WO2017105039A9 - Novel compound and organic light emitting device comprising same - Google Patents
Novel compound and organic light emitting device comprising same Download PDFInfo
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- WO2017105039A9 WO2017105039A9 PCT/KR2016/014449 KR2016014449W WO2017105039A9 WO 2017105039 A9 WO2017105039 A9 WO 2017105039A9 KR 2016014449 W KR2016014449 W KR 2016014449W WO 2017105039 A9 WO2017105039 A9 WO 2017105039A9
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- compound
- light emitting
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
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- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
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- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000063 azene Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000003824 heptacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC6=CC7=CC=CC=C7C=C6C=C5C=C4C=C3C=C12)* 0.000 description 1
- ACJRMEVDTSKFDP-UHFFFAOYSA-N heptaphene Chemical group C1=CC=C2C=C(C=C3C4=CC5=CC6=CC=CC=C6C=C5C=C4C=CC3=C3)C3=CC2=C1 ACJRMEVDTSKFDP-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 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
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 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
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- PGXOVVAJURGPLL-UHFFFAOYSA-N trinaphthylene Chemical group C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4C4=CC5=CC=CC=C5C=C4C3=CC2=C1 PGXOVVAJURGPLL-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
Definitions
- the present application relates to a novel compound and an organic light emitting device comprising the compound as an electron transporting layer or a hole blocking layer.
- an organic light emitting device capable of low-voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is a mainstream of flat panel display devices.
- LCD liquid crystal display
- the material used as the organic material layer in the organic light emitting device may be largely classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
- the light emitting material may be classified into a polymer and a single molecule according to molecular weight, and a fluorescent material derived from a singlet excited state of electrons, a phosphorescent material derived from a triplet excited state of electrons, and a triplet of electrons according to a light emitting mechanism. It can be classified as a delayed fluorescent material resulting from the movement of electrons from a single excited state to a singlet excited state.
- the light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to achieve better natural colors, depending on the color of light emitted.
- a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to give high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host to be used.
- Korean Patent Laid-Open Publication No. 2013-0060953 discloses an anthracene derivative-based organic electroluminescent device.
- the present application is to provide a novel compound and an organic light emitting device comprising the compound as an electron transport layer or a hole blocking layer.
- a first aspect of the present application provides a compound represented by the following Chemical Formula 1:
- R 1 and R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or substituted or unsubstituted C 2 to C 50 is a hetero aryl group
- X is substituted or unsubstituted CR 3 or N
- R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or Substituted or unsubstituted C 2 to C 50 hetero aryl group
- L is substituted or unsubstituted C 6 to C 30 arylene or C 3 to C 20 hetero arylene group
- Z is N or CR 3
- R 1 may form a ring with ⁇ carbon of the surrounding aryl ( ⁇ carbon of the repeating unit m or ⁇ carbon of R 2 )
- m and n are each independently an integer of 0 to 2, provided that
- the second aspect of the present application provides an organic light emitting device comprising at least one organic layer containing a compound according to the first aspect of the present application formed between the anode electrode and the cathode electrode.
- the phosphine oxide unit included in the compound has a strong electron attracting effect and low HOMO (highest occupied molecular orbital) compared to the conventional heterocyclic compound Since it has a level, the electron transporting property and hole blocking property become strong, thereby achieving low voltage high efficiency and high color purity of the organic light emitting element.
- the phosphine oxide unit prevents the increase in the conjugated bond length, it is possible to maintain high singlet energy and triplet energy.
- the X and Y axis coordinates of the CIE color coordinates can be reduced.
- FIG. 1 schematically illustrates a cross section of an organic light emitting device according to an embodiment of the present disclosure.
- FIG. 2 is a graph illustrating current density characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
- FIG. 3 is a graph illustrating current efficiency characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
- FIG. 4 illustrates an electroluminescence spectrum of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
- FIG. 5 is a graph illustrating the lifespan of the organic light emitting diode according to the exemplary embodiment of the present application.
- FIG. 6 is a graph illustrating current density characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
- FIG. 7 is a graph illustrating current efficiency characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
- FIG. 8 illustrates an electroluminescence spectrum of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
- FIG 9 is a graph illustrating the lifespan of the organic light emitting diode according to the exemplary embodiment of the present application.
- the term "combination (s) thereof" included in the expression of a makushi form refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of makushi form, It means to include one or more selected from the group consisting of the above components.
- aromatic ring or “aryl” means to include at least one aromatic hydrocarbon group
- aromatic hetero ring or “hetero aryl” means at least one aromatic hydrocarbon group and at least one hetero atom. As it means to include, it represents that at least one carbon atom of the aromatic hydrocarbon group is substituted by a hetero atom.
- aromatic ring (aryl) or aromatic hetero ring (hetero aryl) includes a plurality of rings
- the aromatic ring or the aromatic hetero ring includes one aromatic ring and as an additional ring, an aromatic ring or a non-aromatic ring It may be to include.
- the plural ring may include at least one aromatic ring and an additional ring bonded to one atom or fused through two or more atoms, but may not be limited thereto.
- the aryl is, for example, a benzene ring, toluene ring, naphthalene ring, anthracene ring, phenanthrene ring, pentarene ring, indene ring, biphenylene ring, phenylene ring, azene ring, heptarene ring, acenaph Tylene ring, fluorene ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl-crysene ring, pysene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexa Pen ring, he
- the heteroaryl may be, for example, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indole Reel group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group, 2-isoindoleyl group, 3-isoindoleyl group, 4- Isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4- Benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl
- hetero atom means an atom other than carbon and hydrogen atoms, for example, the hetero atom is Si, Se, N, O, S, P, As, F, Cl, Br And I, but may include those selected from the group consisting of, but may not be limited thereto.
- halogen or “halo” means that a halogen atom belonging to group 17 of the periodic table is included in the compound in the form of a functional group, and may be, for example, chlorine, bromine, fluorine or iodine. However, this may not be limited.
- substituted or unsubstituted is CN, hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group, or substituted or unsubstituted C 2 It may include a substituent such as C 50 hetero aryl group.
- a first aspect of the present application provides a compound represented by the following Chemical Formula 1:
- R 1 to R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or substituted or unsubstituted C 2 to C 50 is a hetero aryl group
- X is substituted or unsubstituted CR 3 or N
- R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or Substituted or unsubstituted C 2 to C 50 hetero aryl group
- L is substituted or unsubstituted C 6 to C 30 arylene or C 3 to C 20 hetero arylene group
- Z is N or CR 3
- R 1 may form a ring with ⁇ carbon of surrounding aryl
- m and n are each independently an integer of 0 to 2, provided that when X is CR 3 , n is not 0. In this case, the ⁇
- R 1 when R 1 forms a ring with ⁇ carbon of the surrounding aryl, it may have high thermal stability by increasing the rigidity of the molecule.
- the electron transport increasing (LUMO) energy level is lowered by using the compound represented by Chemical Formula 1 as an electron transporting material, a large amount of electrons are injected into the light emitting layer because electrons are facilitated. The efficiency of the organic light emitting device can be increased.
- LUMO electron transport increasing
- by using the compound represented by the formula (1) as a hole blocking layer to prevent holes from leaking to the electron transport layer and the hole remains in the light emitting layer may increase the efficiency of the organic light emitting device.
- each of R 1 to R 3 may include one selected independently from the following substituents, but may not be limited thereto:
- Y is each independently, C, N, or CR 4
- R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
- L may be selected from the following substituents, but may not be limited thereto:
- Y is each independently, C, N, or CR 4
- R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
- the compound may include, but is not limited to, one represented by one of the following formulas:
- the compound may be prepared by a method for preparing a compound represented by Scheme 1, but may not be limited thereto.
- R 1 to R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or substituted or unsubstituted C 2 to C 50 is a hetero aryl group
- X is substituted or unsubstituted CR 3 or N
- R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or Substituted or unsubstituted C 2 to C 50 hetero aryl group
- L is substituted or unsubstituted C 6 to C 30 arylene or C 3 to C 20 hetero arylene group
- Z is N or CR 3
- R 1 may form a ring with ⁇ carbon of surrounding aryl
- m and n are each independently an integer of 0 to 2, provided that when X is CR 3 , n is not 0. In this case, the ⁇
- R 1 when R 1 forms a ring with ⁇ carbon of the surrounding aryl, it may have high thermal stability by increasing the rigidity of the molecule.
