층에 포함된 각 층은 정공주입층(HIL), 정공수송층(HTL), 전자차단층(EBL), 및 발광층(EML)의 순서로 적층될 수 있다. In the present invention, the organic thin film layer further includes a hole injection layer, each layer included in the organic thin film layer is a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), and an emission layer (EML) Can be stacked in the order of.
또한, 상기 유기 박막층은 정공주입층, 발광층, 전자수송층, 및 전자주입층을 더 포함하며, 유기 박막층에 포함된 각 층은 정공주입층(HIL), 정공수송층(HTL), 전자차단층(EBL), 발광층(EML), 전자수송층(ETL), 및 전자주입층(EIL)의 순서로 적층될 수 있다. The organic thin film layer further includes a hole injection layer, a light emitting layer, an electron transport layer, and an electron injection layer, and each layer included in the organic thin film layer includes a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL). ), An emission layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL).
더 나아가서, 상기 유기 박막층은 상기와 같은 적층 구조 외에 효율적인 발광 및 소자의 수명연장을 위하여 이 분야에서 공지되어 있는 다양한 기능을 갖는 층(유기물 층으로 한정되지 않음)들이 더 적층된 구조를 가질 수도 있다. Furthermore, the organic thin film layer may have a structure in which layers having various functions known in the art (not limited to organic layers) are stacked in addition to the laminated structure as described above for efficient light emission and long life of the device. .
이하에서, 본 발명의 유기전계발광소자에 대하여 예를 들어 설명한다. 그러나, 하기에 예시된 내용이 본 발명의 유기전계발광소자를 한정하는 것은 아니다.Hereinafter, the organic electroluminescent device of the present invention will be described by way of example. However, the contents exemplified below do not limit the organic light emitting device of the present invention.
본 발명에 따른 유기전계발광소자의 제조방법으로는, 먼저 기판 표면에 양극용 물질을 통상적인 방법으로 코팅하여 양극을 형성한다. 이때, 사용되는 기판은 투명성, 표면 평활성, 취급 용이성 및 방수성이 우수한 유리기판 또는 투명 플라스틱 기판이 바람직하다. 또한, 양극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등이 사용될 수 있다.In the method of manufacturing an organic light emitting display device according to the present invention, first, a positive electrode is coated on a surface of a substrate by a conventional method to form a positive electrode. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof. In addition, as the positive electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, may be used.
다음으로, 상기 양극 표면에 정공주입층(HIL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 정공주입층을 형성한다. 이러한 정공주입층 물질로는 구리프탈로시아닌(CuPc), 4,4',4"-트리스(3-메틸페닐아미노)트리페닐아민(m-MTDATA), 4,4',4"-트리스(3-메틸페닐아미노)페녹시벤젠(m-MTDAPB), 스타버스트(starburst)형 아민류인 4,4',4"-트리(N-카바졸릴)트리페닐아민(TCTA), 4,4',4"-트리스(N-(2-나프틸)-N-페닐아미노)-트리페닐아민(2-TNATA) 또는 이데미츠사(Idemitsu)에서 구입가능한 IDE406을 예로 들 수 있다.Next, a hole injection layer is formed on the surface of the anode by vacuum thermal evaporation or spin coating of a hole injection layer (HIL) material in a conventional manner. Such hole injection layer materials include copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA), 4,4', 4" -tris (3-methylphenyl Amino) phenoxybenzene (m-MTDAPB), starburst amines 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA), 4,4', 4" -tris Examples include (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA) or IDE406 available from Idemitsu.
상기 정공주입층 표면에 정공수송층(HTL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 정공수송층을 형성한다. 본 발명의 유기전계발광소자에서 정공수송층은 상기 화학식 1로 표시되는 화합물을 적층하여 형성할 수 있다. A hole transport layer is formed on the surface of the hole injection layer by vacuum thermal evaporation or spin coating of a hole transport layer (HTL) material in a conventional manner. In the organic light emitting device of the present invention, the hole transport layer may be formed by stacking the compound represented by Chemical Formula 1.
상기 정공수송층 표면에 발광층(EML) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 발광층을 형성한다. 이때, 사용되는 발광층 물질 중 단독 발광물질 또는 발광 호스트 물질은 녹색의 경우 트리스(8-하이드록시퀴놀리놀라토)알루미늄(Alq3) 등이 사용될 수 있으며, 청색의 경우 Balq(8-하이드록시퀴놀린베릴륨염), DPVBi(4,4'-비스(2,2-바이페닐에테닐)-1,1'-바이페닐)계열, 스파이로(스파이로)물질, 스파이로-DPVBi(스파이로-4,4'-비스(2,2-바이페닐에테닐)-1,1'-바이페닐), LiPBO(2-(2-벤조옥사졸릴)-페놀 리튬염), 비스(바이페닐비닐)벤젠, 알루미늄-퀴놀린 금속착체, 이미다졸, 티아졸 및 옥사졸의 금속착체 등이 사용될 수 있다.The light emitting layer (EML) material on the surface of the hole transport layer by vacuum thermal evaporation or spin coating in a conventional manner to form a light emitting layer. At this time, tris (8-hydroxyquinolinolato) aluminum (Alq3), etc. may be used as the sole light emitting material or the light emitting host material among the light emitting layer materials, and in the case of blue, Balq (8-hydroxyquinolineberyllium) may be used. Salt), DPVBi (4,4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl) series, spiro (spiro) substance, spiro-DPVBi (spiro-4, 4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzooxazolyl) -phenol lithium salt), bis (biphenylvinyl) benzene, aluminum -Quinoline metal complexes, metal complexes of imidazole, thiazole and oxazole and the like can be used.
상기 정공수송층 표면에 전자차단층(EBL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 전자차단층을 형성한다. 상기 전자차단층 물질로는 상기 화학식 2로 표시되는 화합물이 사용될 수 있다. An electron blocking layer is formed on the surface of the hole transport layer by vacuum thermal evaporation or spin coating of an electron blocking layer (EBL) material in a conventional manner. As the electron blocking layer material, a compound represented by Chemical Formula 2 may be used.
발광층 물질 중 발광 호스트와 함께 사용될 수 있는 도펀트(dopant)의 경우 형광 도펀트로서 이데미츠사(Idemitsu)에서 구입 가능한 IDE102, IDE105, 인광 도펀트로는 트리스(2-페닐피리딘)이리듐(III)(Ir(ppy)3), 이리듐(III)비스[(4,6-다이플루오로페닐)피리디나토-N,C-2']피콜린산염(FIrpic) (참조문헌[Chihaya Adachi et al., Appl. Phys. Lett., 2001, 79, 3082-3084]), 플라티늄(II)옥타에틸포르피린(PtOEP), TBE002(코비온사) 등이 사용될 수 있다.In the case of a dopant which can be used together with a light emitting host in the light emitting layer material, IDE102, IDE105, which is available from Idemitsu as a fluorescent dopant, and tris (2-phenylpyridine) iridium (III) (Ir (ppy) as a phosphorescent dopant. 3), iridium (III) bis [(4,6-difluorophenyl) pyridinato-N, C-2 '] picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys Lett., 2001, 79, 3082-3084), platinum (II) octaethyl porphyrin (PtOEP), TBE002 (Kobiion) and the like can be used.
상기 발광층 표면에 전자수송층(ETL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 전자수송층을 형성한다. 이때, 사용되는 전자수송층 물질의 경우 특별히 제한되지 않으며, 바람직하게는 트리스(8-하이드록시퀴놀리놀라토)알루미늄(Alq3)을 사용할 수 있다.An electron transport layer is formed on the surface of the light emitting layer by vacuum thermal evaporation or spin coating of an electron transport layer (ETL) material in a conventional manner. In this case, the electron transport layer material used is not particularly limited, and preferably tris (8-hydroxyquinolinolato) aluminum (Alq 3) may be used.
선택적으로는, 발광층과 전자수송층 사이에 정공 차단층(HBL)을 추가로 형성하고 발광층에 인광 도펀트를 함께 사용함으로써, 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지할 수 있다. Optionally, by forming an additional hole blocking layer (HBL) between the light emitting layer and the electron transporting layer and using a phosphorescent dopant in the light emitting layer, it is possible to prevent the triplet exciton or hole from diffusing into the electron transporting layer.
정공 차단층의 형성은 정공 차단층 물질을 통상적인 방법으로 진공 열증착 및 스핀 코팅하여 실시할 수 있으며, 정공 차단층 물질의 경우 특별히 제한되지는 않으나, 바람직하게는 (8-하이드록시퀴놀리놀라토)리튬(Liq), 비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄비페녹사이드(BAlq), 바쏘쿠프로인 (bathocuproine, BCP) 및 LiF 등을 사용할 수 있다.The hole blocking layer may be formed by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner, and the hole blocking layer material is not particularly limited, but is preferably (8-hydroxyquinolinol). Earth) lithium (Liq), bis (8-hydroxy-2-methylquinolinolato) -aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF and the like can be used.
상기 전자수송층 표면에 전자주입층(EIL) 물질을 통상적인 방법으로 진공 열증착 또는 스핀 코팅하여 전자주입층을 형성한다. 이때, 사용되는 전자주입층 물질은 LiF, Liq, Li2O, BaO, NaCl, CsF 등의 물질이 사용될 수 있다.상기 전자주입층 표면에 음극용 물질을 통상적인 방법으로 진공 열증착하여 음극을 형성한다.An electron injection layer is formed on the surface of the electron transport layer by vacuum thermal evaporation or spin coating of an electron injection layer (EIL) material in a conventional manner. In this case, the material of the electron injection layer may be a material such as LiF, Liq, Li 2 O, BaO, NaCl, CsF, etc. The negative electrode is vacuum-deposited on the surface of the electron injection layer by a conventional method Form.
이때, 사용되는 음극용 물질로는 리튬(Li), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘(Mg), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 사용될 수 있다. 또한, 전면발광 유기전계발광소자의 경우 산화인듐주석(ITO) 또는 산화인듐아연(IZO)를 사용하여 빛이 투과할 수 있는 투명한 음극을 형성할 수도 있다.At this time, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used. In addition, in the case of the front emission organic light emitting diode, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode through which light can pass.
상기 음극의 표면에는 본 발명의 캡핑층 형성용 조성물에 의해 캡핑층(CPL)이 형성될 수 있다. The capping layer CPL may be formed on the surface of the cathode by the composition for capping layer formation of the present invention.
본 발명에 따른 유기전계발광소자는 상술한 바와 같은 순서, 즉 양극/정공주입층/정공수송층/전자차단층/발광층/전자수송층/전자주입층/음극 순으로 제조하여도 되고, 그 반대로 음극/전자주입층/전자수송층/발광층/전자차단층/정공수송층/정공주입층/양극의 순서로 제조하여도 무방하다.The organic light emitting device according to the present invention may be manufactured in the order described above, that is, in the order of anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode, and vice versa. The electron injection layer, the electron transport layer, the light emitting layer, the electron blocking layer, the hole transport layer, the hole injection layer and the anode may be manufactured in the order.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.