- each of R 1 to R 3 may include one selected independently from the following substituents, but may not be limited thereto:
- Y is each independently, C, N, or CR 4
- R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
- L may be selected from the following substituents, but may not be limited thereto:
- Y is each independently, C, N, or CR 4
- R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
- the second aspect of the present application provides an organic light emitting device comprising at least one organic layer containing a compound according to the first aspect of the present application formed between the anode electrode and the cathode electrode.
- the organic light emitting device may include one or more organic material layers including the compound represented by the formula (1).
- the organic material layer including the compound represented by Formula 1 may be an electron transport layer or a hole blocking layer.
- the compound may be used alone or in combination with a known electron injecting material or a compound for an electron transporting material as the electron transporting material, but may not be limited thereto.
- the organic light emitting device is a hole injection layer (HIL), hole transport layer (HTL), light emitting layer (EML), electron transport layer (ETL), electron injection between the anode (anode) and the cathode (cathode)
- HIL hole injection layer
- HTL hole transport layer
- EML light emitting layer
- ETL electron transport layer
- EIL electron injection between the anode (anode) and the cathode (cathode)
- EIL organic material layer
- EIL electron transport layer
- Figure 1 schematically shows a cross-section of an organic light emitting device according to an embodiment of the present application.
- an organic light emitting diode includes an anode electrode 11 formed on a substrate 10, a hole injection layer 12 formed on the anode electrode 11, and the hole injection layer.
- a hole transport layer 13 formed on the hole 12 a light emitting layer 14 formed on the hole transport layer 13, an electron transport layer 15 formed on the light emitting layer 14, and electrons formed on the electron transport layer 15. It may include an injection layer 16 and a cathode electrode 17 formed on the electron injection layer 16, but may not be limited thereto.
- the organic light emitting device according to the embodiment of the present application may be manufactured by the following method.
- an anode electrode 11 is formed by depositing an anode electrode material having a low work function on the substrate 10 to enable injection of holes.
- the substrate 10 may be used without particular limitation as long as it is a substrate used in a conventional organic light emitting device, in particular mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof It may be to include an excellent glass substrate or a transparent plastic substrate, but may not be limited thereto.
- the anode electrode 11 is transparent and has excellent conductivity indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and their It may be to include one selected from the group consisting of combinations, but may not be limited thereto.
- the anode electrode material may be deposited by a conventional anode electrode forming method, for example, may be deposited on a substrate by a deposition method or a spattering method, but may not be limited thereto.
- the hole injection layer 12 may be formed on the anode 11 by vacuum deposition, spin coating, casting, or Langmuir-Bloodjet (LB), but is not limited thereto. Can be.
- the hole injection layer 12 may be formed by a vacuum deposition method which is easy to obtain a uniform film quality and is hard to generate pin holes.
- the compound used as a material of the hole injection layer 12 or the structure and thermal characteristics of the hole injection layer 12 of interest Depending on the deposition conditions, but generally a deposition temperature of about 50 ° C.
- the hole injection layer 12 material may be used without particular limitation, TCTA [4, which is a phthalocyanine compound or starburst type amine derivatives such as copper phthalocyanine disclosed in US Patent No. 4,356,429 4 ', 4 "-tri (N-carbazolyl) triphenylamine], m-MTDATA [4,4', 4" -tris (3-methylphenylamino) triphenylamine], m-MTDAPB [4,4 ' , 4 "-tris (3-methylphenylamino) phenoxybenzene], or HI-406 [N 1 , N 1 '-(biphenyl-4,4'-diyl) bis (N 1-(naphthalen- 1 -yl ) -N 4 , N 4 -diphenylbenzene-1,4-diamine] may be used as the hole injection layer material, but may not be limited thereto.
- TCTA is a phthalocyanine compound or starburs
- the hole transport layer 13 may be formed on the hole injection layer 12 by a method such as vacuum deposition, spin coating, casting, or LB, but may not be limited thereto.
- the hole transport layer 13 may be formed by a vacuum deposition method which is easy to obtain a uniform film quality and is hard to generate pin holes.
- the deposition conditions vary depending on the compound used, but in general, the hole transport layer 13 is preferably selected in a condition range substantially the same as the deposition conditions of the hole injection layer. .
- the material of the hole transport layer 13 may be used without particular limitation, and may be arbitrarily selected from conventionally known materials used as the hole transport layer 13.
- the hole transport layer 13 material is a carbazole derivative such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1, Aromatic condensed rings such as 1-biphenyl] -4,4'-diamine (TPD) or N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine ( ⁇ -NPD) Eggplant can be used a conventional amine derivative and the like.
- the light emitting layer 14 may be formed on the hole transport layer 13 by a method such as vacuum deposition, spin coating, casting, LB, or the like, but may not be limited thereto.
- the light emitting layer 14 may be formed by a vacuum deposition method which is easy to obtain a uniform film quality and is hard to generate pin holes.
- the deposition conditions are different depending on the compound to be used, but in general, it is preferable to select in a condition range almost the same as the deposition conditions of the hole injection layer.
- the light emitting layer 14 may be a known host or dopant.
- the fluorescent dopant may be IDE102 or IDE105 available from Idemitsu, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethyryl).
- Sen-6,12-diamine may be a green phosphorescent dopant ⁇ Ir (ppy) 3 [tris (2-phenylpyridine) iridium] ⁇ , a blue phosphorescent dopant F 2 Irpic ⁇ iridium (III) Bis [4,6-difluorophenyl) -pyridinato-N, C2 '] picolinate) ⁇ , a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped).
- the doping concentration of the dopant is not particularly limited, but it is preferable that the dopant is about 0.01 to about 15 parts by weight based on 100 parts by weight of the host.
- a hole suppressing material (HBL) is further laminated by vacuum deposition or spin coating. It is preferable.
- the hole-suppressing material which can be used at this time is not specifically limited, Any thing can be selected and used from the well-known thing used as a hole-suppressing material.
- the hole suppressing material may include an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole suppressing material described in Japanese Patent Laid-Open No. 11-329734 (A1).
- Bis (8-hydroxy-2-methylquinolinolato) -aluminum biphenoxide], or a phenanthrolines-based compound e.g., UDC Corporation BCP (Basocuproin)
- UDC Corporation BCP Basocuproin
- the electron transport layer 15 is formed on the light emitting layer 14.
- the electron transport layer 15 may be formed by a method such as vacuum deposition, spin coating, casting, or LB, but may not be limited thereto. Preferably, the electron transport layer 15 may be formed.
- the deposition conditions vary depending on the compound used, but in general, the electron transport layer 15 is preferably selected in a condition range substantially the same as the deposition conditions of the hole injection layer. .
- the electron transport layer 15 functions to stably transport electrons injected from an electron injection electrode (cathode electrode 17), and the compound represented by Chemical Formula 1 is used alone. Or known mixtures of electron transport layers may be used.
- the electron transport properties are enhanced by the phosphine oxide unit included in the compound, accordingly the organic light emitting device Low voltage and high efficiency characteristics can be achieved.
- the recombination region is moved by the phosphine oxide unit, so that color coordinates x and y may be reduced.
- the phosphine oxide unit prevents the increase in the conjugated bond length, it is possible to maintain a high triplet energy.
- the electron injection layer (EIL) 16 that is a material having a function of facilitating the injection of electrons from the cathode (cathode electrode 17) on the electron transport layer 15 is laminated It may further include, but may not be limited to this.
- the electron injection layer 16 may be a material selected from the group consisting of LiF, NaCl, CsF, Li 2 O, BaO, and combinations thereof, but may not be limited thereto. .
- a compound represented by Chemical Formula 1 may be further included as the hole blocking layer between the emission layer 14 and the electron transport layer 15, but is not limited thereto. Can be.
- the compound represented by Formula 1 as a hole blocking layer, holes may be prevented from leaking to the electron transport layer, and the holes may remain in the light emitting layer to increase the efficiency of the organic light emitting device.
- the cathode forming metal can be formed on the electron injection layer 16 by vacuum deposition or sputtering and used as the cathode electrode 17.
- the cathode electrode 17 may include one selected from the group consisting of lithium, magnesium, aluminum, calcium, indium, silver, gold, and combinations thereof, but may not be limited thereto.
- a transmissive cathode using ITO, IZO, SnO 2 , or ZnO may be used as the cathode electrode 17 to obtain a front light emitting device, but may not be limited thereto.
- the organic light emitting device is not only an anode, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injection layer, and a cathode structure, but also an organic light emitting device having a variety of structures, 1 It is also possible to form additional layers or intermediate layers of two layers.
- each organic material layer formed in accordance with one embodiment of the present application can be adjusted according to the required degree, preferably may include about 10 nm to about 1,000 nm, more preferably about 20 nm to about 150 It may be one containing nm.
- the organic material layer including the compound represented by the formula (1) has the advantage that the surface is uniform, excellent in shape stability because the thickness of the organic material layer can be adjusted in molecular units.
- Reactant 1 was used instead of Reactant 5 to synthesize the following compounds:
- Reactant 2 was used instead of Reactant 5 to synthesize the following compounds:
- Reactant 1 was used instead of Reactant 2 to synthesize the following compounds:
- the following reactants 1 to 5 were used as reactants for preparing the organic light emitting device.
- Compound 3 was synthesized using the same method as compound 1, but using reactant 2 instead of reactant 1.
- Compound 4 was synthesized using the same method as compound 1, but using reactant 2 instead of reactant 1, and using intermediate 2 instead of intermediate 1.
- Compound 6 was synthesized using the same method as compound 1, but using reactant 3 instead of reactant 1.
- Compound 7 was synthesized using the same method as compound 1, but using reactant 4 instead of reactant 1, and using intermediate 2 instead of intermediate 1.
- Compound 8 was synthesized using the same method as compound 1, but using reactant 4 instead of reactant 1.
- an organic light emitting device according to the present embodiment was manufactured.
- the organic light emitting device is composed of an anode electrode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transport layer 15 / cathode electrode [electron injection electrode 17)] in order.
- the following materials were used as the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of this example and the comparative example:
- the glass substrate coated with the indium tin oxide (ITO) thin film having a thickness of 1500 ⁇ was washed with distilled water ultrasonically. After the distilled water was washed, ultrasonic washing with a solvent such as isopropyl alcohol, acetone, or methanol was dried and dried. The substrate was then transferred to a plasma scrubber and then the substrate was cleaned for 5 minutes using an oxygen plasma. Subsequently, HT01 600 kV as a hole injection layer and Ref. 4 and 250 kV as a hole transport layer were formed into a film using a thermal evaporator on the ITO substrate.
- ITO indium tin oxide
- BH01: BD01 was doped at 5% as a light emitting layer to form a film having a thickness of 250 kHz.
- the prepared compound 1 and Liq were formed into a film having a thickness of 300 ⁇ s at a 1: 1 ratio, and then LiF 10 ⁇ s and aluminum (Al) 1,000 ⁇ s were formed and the device was encapsulated in a glove box.
- An organic light emitting device was manufactured by
- An organic light emitting device was manufactured in the same manner as in Example 1, where an organic light emitting device in which an electron transporting layer was formed using the prepared compounds 2 to 18, respectively.
- An organic light-emitting device was manufactured in the same manner as in Example 1, but using ET-01 instead of Compound 1 as an electron transporting layer.
- the organic light emitting device according to the present embodiment was confirmed that the physical properties compared to the comparative example.
- 2 to 5 are graphs showing current density characteristics, current efficiency characteristics, electroluminescence spectra, and lifetime of the organic light emitting diode according to Example 6, respectively.
- 6 to 9 are graphs showing current density characteristics, current efficiency characteristics, electroluminescence spectra, and lifetime of the organic light emitting diode according to Example 8, respectively.
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Abstract
The present invention relates to a novel compound and an organic light emitting device comprising the compound as an electron transport layer or a hole blocking layer.
Description
본원은, 신규한 화합물 및 상기 화합물을 전자 수송층 또는 정공 저지층으로서 포함하는 유기 발광 소자에 관한 것이다.The present application relates to a novel compound and an organic light emitting device comprising the compound as an electron transporting layer or a hole blocking layer.
최근, 자체 발광형으로 저전압 구동이 가능한 유기 발광 소자는, 평판 표시소자의 주류인 액정디스플레이(liquid crystal display, LCD)에 비해, 시야각, 대조비 등이 우수하고 백라이트가 불필요하여 경량 및 박형이 가능하며 소비전력 측면에서도 유리하고 색 재현 범위가 넓어, 차세대 표시소자로서 주목을 받고 있다.Recently, an organic light emitting device capable of low-voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is a mainstream of flat panel display devices. In terms of power consumption and wide color reproduction range, it is attracting attention as a next-generation display device.
유기 발광 소자에서 유기물층으로 사용되는 재료는 크게 기능에 따라, 발광 재료, 정공 주입 재료, 정공 수송 재료, 전자 수송 재료, 전자 주입 재료 등으로 분류될 수 있다. 상기 발광 재료는 분자량에 따라 고분자와 단분자로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와, 전자의 삼중항 여기상태로부터 유래되는 인광 재료와, 전자의 삼중항 여기상태로부터 일중항 여기상태로의 전자의 이동에 유래되는 지연형광 재료로 분류될 수 있다. 발광 재료는 발광 색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도펀트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도펀트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도펀트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도펀트의 파장대로 이동하므로, 이용하는 도펀트와 호스트의 종류에 따라 원하는 파장의 빛을 수득할 수 있다.The material used as the organic material layer in the organic light emitting device may be largely classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer and a single molecule according to molecular weight, and a fluorescent material derived from a singlet excited state of electrons, a phosphorescent material derived from a triplet excited state of electrons, and a triplet of electrons according to a light emitting mechanism. It can be classified as a delayed fluorescent material resulting from the movement of electrons from a single excited state to a singlet excited state. The light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to achieve better natural colors, depending on the color of light emitted. In addition, a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to give high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host to be used.
현재까지 이러한 유기 발광 소자에 사용되는 물질로서 다양한 화합물들이 알려져 있으나, 이제까지 알려진 물질을 이용한 유기 발광 소자의 경우 높은 구동전압, 낮은 효율 및 짧은 수명으로 인해 실용화하는 데에 많은 어려움이 있었다. 따라서, 우수한 특성을 갖는 물질을 이용하여 저전압 구동, 고휘도 및 장수명을 갖는 유기 발광 소자를 개발하려는 노력이 지속되어 왔다.To date, various compounds are known as materials used in such organic light emitting devices. However, in the case of organic light emitting devices using materials known to date, there are many difficulties in practical use due to high driving voltage, low efficiency, and short lifespan. Therefore, efforts have been made to develop organic light emitting devices having low voltage driving, high brightness and long life using materials having excellent characteristics.
이와 관련하여, 대한민국 공개특허 제2013-0060953호는 안트라센 유도체-기반 유기 전계 발광 소자에 대해 개시하고 있다. In this regard, Korean Patent Laid-Open Publication No. 2013-0060953 discloses an anthracene derivative-based organic electroluminescent device.
그러나, 포스핀 옥사이드-기반 화합물을 전자 수송층 또는 정공 저지층으로서 사용함으로써 유기 발광 소자의 저전압, 고효율, 높은 광학 안정성, 및 장기간 안정성을 달성하기 위한 유기 발광 소자에 대해서는 보고된 바 없다.However, there is no report on organic light emitting devices for achieving low voltage, high efficiency, high optical stability, and long term stability of organic light emitting devices by using phosphine oxide-based compounds as electron transporting layers or hole blocking layers.
본원은, 신규한 화합물 및 상기 화합물을 전자 수송층 또는 정공 저지층으로서 포함하는 유기 발광 소자를 제공하고자 한다.The present application is to provide a novel compound and an organic light emitting device comprising the compound as an electron transport layer or a hole blocking layer.
그러나, 본원이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
본원의 제 1 측면은, 하기 화학식 1로서 표시되는 화합물을 제공한다:A first aspect of the present application provides a compound represented by the following Chemical Formula 1:
[화학식 1][Formula 1]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 화학식 1 중, R1 및 R2은, 각각 독립적으로, 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고, X는 치환 또는 비치환된 CR3 또는 N이고, R3는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고, L은 치환 또는 비치환된 C6 내지 C30의 아릴렌 또는 C3 내지 C20의 헤테로 아릴렌기이고, Z는 N 또는 CR3이고, R1은 주변 아릴의 α 탄소(반복단위 m의 α 탄소 또는 R2의 α 탄소)와 고리를 형성할 수 있고, m 및 n은 각각 독립적으로, 0 내지 2의 정수이며, 단, X가 모두 CR3일 때, n은 0이 아니다.In Formula 1, R 1 and R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or substituted or unsubstituted C 2 to C 50 is a hetero aryl group, X is substituted or unsubstituted CR 3 or N, R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or Substituted or unsubstituted C 2 to C 50 hetero aryl group, L is substituted or unsubstituted C 6 to C 30 arylene or C 3 to C 20 hetero arylene group, Z is N or CR 3 , R 1 may form a ring with α carbon of the surrounding aryl (α carbon of the repeating unit m or α carbon of R 2 ), and m and n are each independently an integer of 0 to 2, provided that X is When all CR 3 , n is not zero.