합성예Synthesis Example
화합물 1-1Compound 1-1
디([1,1'-바이페닐]-4-일)아민 20.00g(62mmol)에 4,4'-디브로모-1,1'-바이페닐 9.71g(31mmol)를 톨루엔 187mL에 용해시킨 후, Pd2dba3 373mg(0.62mmol), t-Bu3P(50% 톨루엔 용해) 1.01g(2.50mmol), t-BuONa 13.16g(137mmol)을 첨가하고 4시간 동안 가열 및 환류하여 반응 완결을 확인한 후 메탄올을 첨가하고 여과한 뒤 흰색 고체를 헥산/메틸렌클로라이드(Hex/MC)로 재결정하여 화합물 1-1 23.44g을 95%의 수율로 얻었다.9.71 g (31 mmol) of 4,4'-dibromo-1,1'-biphenyl was dissolved in 187 mL of toluene in 20.00 g (62 mmol) of di ([1,1'-biphenyl] -4-yl) amine. Then, 373 mg (0.62 mmol) of Pd 2 dba 3 , 1.01 g (2.50 mmol) of t-Bu 3 P (50% toluene dissolved) and 13.16 g (137 mmol) of t-BuONa were added and heated and refluxed for 4 hours to complete the reaction. After confirming, methanol was added, the mixture was filtered, and the white solid was recrystallized from hexane / methylene chloride (Hex / MC) to obtain 23.44 g of compound 1-1 in a yield of 95%.
화합물 1-2Compound 1-2
디([1,1'-바이페닐]-4-일)아민 20.00g(62mmol)에 3,3'-디브로모-1,1'-바이페닐 9.71g(31mmol)를 톨루엔 187mL에 용해시킨 후, Pd2dba3 373mg(0.62mmol), t-Bu3P(50% 톨루엔 용해) 1.01g(2.50mmol), t-BuONa 13.16g(137mmol)을 첨가하고 4시간 동안 가열 및 환류하여 반응 완결을 확인한 후 메탄올을 첨가하고 여과한 뒤 흰색 고체를 헥산/메틸렌클로라이드(Hex/MC)로 재결정하여 화합물 1-2를 21.96g을 89%의 수율로 얻었다. 9.71 g (31 mmol) of 3,3'-dibromo-1,1'-biphenyl was dissolved in 187 mL of toluene in 20.00 g (62 mmol) of di ([1,1'-biphenyl] -4-yl) amine. Then, 373 mg (0.62 mmol) of Pd 2 dba 3 , 1.01 g (2.50 mmol) of t-Bu 3 P (50% toluene dissolved) and 13.16 g (137 mmol) of t-BuONa were added and heated and refluxed for 4 hours to complete the reaction. After confirming that methanol was added and filtered, the white solid was recrystallized from hexane / methylene chloride (Hex / MC) to obtain 21.96 g of compound 1-2 in 89% yield.
화합물 2-1Compound 2-1
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-(4-(9,9'-스파이로바이[플루오렌]-2-일)페닐)-[1,1'-바이페닐]-4-아민 5.60g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류(환류)하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-1 6.82g을 78%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N- (4- (9,9'-spirobi [fluorene] -2-yl) phenyl)-[ 5.60 g (10 mmol) of 1,1'-biphenyl] -4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and Pd. (dba) 2 115 mg (0.2 mmol) was added followed by reflux (reflux) for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 6.82 g of compound 2-1 in a yield of 78%.
1H NMR (CDCl3, 300 MHz): δ=7.88(d, 1H), 7.84(d, 4H), 7.74(d, 1H), 7.61(d, 1H), 7.56(d, 2H), 7.48(d, 2H), 7.42-7.34(m, 9H), 7.29(t, 1H), 7.22(d, 2H), 7.18-7.04(m, 11H), 6.97(t, 1H), 6.93(s, 1H), 6.79-6.70(m, 5H), 6.65(d, 1H), 6.63(d, 1H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.88 (d, 1H), 7.84 (d, 4H), 7.74 (d, 1H), 7.61 (d, 1H), 7.56 (d, 2H), 7.48 ( d, 2H), 7.42-7.34 (m, 9H), 7.29 (t, 1H), 7.22 (d, 2H), 7.18-7.04 (m, 11H), 6.97 (t, 1H), 6.93 (s, 1H) , 6.79-6.70 (m, 5H), 6.65 (d, 1H), 6.63 (d, 1H) ppm.
화합물 2-2Compound 2-2
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-([1,1'-바이페닐]-4-일)-9-페닐-9H-카바졸-3-아민 4.10g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-2 4.71g을 65%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N-([1,1'-biphenyl] -4-yl) -9-phenyl-9H-carbazole- 4.10 g (10 mmol) of 3-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and 115 mg (0.2 mmol) of Pd (dba) 2 It was refluxed for 3 hours after the addition. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 4.71 g of compound 2-2 in a yield of 65%.
1H NMR (CDCl3, 300 MHz): δ =8.03(d, 1H), 7.76(d, 1H), 7.68(s, 1H), 7.64-7.57(m, 5H), 7.50(t, 2H), 7.41(d, 1H), 7.32-7.30(m, 3H), 7.26(t, 2H), 7.21(t, 2H), 7.17-7.11(m, 6H), 7.10-7.02(m, 5H), 6.98(d, 2H), 6.89(t, 1H), 6.86(d, 2H), 6.66(d, 1H), 6.61(d, 1H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 8.03 (d, 1H), 7.76 (d, 1H), 7.68 (s, 1H), 7.64-7.57 (m, 5H), 7.50 (t, 2H), 7.41 (d, 1H), 7.32-7.30 (m, 3H), 7.26 (t, 2H), 7.21 (t, 2H), 7.17-7.11 (m, 6H), 7.10-7.02 (m, 5H), 6.98 ( d, 2H), 6.89 (t, 1H), 6.86 (d, 2H), 6.66 (d, 1H), 6.61 (d, 1H) ppm.
화합물 2-3Compound 2-3
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-([1,1'-바이페닐]-4-일)-9,9'-스파이로바이[플루오렌]-2-아민 4.84g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-3 5.59g을 70%의 수율로 얻었다.4-bromo-9,9'-spirobi [flowene] 3.95 g (10 mmol) and N-([1,1'-biphenyl] -4-yl) -9,9'-spirobi [ 4.84 g (10 mmol) of fluorene] -2-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and 115 mg of Pd (dba) 2 (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 5.59 g of the compound 2-3 in a yield of 70%.
1H NMR (CDCl3, 300 MHz): δ =7.82(d, 2H), 7.79(t, 2H), 7.73(t, 2H), 7.51(d, 2H), 7.47(m, 1H), 7.42-7.33(m, 7H), 7.31-7.26(m, 3H), 7.19-7.08(m, 6H), 7.04-6.94(m, 5H), 6.92(t, 1H), 6.85(d, 1H), 6.72(d, 2H), 6.65-6.57(m, 3H), 6.50(d, 1H), 6.29(d, 1H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.82 (d, 2H), 7.79 (t, 2H), 7.73 (t, 2H), 7.51 (d, 2H), 7.47 (m, 1H), 7.42- 7.33 (m, 7H), 7.31-7.26 (m, 3H), 7.19-7.08 (m, 6H), 7.04-6.94 (m, 5H), 6.92 (t, 1H), 6.85 (d, 1H), 6.72 ( d, 2H), 6.65-6.57 (m, 3H), 6.50 (d, 1H), 6.29 (d, 1H) ppm.
화합물 2-4Compound 2-4
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-(3-(9,9'-스파이로바이[플루오렌]-2-일)페닐)-[1,1'-바이페닐]-4-아민 5.60g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-4 5.68g을 65%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N- (3- (9,9'-spirobi [fluorene] -2-yl) phenyl)-[ 5.60 g (10 mmol) of 1,1'-biphenyl] -4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and Pd. (dba) 2 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 5.68 g of compound 2-4 in a yield of 65%.
1H NMR (CDCl3, 300 MHz): δ =7.70(d, 1H), 7.66-7.63(m, 3H), 7.58(d, 2H), 7.35(d, 1H), 7.26(t, 1H), 7.23(t, 2H), 7.20-7.11(m, 9H), 7.07(d, 2H), 7.03(t, 1H), 7.01(t, 1H), 6.99-6.97(m, 4H), 6.94(t, 4H), 6.82(s, 1H), 6.74(d, 1H), 6.72(d, 2H), 6.69-6.67(m, 2H), 6.63(d, 2H), 6.60(t, 1H), 6.56(d, 1H), 6.49(d, 1H), 6.33(d, 1H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.70 (d, 1H), 7.66-7.63 (m, 3H), 7.58 (d, 2H), 7.35 (d, 1H), 7.26 (t, 1H), 7.23 (t, 2H), 7.20-7.11 (m, 9H), 7.07 (d, 2H), 7.03 (t, 1H), 7.01 (t, 1H), 6.99-6.97 (m, 4H), 6.94 (t, 4H), 6.82 (s, 1H), 6.74 (d, 1H), 6.72 (d, 2H), 6.69-6.67 (m, 2H), 6.63 (d, 2H), 6.60 (t, 1H), 6.56 (d , 1H), 6.49 (d, 1H), 6.33 (d, 1H) ppm.
화합물 2-5Compound 2-5
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-(4-(9H-카바졸-9-일)페닐)-[1,1'-바이페닐]-4-아민 4.11g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-5 3.99g을 55%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N- (4- (9H-carbazol-9-yl) phenyl)-[1,1'-biphenyl] 4.11 g (10 mmol) of 4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and 115 mg (0.2 mmol) of Pd (dba) 2 ) Was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to obtain 3.99 g of compound 2-5 in a yield of 55%.
1H NMR (CDCl3, 300 MHz): δ =8.14(d, 2H), 7.87(t, 3H), 7.60(t, 4H), 7.48-7.35(m, 14H), 7.34-7.12(m, 8H), 7.06(t, 1H), 6.80(d, 2H), 6.71(t, 2H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 8.14 (d, 2H), 7.87 (t, 3H), 7.60 (t, 4H), 7.48-7.35 (m, 14H), 7.34-7.12 (m, 8H) ), 7.06 (t, 1H), 6.80 (d, 2H), 6.71 (t, 2H) ppm.
화합물 2-6Compound 2-6
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-(4-(9,9-디메틸-9H-플루오렌-2-일)페닐)-[1,1'-바이페닐]-4-아민 4.38g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-6 5.72g을 76%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N- (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl)-[1, 4.38 g (10 mmol) of 1'-biphenyl] -4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and Pd (dba). 2 ) 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 5.72 g of compound 2-6 in a yield of 76%.
1H NMR (CDCl3, 300 MHz): δ =7.92(d, 1H), 7.63(d, 2H), 7.59(d, 1H), 7.55(d, 1H), 7.35(s, 1H), 7.33(d, 1H), 7.27-7.25(m, 4H), 7.23(t, 2H), 7.20(d, 1H), 7.16-7.12(m, 9H), 7.06(t, 1H), 7.01(t, 2H), 7.00(t, 1H), 6.99(d, 2H), 6.87(t, 1H), 6.78(d, 2H), 6.63-6.60(m, 3H), 1.51(s, 6H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.92 (d, 1H), 7.63 (d, 2H), 7.59 (d, 1H), 7.55 (d, 1H), 7.35 (s, 1H), 7.33 ( d, 1H), 7.27-7.25 (m, 4H), 7.23 (t, 2H), 7.20 (d, 1H), 7.16-7.12 (m, 9H), 7.06 (t, 1H), 7.01 (t, 2H) , 7.00 (t, 1H), 6.99 (d, 2H), 6.87 (t, 1H), 6.78 (d, 2H), 6.63-6.60 (m, 3H), 1.51 (s, 6H) ppm.
화합물 2-7Compound 2-7
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-([1,1'-바이페닐]-4-yl)-[1,1':4',1''-터페닐]-4-아민 3.98g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-7 3.70g을 52%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 3.98 g (10 mmol) of 1 ''-terphenyl] -4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and Pd ( dba) 2 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 3.70 g of compound 2-7 in a yield of 52%.