본원의 제 2 측면은, 애노드 전극, 캐소드 전극 사이에 형성된 본원의 제 1 측면에 따른 화합물을 함유하는 1 층 이상의 유기물층을 포함하는 유기 발광 소자를 제공한다.The second aspect of the present application provides an organic light emitting device comprising at least one organic layer containing a compound according to the first aspect of the present application formed between the anode electrode and the cathode electrode.
본원의 일 구현예에 따른 화합물을 전자 수송층 또는 정공 저지층으로서 사용함으로써, 상기 화합물에 포함되는 포스핀 옥사이드 유닛에 의해 종래의 헤테로 고리 화합물에 비해 강한 전자 끌게 효과 및 낮은 HOMO(highest occupied molecular orbital) 레벨을 가지기 때문에, 전자의 수송 특성 및 정공 저지 특성이 강해지고, 이에 따라 유기 발광 소자의 저전압 고효율, 및 고색순도를 달성할 수 있다. 또한, 상기 포스핀 옥사이드 유닛은 공액 결합 길이의 증가를 방지하여, 높은 일중항 에너지 및 삼중항 에너지의 유지가 가능하다. By using the compound according to one embodiment of the present application as an electron transporting layer or a hole blocking layer, the phosphine oxide unit included in the compound has a strong electron attracting effect and low HOMO (highest occupied molecular orbital) compared to the conventional heterocyclic compound Since it has a level, the electron transporting property and hole blocking property become strong, thereby achieving low voltage high efficiency and high color purity of the organic light emitting element. In addition, the phosphine oxide unit prevents the increase in the conjugated bond length, it is possible to maintain high singlet energy and triplet energy.
더불어, 본원의 일 구현예에 따른 화합물에 의해 재결합 영역을 이동시킴으로써 CIE 색좌표의 X 축 및 Y축 좌표를 감소시킬 수 있다.In addition, by shifting the recombination region by the compound according to one embodiment of the present application, the X and Y axis coordinates of the CIE color coordinates can be reduced.
상기 유기 발광 소자의 저전압, 고효율, 높은 광학 안정성으로 인해 장기간 소자 구동 안정성 또한 향상된다.Due to the low voltage, high efficiency, and high optical stability of the organic light emitting diode, long-term device driving stability is also improved.
도 1은 본원의 일 구현예에 따른 유기 발광 소자의 단면을 개략적으로 도시한 것이다.1 schematically illustrates a cross section of an organic light emitting device according to an embodiment of the present disclosure.
도 2는 본원의 일 실시예에 있어서, 유기 발광 소자의 전류 밀도 특성을 나타낸 그래프이다.2 is a graph illustrating current density characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
도 3은 본원의 일 실시예에 있어서, 유기 발광 소자의 전류 효율 특성을 나타낸 그래프이다.3 is a graph illustrating current efficiency characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
도 4는 본원의 일 실시예에 있어서, 유기 발광 소자의 전계 발광 스펙트럼을 나타낸 것이다.4 illustrates an electroluminescence spectrum of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
도 5는 본원의 일 실시예에 있어서, 유기 발광 소자의 수명을 나타낸 그래프이다.5 is a graph illustrating the lifespan of the organic light emitting diode according to the exemplary embodiment of the present application.
도 6은 본원의 일 실시예에 있어서, 유기 발광 소자의 전류 밀도 특성을 나타낸 그래프이다.6 is a graph illustrating current density characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
도 7은 본원의 일 실시예에 있어서, 유기 발광 소자의 전류 효율 특성을 나타낸 그래프이다.7 is a graph illustrating current efficiency characteristics of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
도 8은 본원의 일 실시예에 있어서, 유기 발광 소자의 전계 발광 스펙트럼을 나타낸 것이다.8 illustrates an electroluminescence spectrum of an organic light emitting diode according to an exemplary embodiment of the present disclosure.
도 9는 본원의 일 실시예에 있어서, 유기 발광 소자의 수명을 나타낸 그래프이다.9 is a graph illustrating the lifespan of the organic light emitting diode according to the exemplary embodiment of the present application.
아래에서는 첨부한 도면을 참조하여 본원이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본원의 실시예를 상세히 설명한다. 그러나 본원은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 그리고 도면에서 본원을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.
본원 명세서 전체에서, 어떤 부분이 다른 부분과 “연결”되어 있다고 할 때, 이는 “직접적으로 연결”되어 있는 경우뿐 아니라, 그 중간에 다른 소자를 사이에 두고 “전기적으로 연결”되어 있는 경우도 포함한다. Throughout this specification, when a part is said to be "connected" with another part, this includes not only the "directly connected" but also the "electrically connected" between other elements in between. do.
본원 명세서 전체에서, 어떤 부재가 다른 부재 “상에” 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.Throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 “포함” 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. 본원 명세서 전체에서 사용되는 정도의 용어 “약”, “실질적으로” 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본원의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다. 본원 명세서 전체에서 사용되는 정도의 용어 “~(하는) 단계” 또는 “~의 단계”는 “~ 를 위한 단계”를 의미하지 않는다.Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided, and an understanding of the present application may occur. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.
본원 명세서 전체에서, 마쿠시 형식의 표현에 포함된 “이들의 조합(들)”의 용어는 마쿠시 형식의 표현에 기재된 구성 요소들로 이루어진 군에서 선택되는 하나 이상의 혼합 또는 조합을 의미하는 것으로서, 상기 구성 요소들로 이루어진 군에서 선택되는 하나 이상을 포함하는 것을 의미한다.Throughout this specification, the term "combination (s) thereof" included in the expression of a makushi form refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of makushi form, It means to include one or more selected from the group consisting of the above components.
본원 명세서 전체에서, “A 및/또는 B”의 기재는 “A 또는 B, 또는 A 및 B”를 의미한다.Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.
본원 명세서 전체에서, 용어 "방향족 고리" 또는 "아릴"은 적어도 하나의 방향족 탄화수소기를 포함하는 것을 의미하며, 용어 "방향족 헤테로 고리" 또는 "헤테로 아릴"은 적어도 하나의 방향족 탄화수소기와 적어도 하나의 헤테로 원자를 포함하는 것을 의미하는 것으로서, 상기 방향족 탄화수소기의 적어도 하나의 탄소 원자가 헤테로 원자에 의해 치환된 것을 나타낸다. 상기 방향족 고리(아릴) 또는 방향족 헤테로 고리(헤테로 아릴)가 복수환을 포함하는 경우, 상기 방향족 고리 또는 상기 방향족 헤테로 고리는, 하나의 방향족 고리를 포함하고 부가적인 고리로서 방향족 고리 또는 비방향족 고리를 포함하는 것일 수 있다. 이때, 상기 복수환은 적어도 하나의 방향족 고리와 부가적인 고리가 하나의 원자를 통해 결합된 것 또는 둘 이상의 원자를 통해 융합된 것을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. 상기 아릴은, 예를 들어, 벤젠 고리, 톨루엔 고리, 나프탈렌 고리, 안트라센 고리, 페난트렌 고리, 펜타렌 고리, 인덴 고리, 비페닐렌 고리, 페날렌 고리, 아즈렌 고리, 헵타렌 고리, 아세나프틸렌 고리, 플루오렌 고리, 테트라센 고리, 트리페닐렌 고리, 피렌 고리, 크리센 고리, 에틸-크리센 고리, 피센 고리, 페릴렌 고리, 펜타펜 고리, 펜타센 고리, 테트라페닐렌 고리, 헥사펜 고리, 헥사센고리, 루비센 고리, 코로넨 고리, 트리나프틸렌 고리, 헵타펜 고리, 헵타센 고리, 피란트렌 고리, 오바렌 고리, 플로란센 고리, 벤조플로란센 고리, 비페닐기, 트리페닐기, 터페닐기, 9-안트릴기, 2-안트릴기, 9-페난트릴기, 2-페난트릴기, 1-피렌일기, 크라이센일기, 나프타센일기 및 코로닐기를 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. Throughout this specification, the term “aromatic ring” or “aryl” means to include at least one aromatic hydrocarbon group, and the term “aromatic hetero ring” or “hetero aryl” means at least one aromatic hydrocarbon group and at least one hetero atom. As it means to include, it represents that at least one carbon atom of the aromatic hydrocarbon group is substituted by a hetero atom. When the aromatic ring (aryl) or aromatic hetero ring (hetero aryl) includes a plurality of rings, the aromatic ring or the aromatic hetero ring includes one aromatic ring and as an additional ring, an aromatic ring or a non-aromatic ring It may be to include. In this case, the plural ring may include at least one aromatic ring and an additional ring bonded to one atom or fused through two or more atoms, but may not be limited thereto. The aryl is, for example, a benzene ring, toluene ring, naphthalene ring, anthracene ring, phenanthrene ring, pentarene ring, indene ring, biphenylene ring, phenylene ring, azene ring, heptarene ring, acenaph Tylene ring, fluorene ring, tetracene ring, triphenylene ring, pyrene ring, chrysene ring, ethyl-crysene ring, pysene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring, hexa Pen ring, hexasen ring, rubisen ring, coronene ring, trinaphthylene ring, heptaphen ring, heptacene ring, pyrantrene ring, ovaren ring, florene ring, benzofloransen ring, biphenyl group, Triphenyl group, terphenyl group, 9- anthryl group, 2- anthryl group, 9-phenanthryl group, 2-phenanthryl group, 1-pyrenyl group, chrysenyl group, naphthacenyl group and coronyl group However, this may not be limited.