1H NMR (CDCl3, 300 MHz): δ =7.87(d, 2H), 7.84(d, 1H), 7.70-7.53(m, 12H), 7.48-7.28(m, 12H), 7.19-7.11(m, 5H), 7.02(t, 1H), 6.79(d, 2H), 6.71-6.66(m, 2H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.87 (d, 2H), 7.84 (d, 1H), 7.70-7.53 (m, 12H), 7.48-7.28 (m, 12H), 7.19-7.11 (m , 5H), 7.02 (t, 1H), 6.79 (d, 2H), 6.71-6.66 (m, 2H) ppm.
화합물 2-8Compound 2-8
2-(3-브로모페닐)-9,9'-스파이로바이[플로우렌] 4.71g(10mmol)과 N-([1,1'-바이페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 3.62g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-8 5.94g을 79%의 수율로 얻었다.4.71 g (10 mmol) of 2- (3-bromophenyl) -9,9'-spirobi [flowene] and N-([1,1'-biphenyl] -4-yl) -9,9- 3.62 g (10 mmol) of dimethyl-9H-fluorene-2-amine was dissolved in 30 ml of toluene, then 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), Pd (dba) 2 ) 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 5.94 g of compound 2-8 in a yield of 79%.
1H NMR (CDCl3, 300 MHz): δ =7.90-7.80(m, 2H), 7.80-7.70(m, 2H), 7.70-7.60(d, 1H), 7.60-7.00(m, 26H), 6.90-6.65(m, 4H), 1.38(s, 6H)ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.90-7.80 (m, 2H), 7.80-7.70 (m, 2H), 7.70-7.60 (d, 1H), 7.60-7.00 (m, 26H), 6.90 -6.65 (m, 4H), 1.38 (s, 6H) ppm.
화합물 2-9Compound 2-9
4-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-(3-(9,9-디메틸-9H-플루오렌-2-일)페닐)-[1,1'-바이페닐]-4-아민 4.38g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-9 5.56g을 74%의 수율로 얻었다.4.95 g (10 mmol) of 4-bromo-9,9'-spirobi [flowene] and N- (3- (9,9-dimethyl-9H-fluoren-2-yl) phenyl)-[1, 4.38 g (10 mmol) of 1'-biphenyl] -4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and Pd (dba). 2 ) 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 5.56 g of compound 2-9 in a yield of 74%.
1H NMR (CDCl3, 300 MHz): δ =8.13(d, 1H), 7.57(d, 2H), 7.54(d, 1H), 7.51(d, 1H), 7.44(d, 1H), 7.34(t, 1H), 7.26-7.21(m, 5H), 7.20-7.16(m, 9H), 7.13(t, 1H), 7.11(t, 1H), 7.05-7.03(m, 3H), 6.98(t, 1H), 6.95(d, 1H), 6.84(s, 1H), 6.83(t, 2H), 6.67-6.64(m, 3H), 6.63(d, 1H), 1.28(s, 6H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 8.13 (d, 1H), 7.57 (d, 2H), 7.54 (d, 1H), 7.51 (d, 1H), 7.44 (d, 1H), 7.34 ( t, 1H), 7.26-7.21 (m, 5H), 7.20-7.16 (m, 9H), 7.13 (t, 1H), 7.11 (t, 1H), 7.05-7.03 (m, 3H), 6.98 (t, 1H), 6.95 (d, 1H), 6.84 (s, 1H), 6.83 (t, 2H), 6.67-6.64 (m, 3H), 6.63 (d, 1H), 1.28 (s, 6H) ppm.
화합물 2-10Compound 2-10
2-브로모-9,9'-스파이로바이[플로우렌] 3.95g(10mmol)과 N-(4-(9,9'-스파이로바이[플루오렌]-2-일)페닐)-[1,1'-바이페닐]-4-아민 5.60g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-10 5.94g을 68%의 수율로 얻었다.2.95 g (10 mmol) of 2-bromo-9,9'-spirobi [flowene] and N- (4- (9,9'-spirobi [fluorene] -2-yl) phenyl)-[ 5.60 g (10 mmol) of 1,1'-biphenyl] -4-amine was dissolved in 30 ml of toluene, followed by 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), and Pd. (dba) 2 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 5.94 g of compound 2-10 in a yield of 68%.
1H NMR (CDCl3, 300 MHz): δ =7.90-7.87(d, 1H), 7.87-7.82(d, 5H), 7.80-7.70(d, 1H), 7.65-6.90(m, 30H), 6.80-6.60(m, 6H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 7.90-7.87 (d, 1H), 7.87-7.82 (d, 5H), 7.80-7.70 (d, 1H), 7.65-6.90 (m, 30H), 6.80 -6.60 (m, 6H) ppm.
화합물 2-11Compound 2-11
2-(4-브로모페닐)-9,9'-스파이로바이[플로우렌] 4.71g(10mmol)과 N-([1,1'-바이페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 3.62g(10mmol)을 톨루엔 30ml에 녹인 후 t-BuONa 2.88g(30mmol), t-Bu3P(50% in 톨루엔) 161mg(0.4mmol), Pd(dba)2 115mg(0.2mmol)을 첨가한 후 3시간 동안 환류하였다. 반응 완결 후 상온으로 식히고 에틸 아세테이트 50ml와 H2O 50ml를 첨가하여 유기층을 추출하였다. 유기층을 MgSO4로 건조 후 증류하고 n-헥산/메틸렌 클로라이드로 컬럼하여 화합물 2-11 6.17g을 82%의 수율로 얻었다.4.71 g (10 mmol) of 2- (4-bromophenyl) -9,9'-spirobi [flowene] and N-([1,1'-biphenyl] -4-yl) -9,9- 3.62 g (10 mmol) of dimethyl-9H-fluorene-2-amine was dissolved in 30 ml of toluene, then 2.88 g (30 mmol) of t-BuONa, 161 mg (0.4 mmol) of t-Bu 3 P (50% in toluene), Pd (dba) 2 ) 115 mg (0.2 mmol) was added and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of ethyl acetate and 50 ml of H 2 O were added to extract an organic layer. The organic layer was dried over MgSO 4 , distilled, and columned with n-hexane / methylene chloride to give 6.17 g of compound 2-11 in 82% yield.