상기 헤테로 아릴은, 예를 들어, 1-피롤릴기, 2-피롤릴기, 3-피롤릴기, 피라진일기, 2-피리딘일기, 3-피리딘일기, 4-피리딘일기, 1-인돌릴기, 2-인돌릴기, 3-인돌릴기, 4-인돌릴기, 5-인돌릴기, 6-인돌릴기, 7-인돌릴기, 1-아이소인돌릴기, 2-아이소인돌릴기, 3-아이소인돌릴기, 4-아이소인돌릴기, 5-아이소인돌릴기, 6-아이소인돌릴기, 7-아이소인돌릴기, 2-퓨릴기, 3-퓨릴기, 2-벤조퓨란일기, 3-벤조퓨란일기, 4-벤조퓨란일기, 5-벤조퓨란일기, 6-벤조퓨란일기, 7-벤조퓨란일기, 1-아이소벤조퓨란일기, 3-아이소벤조퓨란일기, 4-아이소벤조퓨란일기, 5-아이소벤조퓨란일기, 6-아이소벤조퓨란일기, 7-아이소벤조퓨란일기, 퀴놀릴기, 3-퀴놀릴기, 4-퀴놀릴기, 5-퀴놀릴기, 6-퀴놀릴기, 7-퀴놀릴기, 8-퀴놀릴기, 1-아이소퀴놀릴기, 3-아이소퀴놀릴기, 4-아이소퀴놀릴기, 5-아이소퀴놀릴기, 6-아이소퀴놀릴기, 7-아이소퀴놀릴기, 8-아이소퀴놀릴기, 2-퀴녹살린일기, 5-퀴녹살린일기, 6-퀴녹살린일기, 1-카바졸릴기, 2-카바졸릴기, 3-카바졸릴기, 4-카바졸릴기, 9-카바졸릴기, 1-페난트리딘일기, 2-페난트리딘일기, 3-페난트리딘일기, 4-페난트리딘일기, 6-페난트리딘일기, 7-페난트리딘일기, 8-페난트리딘일기, 9-페난트리딘일기, 10-페난트리딘일기, 1-아크리딘일기, 2-아크리딘일기, 3-아크리딘일기, 4-아크리딘일기, 9-아크리딘일기, 1,7-페난트롤린-2-일기, 1,7-페난트롤린-3-일기, 1,7-페난트롤린-4-일기, 1,7-페난트롤린-5-일기, 1,7-페난트롤린-6-일기, 1,7-페난트롤린-8-일기, 1,7-페난트롤린-9-일기, 1,7-페난트롤린-10-일기, 1,8-페난트롤린-2-일기, 1,8-페난트롤린-3-일기, 1,8-페난트롤린-4-일기, 1,8-페난트롤린-5-일기, 1,8-페난트롤린-6-일기,1,8-페난트롤린-7-일기, 1,8-페난트롤린-9-일기, 1,8-페난트롤린-10-일기, 1,9-페난트롤린-2-일기, 1,9-페난트롤린-3-일기, 1,9-페난트롤린-4-일기, 1,9-페난트롤린-5-일기, 1,9-페난트롤린-6-일기, 1,9-페난트롤린-7-일기, 1,9-페난트롤린-8-일기, 1,9-페난트롤린-10-일기, 1,10-페난트롤린-2-일기, 1,10-페난트롤린-3-일기, 1,10-페난트롤린-4-일기, 1,10-페난트롤린-5-일기, 2,9-페난트롤린-1-일기, 2,9-페난트롤린-3-일기, 2,9-페난트롤린-4-일기, 2,9-페난트롤린-5-일기, 2,9-페난트롤린-6-일기, 2,9-페난트롤린-7-일기, 2,9-페난트롤린-8-일기, 2,9-페난트롤린-10-일기, 2,8-페난트롤린-1-일기, 2,8-페난트롤린-3-일기, 2,8-페난트롤린-4-일기, 2,8-페난트롤린-5-일기, 2,8-페난트롤린-6-일기, 2,8-페난트롤린-7-일기, 2,8-페난트롤린-9-일기, 2,8-페난트롤린-10-일기, 2,7-페난트롤린-1-일기, 2,7-페난트롤린-3-일기, 2,7-페난트롤린-4-일기, 2,7-페난트롤린-5-일기, 2,7-페난트롤린-6-일기, 2,7-페난트롤린-8-일기, 2,7-페난트롤린-9-일기, 2,7-페난트롤린-10-일기, 1-페나진일기, 2-페나진일기, 1-페노싸이아진일기,2-페노싸이아진일기, 3-페노싸이아진일기, 4-페노싸이아진일기, 10-페노싸이아진일기, 1-페녹사딘일기, 2-페녹사딘일기, 3-페녹사딘일기, 4-페녹사딘일기, 10-페녹사딘일기, 2-옥사졸릴기, 4-옥사졸릴기, 5-옥사졸릴기, 2-옥사다이아졸릴기, 5-옥사다이아졸릴기, 3-퓨라잔일기, 2-싸이엔일기, 3-싸이엔일기, 2-메틸피롤-1-일기, 2-메틸피롤-3-일기, 2-메틸피롤-4-일기, 2-메틸피롤-5-일기, 3-메틸피롤-1-일기, 3-메틸피롤-2-일기, 3-메틸피롤-4-일기, 3-메틸피롤-5-일기, 2-t-부틸피롤-4-일기, 3-(2-페닐프로필)피롤-1-일기, 2-메틸-1-인돌릴기, 4-메틸-1-인돌릴기, 2-메틸-3-인돌릴기, 4-메틸-3-인돌릴기, 2-t-부틸-1-인돌릴기, 4-t-부틸-1-인돌릴기, 2-t-부틸-3-인돌릴기, 및 4-t-부틸-3-인돌릴기일 수 있으나, 이에 제한되지 않을 수 있다.The heteroaryl may be, for example, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indole Reel group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group, 2-isoindoleyl group, 3-isoindoleyl group, 4- Isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4- Benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8- Quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinol Group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carba Zolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridineyl group, 4-phenanthridineyl group, 6 -Phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3- Acridinyl, 4-acridinyl, 9-acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline -4-yl, 1,7-phenanthroline-5-diary, 1,7-phenanthroline-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline-9 -Diary, 1,7-phenanthroline-10-diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl , 1,8-phenanthroline-5-diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary, 1, 8-phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9- Phenanthroline-4-yl, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenanthrole Lin-8- diary, 1,9-phenanthroline-10- diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline- 4-diary, 1,10-phenanthroline-5-diary, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4- Diary, 2,9-phenanthroline-5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary, 2,9-phenanthroline-10- diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2, 8-phenanthroline-5-diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8- Phenanthroline-10- diary, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7- Phenanthroline-5-diary, 2,7-phenanthroline-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthrole Rin-10- diary, 1-phenazine diary, 2-phenazine diary, 1-phenothiazin diary, 2-phenothiazin diary, 3-phenothiazin diary, 4-phenothiazin diary, 10-phenosia Azinyl group, 1-phenoxadinyl group, 2-phenoxadinyl group, 3-phenoxadinyl group, 4-phenoxadinyl group, 10-phenoxadinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methyl Pyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4-yl group , 3-methylpyrrole-5-yl group, 2-t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1- Indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4- t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, and 4-t-butyl-3-indolyl group, but may not be limited thereto.
본원 명세서 전체에서, 용어 "헤테로 원자"는 탄소 및 수소 원자 이외의 원자를 의미하는 것으로서, 예를 들어, 상기 헤테로 원자는 Si, Se, N, O, S, P, As, F, Cl, Br 및 I로 이루어진 군에서 선택되는 것을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다.Throughout this specification, the term "hetero atom" means an atom other than carbon and hydrogen atoms, for example, the hetero atom is Si, Se, N, O, S, P, As, F, Cl, Br And I, but may include those selected from the group consisting of, but may not be limited thereto.
본원 명세서 전체에서, 용어 "할로겐" 또는 "할로"는 주기율표의 17 족에 속하는 할로겐 원자가 작용기의 형태로서 화합물에 포함되어 있는 것을 의미하는 것으로서, 예를 들어, 염소, 브롬, 불소 또는 요오드일 수 있으나, 이에 제한되지 않을 수 있다.Throughout this specification, the term "halogen" or "halo" means that a halogen atom belonging to group 17 of the periodic table is included in the compound in the form of a functional group, and may be, for example, chlorine, bromine, fluorine or iodine. However, this may not be limited.
본원 명세서 전체에서, "치환 또는 비치환"의 용어는 CN, 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기 등의 치환기를 포함하는 것일 수 있다.Throughout this specification, the term "substituted or unsubstituted" is CN, hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group, or substituted or unsubstituted C 2 It may include a substituent such as C 50 hetero aryl group.
본원의 제 1 측면은, 하기 화학식 1로서 표시되는, 화합물을 제공한다:A first aspect of the present application provides a compound represented by the following Chemical Formula 1:
[화학식 1] [Formula 1]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 화학식 1 중, R1 내지 R2은, 각각 독립적으로, 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고, X는 치환 또는 비치환된 CR3 또는 N이고, R3는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고, L은 치환 또는 비치환된 C6 내지 C30의 아릴렌 또는 C3 내지 C20의 헤테로 아릴렌기이고, Z는 N 또는 CR3이고, R1은 주변 아릴 의 α 탄소와 고리를 형성할 수 있고, m 및 n은 각각 독립적으로, 0 내지 2의 정수이며, 단, X가 모두 CR3일 때, n은 0이 아니다. 이때, 상기 주변 아릴의 α 탄소는 m 반복단위의 α 탄소 또는 R2의 α 탄소이다. In Formula 1, R 1 to R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or substituted or unsubstituted C 2 to C 50 is a hetero aryl group, X is substituted or unsubstituted CR 3 or N, R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or Substituted or unsubstituted C 2 to C 50 hetero aryl group, L is substituted or unsubstituted C 6 to C 30 arylene or C 3 to C 20 hetero arylene group, Z is N or CR 3 , R 1 may form a ring with α carbon of surrounding aryl, and m and n are each independently an integer of 0 to 2, provided that when X is CR 3 , n is not 0. In this case, the α carbon of the peripheral aryl is α carbon of m repeating units or α carbon of R 2 .
본원의 일 구현예에 있어서, 상기 R1이 주변 아릴의 α 탄소와 고리를 형성할 경우, 분자의 강직성을 증가시켜 높은 열 안정성을 가질 수 있다.In one embodiment of the present application, when R 1 forms a ring with α carbon of the surrounding aryl, it may have high thermal stability by increasing the rigidity of the molecule.
본원의 일 구현예에 있어서, 상기 화학식 1로서 표시되는 화합물을 전자 수송 재료로서 사용함으로써 전자 수송 증가(LUMO) 에너지 준위가 낮아지므로, 전자의 이동이 수월해지기 때문에, 발광층으로 다량의 전자가 주입되어 유기발광소자의 효율이 증가될 수 있다.In one embodiment of the present application, since the electron transport increasing (LUMO) energy level is lowered by using the compound represented by Chemical Formula 1 as an electron transporting material, a large amount of electrons are injected into the light emitting layer because electrons are facilitated. The efficiency of the organic light emitting device can be increased.
본원의 일 구현예에 있어서, 상기 화학식 1로서 표시되는 화합물을 정공 저지층으로서 사용함으로써 전자 수송층으로 정공이 새는 것을 방지하고 상기 정공이 발광층 내에 남아 유기발광소자의 효율이 증가될 수 있다. In one embodiment of the present application, by using the compound represented by the formula (1) as a hole blocking layer to prevent holes from leaking to the electron transport layer and the hole remains in the light emitting layer may increase the efficiency of the organic light emitting device.
본원의 일 구현예에 있어서, 상기 R1 내지 R3 각각은 하기 치환기로부터 독립적으로 선택되는 것을 포함할 수 있으나, 이에 제한되지 않을 수 있다:In one embodiment of the present disclosure, each of R 1 to R 3 may include one selected independently from the following substituents, but may not be limited thereto:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 화학식들 중, -*는 결합부위이고, Y는 각각 독립적으로, C, N, 또는 CR4이고, R4는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이다.In the above formulas,-* is a bonding site, Y is each independently, C, N, or CR 4 , R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
본원의 일 구현예에 있어서, 상기 L은 하기 치환기로부터 선택되는 것일 수 있으나, 이에 제한되지 않을 수 있다:In one embodiment of the present application, L may be selected from the following substituents, but may not be limited thereto:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 화학식들 중, -*는 결합부위이고, Y는 각각 독립적으로, C, N, 또는 CR4이고, R4는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이다.In the above formulas,-* is a bonding site, Y is each independently, C, N, or CR 4 , R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
본원의 일 구현예에 있어서, 상기 화합물은 하기 화학식들 중 어느 하나로 표시되는 것을 포함할 수 있으나, 이에 제한되지 않을 수 있다:In one embodiment of the present disclosure, the compound may include, but is not limited to, one represented by one of the following formulas:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
본원의 일 구현예에 있어서, 상기 화합물은 하기 반응식 1로서 표시되는 화합물의 제조 방법에 의해 제조되는 것일 수 있으나, 이에 제한되지 않을 수 있다:In one embodiment of the present application, the compound may be prepared by a method for preparing a compound represented by Scheme 1, but may not be limited thereto.
[반응식 1] Scheme 1
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 반응식 1 중, R1 내지 R2은, 각각 독립적으로, 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고, X는 치환 또는 비치환된 CR3 또는 N이고, R3는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고, L은 치환 또는 비치환된 C6 내지 C30의 아릴렌 또는 C3 내지 C20의 헤테로 아릴렌기이고, Z는 N 또는 CR3이고, R1은 주변 아릴 의 α 탄소와 고리를 형성할 수 있고, m 및 n은 각각 독립적으로, 0 내지 2의 정수이며, 단, X가 모두 CR3일 때, n은 0이 아니다. 이때, 상기 주변 아릴의 α 탄소는 m 반복단위의 α 탄소 또는 R2의 α 탄소이다.In the above Scheme 1, R 1 to R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or substituted or unsubstituted C 2 to C 50 is a hetero aryl group, X is substituted or unsubstituted CR 3 or N, R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl, or Substituted or unsubstituted C 2 to C 50 hetero aryl group, L is substituted or unsubstituted C 6 to C 30 arylene or C 3 to C 20 hetero arylene group, Z is N or CR 3 , R 1 may form a ring with α carbon of surrounding aryl, and m and n are each independently an integer of 0 to 2, provided that when X is CR 3 , n is not 0. In this case, the α carbon of the peripheral aryl is α carbon of m repeating units or α carbon of R 2 .
본원의 일 구현예에 있어서, 상기 R1이 주변 아릴의 α 탄소와 고리를 형성할 경우, 분자의 강직성을 증가시켜 높은 열 안정성을 가질 수 있다.In one embodiment of the present application, when R 1 forms a ring with α carbon of the surrounding aryl, it may have high thermal stability by increasing the rigidity of the molecule.
본원의 일 구현예에 있어서, 상기 R1 내지 R3 각각은 하기 치환기로부터 독립적으로 선택되는 것을 포함할 수 있으나, 이에 제한되지 않을 수 있다:In one embodiment of the present disclosure, each of R 1 to R 3 may include one selected independently from the following substituents, but may not be limited thereto:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 화학식들 중, -*는 결합부위이고, Y는 각각 독립적으로, C, N, 또는 CR4이고, R4는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이다.In the above formulas,-* is a bonding site, Y is each independently, C, N, or CR 4 , R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
본원의 일 구현예에 있어서, 상기 L은 하기 치환기로부터 선택되는 것일 수 있으나, 이에 제한되지 않을 수 있다:In one embodiment of the present application, L may be selected from the following substituents, but may not be limited thereto:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 화학식들 중, -*는 결합부위이고, Y는 각각 독립적으로, C, N, 또는 CR4이고, R4는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이다.In the above formulas,-* is a bonding site, Y is each independently, C, N, or CR 4 , R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 heteroaryl group.