1H NMR (CDCl3, 300 MHz): δ =8.10-7.95(m, 4H), 7.75-6.90(m, 27H), 6.90-6.55(m, 4H), 1.35(s, 6H) ppm. 1 H NMR (CDCl 3 , 300 MHz): δ = 8.10-7.95 (m, 4H), 7.75-6.90 (m, 27H), 6.90-6.55 (m, 4H), 1.35 (s, 6H) ppm.
실시예Example
1: One:
유기전계발광소자Organic light emitting diode
제조 Produce
반사층이 형성된 기판 위에 ITO로 양극을 형성하고, N2 플라즈마 또는 UV-오존으로 표면처리 하였다. 그 위에 정공주입층(HIL)으로 HAT-CN을 10nm의 두께로 증착시켰다. 이어서 본 발명의 화합물 1-1을 80nm 두께로 증착시켜 정공수송층(HTL)을 형성하였다. 상기 정공수송층 상부에 화합물 2-1을 150 Å 두께로 진공 증착하여 전자차단층(EBL)을 형성하고, 상기 전자차단층(EBL) 상부에 발광층(EML)으로 blue EML을 형성할 수 있는 9,10-Bis(2-naphthyl)anthraces(ADN)을 25nm 증착 시키면서 Dopant로 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene)을 약 5%정도 dopping 하였다. 그 위에 안트라센 유도체와 LiQ를 1:1로 혼합하여 30nm의 두께로 전자수송층(ETL)을 증착하였으며, 그 위에 전자주입층(EIL)으로 LiQ를 10nm 두께로 증착시켰다. 그 후, 음극으로 마그네슘과 은(Ag)을 9:1로 혼합한 혼합물을 15nm의 두께로 증착시켰으며, 상기 음극 위에 캡핑 층(capping layer)로 N4,N4'-비스[4-[비스(3-메틸페닐)아미노]페닐]-N4,N4'-디페닐-[1,1'-바이페닐]-4,4'-디아민(DNTPD)을 65nm 두께로 증착시켰다. 그 위에 UV 경화형 접착제로 흡습제가 함유된 씰 캡(seal cap)을 합착하여 대기중의 O2나 수분으로부터 유기전계발광소자를 보호할 수 있게 하여 유기전계발광소자를 제조하였다.An anode was formed on the substrate on which the reflective layer was formed by ITO and surface-treated with N2 plasma or UV-ozone. On it, HAT-CN was deposited to a thickness of 10 nm with a hole injection layer (HIL). Subsequently, Compound 1-1 of the present invention was deposited to a thickness of 80 nm to form a hole transport layer (HTL). 9, which may form an electron blocking layer (EBL) by vacuum depositing Compound 2-1 on the hole transport layer to a thickness of 150, and form a light emitting layer (EML) on the electron blocking layer (EBL). 10-Bis (2-naphthyl) anthraces (ADN) was doped with 25 nm of 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) as a dopant. Anthracene derivative and LiQ were mixed 1: 1 to deposit an electron transport layer (ETL) with a thickness of 30 nm, and LiQ was deposited with an electron injection layer (EIL) on a thickness of 10 nm. Thereafter, a mixture of magnesium and silver (Ag) in a 9: 1 mixture was deposited to a thickness of 15 nm, and N4, N4'-bis [4- [bis () was formed as a capping layer on the cathode. 3-methylphenyl) amino] phenyl] -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic electroluminescent device was manufactured by bonding a seal cap containing a hygroscopic agent with a UV curable adhesive to protect the organic electroluminescent device from O 2 or moisture in the air.
실시예Example
2 ~ 13 2 to 13
상기 실시예 1에서 전자차단물질을 화합물 2-1 대신에 2-2 ~ 2-11을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 유기전계발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 1 except for using the electron blocking material 2-2 to 2-11 instead of the compound 2-1 in Example 1.
*실시예
14 ~ 16
Examples 14-16
상기 실시예 1에서 정공수송물질을 화합물 1-1 대신 화합물 1-2를 사용하고, 전자차단물질을 화합물 2-1 대신에 각각 화합물 2-3, 화합물 2-4, 화합물 2-8을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 유기전계발광소자를 제조하였다.In Example 1, the compound 1-1 was used instead of compound 1-1, and the electron blocking material was used compound 2-3, compound 2-4, and compound 2-8 instead of compound 2-1. An organic light emitting display device was manufactured in the same manner as in Example 1.
비교예Comparative example
1~2 1 ~ 2
상기 실시예 1에서 전자차단물질인 화합물 2-1을 대신하여 상기 화합물 1-1, NPB를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기전계발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound 1-1 and NPB instead of the compound 2-1 as the electron blocking material in Example 1.
비교예Comparative example
3 3
상기 실시예 8에서 정공수송물질인 화합물 1-1을 대신하여 NPB를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기전계발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 1 except for using NPB instead of the compound 1-1 as the hole transport material in Example 8.