본원의 제 2 측면은, 애노드 전극, 캐소드 전극 사이에 형성된 본원의 제 1 측면에 따른 화합물을 함유하는 1 층 이상의 유기물층을 포함하는 유기 발광 소자를 제공한다.The second aspect of the present application provides an organic light emitting device comprising at least one organic layer containing a compound according to the first aspect of the present application formed between the anode electrode and the cathode electrode.
본원의 제 2 측면에 따른 유기 발광 소자에 대하여, 본원의 제 1 측면과 중복되는 부분들에 대해서는 상세한 설명을 생략하였으나, 그 설명이 생략되었더라도 본원의 제 1 측면에 기재된 내용은 본원의 제 2 측면에 동일하게 적용될 수 있다.With respect to the organic light emitting device according to the second aspect of the present application, detailed descriptions of portions overlapping with the first side of the present application have been omitted, but the contents described in the first aspect of the present application may be omitted even if the description thereof is omitted. The same applies to.
본원의 일 구현예에 있어서, 상기 유기 발광 소자는 상기 화학식 1로서 표시되는 화합물을 포함하는 1층 이상의 유기물층을 포함하는 것일 수 있다.In one embodiment of the present application, the organic light emitting device may include one or more organic material layers including the compound represented by the formula (1).
본원의 일 구현예에 있어서, 상기 화학식 1로서 표시되는 화합물을 포함하는 상기 유기물층은 전자 수송층 또는 정공 저지층일 수 있다. 이때, 상기 화합물은 전자 수송 물질로서 단독 또는 공지의 전자 주입 물질 또는 전자 수송 물질용 화합물과 함께 사용될 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the organic material layer including the compound represented by Formula 1 may be an electron transport layer or a hole blocking layer. In this case, the compound may be used alone or in combination with a known electron injecting material or a compound for an electron transporting material as the electron transporting material, but may not be limited thereto.
본원의 일 구현예에 있어서, 상기 유기 발광 소자는 애노드(anode)와 캐소드(cathode) 사이에 정공 주입층(HIL), 정공 수송층(HTL), 발광층(EML), 전자 수송층(ETL), 전자 주입층(EIL)등의 유기물층을 1 층 이상 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present invention, the organic light emitting device is a hole injection layer (HIL), hole transport layer (HTL), light emitting layer (EML), electron transport layer (ETL), electron injection between the anode (anode) and the cathode (cathode) One or more layers of an organic material layer such as a layer (EIL) may be included, but may not be limited thereto.
이와 관련하여, 도 1은 본원의 일 구현예에 따른 유기 발광 소자의 단면을 개략적으로 도시한 것이다.In this regard, Figure 1 schematically shows a cross-section of an organic light emitting device according to an embodiment of the present application.
도 1을 참조하면, 본원의 일 구현예에 따른 유기 발광 소자는 기판(10) 상에 형성된 애노드 전극(11), 상기 애노드 전극(11) 상에 형성된 정공 주입층(12), 상기 정공 주입층(12) 상에 형성된 정공 수송층(13), 상기 정공 수송층(13) 상에 형성된 발광층(14), 상기 발광층(14) 상에 형성된 전자 수송층(15), 상기 전자 수송층(15) 상에 형성된 전자 주입층(16), 및 상기 전자 주입층(16) 상에 형성된 캐소드 전극(17)을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다.Referring to FIG. 1, an organic light emitting diode according to an exemplary embodiment of the present disclosure includes an anode electrode 11 formed on a substrate 10, a hole injection layer 12 formed on the anode electrode 11, and the hole injection layer. A hole transport layer 13 formed on the hole 12, a light emitting layer 14 formed on the hole transport layer 13, an electron transport layer 15 formed on the light emitting layer 14, and electrons formed on the electron transport layer 15. It may include an injection layer 16 and a cathode electrode 17 formed on the electron injection layer 16, but may not be limited thereto.
본원의 일 구현예에 따른 상기 유기 발광 소자는 하기와 같은 방법에 의해 제조될 수 있다.The organic light emitting device according to the embodiment of the present application may be manufactured by the following method.
먼저, 기판(10) 상부에 정공의 주입이 가능하도록 낮은 일함수를 갖는 애노드 전극용 물질을 증착시켜 애노드 전극(11)을 형성한다. First, an anode electrode 11 is formed by depositing an anode electrode material having a low work function on the substrate 10 to enable injection of holes.
본원의 일 구현예에 있어서, 상기 기판(10)은 통상의 유기 발광 소자에서 사용되는 기판이라면 특별히 제한되지 않고 사용될 수 있으며, 특히 기계적 강도, 열적 안정성, 투명성, 표면 평활성, 취급 용이성, 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. In one embodiment of the present application, the substrate 10 may be used without particular limitation as long as it is a substrate used in a conventional organic light emitting device, in particular mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof It may be to include an excellent glass substrate or a transparent plastic substrate, but may not be limited thereto.
본원의 일 구현예에 있어서, 상기 애노드 전극(11)은 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO), 및 이들의 조합들로 이루어진 군으로부터 선택되는 것을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. 상기 애노드 전극 물질은 통상의 애노드 전극 형성방법에 의해 증착되는 것일 수 있으며, 예를 들어, 증착법 또는 스파터링법에 의해 기판 상에 증착되는 것일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the anode electrode 11 is transparent and has excellent conductivity indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and their It may be to include one selected from the group consisting of combinations, but may not be limited thereto. The anode electrode material may be deposited by a conventional anode electrode forming method, for example, may be deposited on a substrate by a deposition method or a spattering method, but may not be limited thereto.
이어서, 상기 애노드 전극(11) 상에 상기 정공 주입층(12)을 진공증착법, 스핀코팅법, 캐스트법, 또는 랭뮤어-블로드젯(LB)법에 의해 형성할 수 있으나, 이에 제한되지 않을 수 있다. 바람직하게는, 균일한 막질을 수득하기 용이하고, 핀 정공이 발생하기 어려운 진공증착법에 의해 상기 정공 주입층(12)을 형성하는 것일 수 있다. 예를 들어, 상기 진공증착법에 의해 상기 정공 주입층(12)을 형성할 경우, 상기 정공 주입층(12)의 재료로서 사용하는 화합물, 또는 목적하는 정공 주입층(12)의 구조 및 열적특성 등에 따라 증착 조건은 상이하지만, 일반적으로 약 50℃ 내지 약 500℃의 증착온도, 약 10-8 torr 내지 약 10-3 torr의 진공도, 약 0.01 Å/sec 내지 약 100 Å/sec의 증착 속도, 및 약 10 Å 내지 약 5 ㎛의 층 두께 범위에서 증착하는 것이 바람직하다.Subsequently, the hole injection layer 12 may be formed on the anode 11 by vacuum deposition, spin coating, casting, or Langmuir-Bloodjet (LB), but is not limited thereto. Can be. Preferably, the hole injection layer 12 may be formed by a vacuum deposition method which is easy to obtain a uniform film quality and is hard to generate pin holes. For example, when the hole injection layer 12 is formed by the vacuum deposition method, the compound used as a material of the hole injection layer 12 or the structure and thermal characteristics of the hole injection layer 12 of interest. Depending on the deposition conditions, but generally a deposition temperature of about 50 ° C. to about 500 ° C., a vacuum degree of about 10 −8 torr to about 10 −3 torr, a deposition rate of about 0.01 μs / sec to about 100 μs / sec, and It is desirable to deposit in a layer thickness ranging from about 10 mm 3 to about 5 μm.
본원의 일 구현예에 있어서, 상기 정공 주입층(12) 물질은 특별히 제한되지 않고 사용될 수 있으며, 미국특허 제4,356,429호에 개시된 구리 프탈로시아닌 등의 프탈로시아닌 화합물 또는 스타버스트형 아민 유도체류인 TCTA[4,4',4"-트리(N-카바졸릴)트리페닐아민], m-MTDATA[4,4',4"-트리스(3-메틸페닐아미노)트리페닐아민], m-MTDAPB[4,4',4"-트리스(3-메틸페닐아미노)페녹시벤젠], 또는 HI-406[N1,N1'-(비페닐-4,4'-디일)비스(N1-(나프탈렌-1-일)-N4,N4-디페닐벤젠-1,4-디아민] 등을 정공 주입층 물질로서 사용할 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the hole injection layer 12 material may be used without particular limitation, TCTA [4, which is a phthalocyanine compound or starburst type amine derivatives such as copper phthalocyanine disclosed in US Patent No. 4,356,429 4 ', 4 "-tri (N-carbazolyl) triphenylamine], m-MTDATA [4,4', 4" -tris (3-methylphenylamino) triphenylamine], m-MTDAPB [4,4 ' , 4 "-tris (3-methylphenylamino) phenoxybenzene], or HI-406 [N 1 , N 1 '-(biphenyl-4,4'-diyl) bis (N 1-(naphthalen- 1 -yl ) -N 4 , N 4 -diphenylbenzene-1,4-diamine] may be used as the hole injection layer material, but may not be limited thereto.