| HTLHTL | EBLEBL | VoltVolt | CdCD /A/ A | Cd/m²Cd / m² | lm/Wlm / W | EQEEQE (%)(%) | CIExCIEx | CIEyCIEy | |
| 실시예1Example 1 | 화합물1-1Compound 1-1 | 화합물2-1Compound 2-1 | 4.34.3 | 4.94.9 | 493493 | 3.63.6 | 9.49.4 | 0.1370.137 | 0.0520.052 |
| 실시예2Example 2 | 화합물1-1Compound 1-1 | 화합물2-2Compound 2-2 | 4.64.6 | 5.15.1 | 505505 | 3.53.5 | 9.19.1 | 0.1340.134 | 0.0570.057 |
| 실시예4Example 4 | 화합물1-1Compound 1-1 | 화합물2-4Compound 2-4 | 4.14.1 | 4.64.6 | 462462 | 3.53.5 | 8.98.9 | 0.1370.137 | 0.0510.051 |
| 실시예5Example 5 | 화합물1-1Compound 1-1 | 화합물2-5Compound 2-5 | 3.93.9 | 5.25.2 | 517517 | 4.24.2 | 9.19.1 | 0.1330.133 | 0.0590.059 |
| 실시예6Example 6 | 화합물1-1Compound 1-1 | 화합물2-6Compound 2-6 | 4.14.1 | 5.25.2 | 520520 | 4.04.0 | 9.49.4 | 0.1330.133 | 0.0560.056 |
| 실시예7Example 7 | 화합물1-1Compound 1-1 | 화합물2-7Compound 2-7 | 4.64.6 | 5.05.0 | 500500 | 3.43.4 | 9.29.2 | 0.1350.135 | 0.0550.055 |
| 실시예8Example 8 | 화합물1-1Compound 1-1 | 화합물2-8Compound 2-8 | 3.93.9 | 4.84.8 | 483483 | 3.93.9 | 8.98.9 | 0.1350.135 | 0.0550.055 |
| 실시예10Example 10 | 화합물1-1Compound 1-1 | 화합물2-10Compound 2-10 | 4.04.0 | 5.65.6 | 555555 | 4.34.3 | 10.410.4 | 0.1360.136 | 0.0530.053 |
| 실시예11Example 11 | 화합물1-1Compound 1-1 | 화합물2-11Compound 2-11 | 4.04.0 | 4.94.9 | 491491 | 3.83.8 | 9.09.0 | 0.1350.135 | 0.0550.055 |
| 실시예12Example 12 | 화합물1-1Compound 1-1 | 화합물2-12Compound 2-12 | 4.04.0 | 4.84.8 | 482482 | 3.83.8 | 8.88.8 | 0.1340.134 | 0.0560.056 |
| 실시예13Example 13 | 화합물1-1Compound 1-1 | 화합물2-13Compound2-13 | 3.93.9 | 5.15.1 | 514514 | 4.14.1 | 9.49.4 | 0.1350.135 | 0.0550.055 |
| 실시예14Example 14 | 화합물1-2Compound 1-2 | 화합물2-4Compound 2-4 | 3.93.9 | 4.94.9 | 488488 | 3.93.9 | 9.19.1 | 0.1360.136 | 0.0530.053 |
| 실시예15Example 15 | 화합물1-2Compound 1-2 | 화합물2-5Compound 2-5 | 3.93.9 | 5.25.2 | 520520 | 4.24.2 | 9.59.5 | 0.1340.134 | 0.0560.056 |
| 실시예16Example 16 | 화합물1-2Compound 1-2 | 화합물2-8Compound 2-8 | 3.93.9 | 6.36.3 | 633633 | 5.15.1 | 11.711.7 | 0.1350.135 | 0.0550.055 |
| 비교예1Comparative Example 1 | 화합물1-1Compound 1-1 | 화합물1-1Compound 1-1 | 3.93.9 | 4.34.3 | 432432 | 3.53.5 | 8.38.3 | 0.1370.137 | 0.0510.051 |
| 비교예2Comparative Example 2 | 화합물1-1Compound 1-1 | NPBNPB | 4.24.2 | 5.15.1 | 509509 | 3.83.8 | 8.78.7 | 0.1320.132 | 0.0610.061 |
| 비교예3Comparative Example 3 | NPBNPB | 화합물2-8Compound 2-8 | 4.14.1 | 4.44.4 | 436436 | 3.33.3 | 7.97.9 | 0.1340.134 | 0.0560.056 |
상기 표 1의 소자평가 결과를 통해 본 발명의 [화학식 1] 및 [화학식 2]에 대응되는 화합물을 각각 유기전계발광소자의 정공수송층 및 전자차단층에 적용했을 경우 비교예 대비 외부 양자효율이 102 ~ 150%까지 향상되는 것을 확인할 수 있었다. 따라서, 본 발명의 유기전계발광소자의 구성에 있어서 특정 재료계를 이용함으로써 고효율을 실현할 수 있음을 확인할 수 있다.When the compounds corresponding to [Chemical Formula 1] and [Chemical Formula 2] of the present invention are applied to the hole transport layer and the electron blocking layer of the organic light emitting device through the device evaluation results of Table 1, the external quantum efficiency is 102 It was confirmed that the improvement to ~ 150%. Therefore, it can be confirmed that high efficiency can be achieved by using a specific material system in the configuration of the organic light emitting device of the present invention.
본 발명은 유기전계발광소자에 관한 것이다. 더욱 상세하게는 특정의 정공수송물질과 특정의 전자차단물질을 포함하는 것을 특징으로 하는 유기전계발광소자에 관한 것이다.The present invention relates to an organic electroluminescent device. More particularly, the present invention relates to an organic light emitting display device comprising a specific hole transport material and a specific electron blocking material.
Claims (11)
- 양극, 음극, 및 상기 양극과 음극 사이에 적어도 한 층 이상의 유기막을 포함하는 유기 전계 발광소자로서,An organic electroluminescent device comprising an anode, a cathode, and at least one organic film between the anode and the cathode,상기 유기막은 발광층을 포함하며,The organic layer includes a light emitting layer,상기 양극과 발광층 사이에 하기 화학식 1로 표시되는 화합물을 포함하는 유기막 및 하기 화학식 2로 표시되는 화합물을 포함하는 유기막을 포함하는 유기전계발광소자:An organic electroluminescent device comprising an organic film comprising a compound represented by Formula 1 and an organic film comprising a compound represented by Formula 2 between the anode and the light emitting layer:[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서, here,m 및 n은 각각 0 내지 5의 정수이며,m and n are each an integer of 0 to 5,p, q 및 r은 각각 0 내지 4의 정수이며,p, q and r are each an integer of 0 to 4,Ar1은 단일결합, C6~C18의 아릴렌기 또는 핵원자수 5 내지 18개의 헤테로아릴렌기이며,Ar 1 is a single bond, an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 5 to 18 nuclear atoms,Ar2 내지 Ar5는 서로 동일하거나 상이하고, 각각 독립적으로 아민기, C1~C10의 알킬기, C2~C10의 알케닐기, C2~C10의 알키닐기, C3~C10의 시클로알킬기, 핵원자수 3 내지 10개의 헤테로시클로알킬기, C4~C60의 아릴기 및 핵원자수 5 내지 20개의 헤테로아릴기로 이루어진 군으로부터 선택되며,The Ar 2 to Ar 5 are the same or group different and each is independently selected from amines with each other, C 1 ~ C 10 alkyl group, C 2 ~ C 10 alkenyl group, C 2 ~ C 10 alkynyl group, C 3 ~ C 10 of the It is selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group of 3 to 10 nuclear atoms, an aryl group of C 4 ~ C 60 and a heteroaryl group of 5 to 20 nuclear atoms,R1 내지 R3은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소(D), 할로겐, 시아노, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 40개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40개의 헤테로시클로알킬기로 이루어진 군으로부터 선택되며,R 1 to R 3 are each other the same or different, each independently represent hydrogen, deuterium (D), halogen, cyano, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of the Alkynyl group, C 6 ~ C 60 Aryl group, Nucleotide 5 to 40 heteroaryl group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryl An amine group, a C 3 to C 40 cycloalkyl group and a nuclear atom having 3 to 40 heterocycloalkyl groups,L1 내지 L3는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합, C6~C40의 아릴렌기 또는 핵원자수 5 내지 40개의 헤테로아릴렌기이며, L 1 to L 3 is the same as or different from each other, and each independently a single bond, an arylene group having 6 to 40 carbon atoms, or a heteroarylene group having 5 to 40 nuclear atoms,상기 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴옥시기,알킬옥시기, 아릴아민기, 아릴기 및 헤테로아릴기 각각은 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, 할로겐C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다.The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryloxy group, alkyloxy group, arylamine group, aryl group and heteroaryl group are each deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, halogen C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 6 to C 60 aryl group, nuclear atom 5 to 60 heteroaryl group , C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 arylamine group, C 3 ~ C 40 cycloalkyl group, 3 to 40 heterocycloalkyl group , C 1 ~ C 40 Alkylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 Mono or dia Reel Phosphinicosuccinic group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ substituted by one or more substituent species selected from the group consisting of C 60 or silyl aryl is unsubstituted, the plurality of substitution When substituted with, they may be the same or different from each other. - 제 1항에 있어서,The method of claim 1,상기 화학식 2로 표시되는 화합물은 하기 화학식 3으로 표시되는 화합물인 유기전계발광소자:Compound represented by the formula (2) is an organic light emitting device is a compound represented by the formula (3):[화학식 3][Formula 3]
여기서,here,R1, R2, R3, Ar4, Ar5, p, q 및 r 각각은 상기 제1항에서 정의한 바와 같다. R 1 , R 2 , R 3 , Ar 4 , Ar 5 , p, q and r are each as defined in claim 1 above. - 제 1항에 있어서,The method of claim 1,상기 화학식 2로 표시되는 화합물은 하기 화학식 4으로 표시되는 화합물인 유기전계발광소자:The compound represented by Formula 2 is an organic light emitting device that is a compound represented by the formula (4):[화학식 4][Formula 4]
여기서, here,R1, R2, R3, Ar4, Ar5, L3, p, q 및 r 각각은 상기 제1항에서 정의한 바와 같다. R 1 , R 2 , R 3 , Ar 4 , Ar 5 , L 3 , p, q and r are each as defined in claim 1 above. - 제 1항에 있어서, The method of claim 1,상기 Ar1은 단일 결합 또는 C6~C19의 아릴렌기인 유기전계발광소자.Ar 1 is a single bond or an C 6 ~ C 19 arylene group organic electroluminescent device.
- 제 1항에 있어서, The method of claim 1,상기 Ar4는 C4~C60의 아릴기 또는 핵원자수 5 내지 20개의 헤테로아릴기인 유기전계발광소자.Ar 4 is an organic electroluminescent device which is an aryl group having 4 to 60 carbon atoms or a heteroaryl group having 5 to 20 nuclear atoms.
- 제 1항에 있어서, The method of claim 1,상기 Ar5는 C4~C60의 아릴기인 유기전계발광소자.Ar 5 is an organic luminescent device of C 4 ~ C 60 An aryl group.
- 제 1항에 있어서,The method of claim 1,상기 화학식 1로 표시되는 화합물은 아래 화합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 화합물:Compound represented by Formula 1 is selected from the group consisting of the following compounds:
- 제 7항에 있어서,The method of claim 7, wherein상기 화학식 1로 표시되는 화합물은 아래 화합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 화합물:Compound represented by Formula 1 is selected from the group consisting of the following compounds:
- 제 1항에 있어서,The method of claim 1,상기 화학식 2로 표시되는 화합물은 아래 화합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 화합물:Compound represented by the formula (2) is characterized in that the compound selected from the group consisting of:
- 제 1항에 있어서,The method of claim 1,상기 화학식 1로 표시되는 화합물을 포함하는 유기막은 정공수송층인 유기전계발광소자.An organic film comprising the compound represented by Formula 1 is an organic light emitting device that is a hole transport layer.
- 제 1항에 있어서,The method of claim 1,상기 화학식 2로 표시되는 화합물을 포함하는 유기막은 전자차단층인 유기전계발광소자.The organic film containing the compound represented by Formula 2 is an organic light emitting device that is an electron blocking layer.
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