이어서, 상기 정공 주입층(12) 상부에 정공 수송층(13)을 진공증착법, 스핀코팅법, 캐스트법, 또는 LB법 등과 같은 방법에 의해 형성할 수 있으나, 이에 제한되지 않을 수 있다. 바람직하게는, 균일한 막질을 수득하기 용이하고, 핀 정공이 발생하기 어려운 진공증착법에 의해 상기 정공 수송층(13)을 형성하는 것일 수 있다. 예를 들어, 상기 진공 증착법에 의해 상기 정공 수송층(13)을 형성하는 경우 그 증착 조건은 사용하는 화합물에 따라 다르지만, 일반적으로 상기 정공 주입층의 증착 조건과 거의 동일한 조건 범위에서 선택하는 것이 바람직하다.Subsequently, the hole transport layer 13 may be formed on the hole injection layer 12 by a method such as vacuum deposition, spin coating, casting, or LB, but may not be limited thereto. Preferably, the hole transport layer 13 may be formed by a vacuum deposition method which is easy to obtain a uniform film quality and is hard to generate pin holes. For example, when the hole transport layer 13 is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the hole transport layer 13 is preferably selected in a condition range substantially the same as the deposition conditions of the hole injection layer. .
또한, 상기 정공 수송층(13) 물질은 특별히 제한되지 않고 사용될 수 있으며, 상기 정공 수송층(13)으로서 사용되는 통상의 공지 물질 중에서 임의로 선택하여 사용할 수 있다. 구체적으로, 상기 정공 수송층(13) 물질은 N-페닐카바졸, 폴리비닐카바졸 등의 카바졸 유도체, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), 또는 N.N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상의 아민 유도체 등이 사용될 수 있다. In addition, the material of the hole transport layer 13 may be used without particular limitation, and may be arbitrarily selected from conventionally known materials used as the hole transport layer 13. Specifically, the hole transport layer 13 material is a carbazole derivative such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1, Aromatic condensed rings such as 1-biphenyl] -4,4'-diamine (TPD) or N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) Eggplant can be used a conventional amine derivative and the like.
그 후, 상기 정공 수송층(13) 상부에 상기 발광층(14)을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있으나, 이에 제한되지 않을 수 있다. 바람직하게는, 균일한 막질을 수득하기 용이하고, 핀 정공이 발생하기 어려운 진공증착법에 의해 상기 발광층(14)을 형성하는 것일 수 있다. 상기 진공 증착법에 의해 상기 발광층(14)을 형성하는 경우 그 증착 조건은 사용하는 화합물에 따라 상이하지만 일반적으로 상기 정공 주입층의 증착 조건과 거의 동일한 조건 범위에서 선택하는 것이 바람직하다. 또한, 상기 발광층(14) 재료는 공지의 호스트 또는 도펀트를 사용할 수 있다. 예를 들어, 상기 형광 도펀트는 이데미츠사(Idemitsu사)에서 구입 가능한 IDE102 또는 IDE105, 또는 BD142(N6,N12-비스(3,4-디메틸페닐)-N6,N12-디메시틸크리센-6,12-디아민)를 사용할 수 있으며, 상기 인광 도펀트는 녹색 인광 도펀트 {Ir(ppy)3[트리스(2-페닐피리딘) 이리듐]}, 청색 인광 도펀트인 F2Irpic{이리듐(Ⅲ)비스[4,6-다이플루오로페닐)-피리디나토-N,C2']피콜린산염)}, UDC사의 적색 인광 도펀트 RD61 등이 공동 진공증착(도핑)될 수 있다. 도펀트의 도핑 농도는 특별히 제한되지 않으나, 호스트 100 중량부에 대하여 도펀트가 약 0.01 내지 약 15 중량부로 도핑하는 것이 바람직하다.Thereafter, the light emitting layer 14 may be formed on the hole transport layer 13 by a method such as vacuum deposition, spin coating, casting, LB, or the like, but may not be limited thereto. Preferably, the light emitting layer 14 may be formed by a vacuum deposition method which is easy to obtain a uniform film quality and is hard to generate pin holes. In the case of forming the light emitting layer 14 by the vacuum deposition method, the deposition conditions are different depending on the compound to be used, but in general, it is preferable to select in a condition range almost the same as the deposition conditions of the hole injection layer. In addition, the light emitting layer 14 may be a known host or dopant. For example, the fluorescent dopant may be IDE102 or IDE105 available from Idemitsu, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethyryl). Sen-6,12-diamine), and the phosphorescent dopant may be a green phosphorescent dopant {Ir (ppy) 3 [tris (2-phenylpyridine) iridium]}, a blue phosphorescent dopant F 2 Irpic {iridium (III) Bis [4,6-difluorophenyl) -pyridinato-N, C2 '] picolinate)}, a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped). The doping concentration of the dopant is not particularly limited, but it is preferable that the dopant is about 0.01 to about 15 parts by weight based on 100 parts by weight of the host.
또한, 상기 발광층(14)에 인광 도펀트와 함께 사용할 경우에는 삼중항 여기자 또는 정공이 전자 수송층으로 확산되는 현상을 방지하기 위하여 정공 억제 재료(HBL)를 진공증착법 또는 스핀코팅법에 의해 추가로 적층시키는 것이 바람직하다. 이때 사용할 수 있는 상기 정공 억제 재료는 특별히 제한되지는 않고, 정공 억제 재료로 사용되고 있는 공지의 것에서 임의의 것을 선택해서 이용할 수 있다. 예를 들어, 상기 정공 억제 재료는 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, 또는 일본 특개평 11-329734(A1)에 기재되어 있는 정공억제재료 등을 들 수 있으며, 대표적으로 Balq[비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄 비페녹사이드], 또는 페난트롤린(phenanthrolines)계 화합물[예: UDC사BCP(바쏘쿠프로인)] 등을 사용할 수 있으나, 이에 제한되지 않을 수 있다.In addition, when used together with a phosphorescent dopant in the light emitting layer 14, in order to prevent the triplet exciton or hole from diffusing into the electron transporting layer, a hole suppressing material (HBL) is further laminated by vacuum deposition or spin coating. It is preferable. The hole-suppressing material which can be used at this time is not specifically limited, Any thing can be selected and used from the well-known thing used as a hole-suppressing material. For example, the hole suppressing material may include an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole suppressing material described in Japanese Patent Laid-Open No. 11-329734 (A1). Bis (8-hydroxy-2-methylquinolinolato) -aluminum biphenoxide], or a phenanthrolines-based compound (e.g., UDC Corporation BCP (Basocuproin)); This may not be limited.
이어서, 상기 발광층(14) 상에 상기 전자 수송층(15)을 형성한다. Subsequently, the electron transport layer 15 is formed on the light emitting layer 14.
상기 전자 수송층(15)은 진공증착법, 스핀코팅법, 캐스트법, 또는 LB법 등과 같은 방법에 의해 형성할 수 있으나, 이에 제한되지 않을 수 있다. 바람직하게는, 상기 전자 수송층(15)을 형성하는 것일 수 있다. 예를 들어, 상기 진공 증착법에 의해 상기 전자 수송층(15)을 형성하는 경우 그 증착 조건은 사용하는 화합물에 따라 다르지만, 일반적으로 상기 정공 주입층의 증착 조건과 거의 동일한 조건 범위에서 선택하는 것이 바람직하다.The electron transport layer 15 may be formed by a method such as vacuum deposition, spin coating, casting, or LB, but may not be limited thereto. Preferably, the electron transport layer 15 may be formed. For example, when the electron transport layer 15 is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the electron transport layer 15 is preferably selected in a condition range substantially the same as the deposition conditions of the hole injection layer. .
본원의 일 구현예에 있어서, 상기 전자 수송층(15)은 전자 주입 전극[캐소드 전극(17)]으로부터 주입된 전자를 안정하게 수송하는 기능을 하는 것으로서, 상기 화학식 1로서 표시되는 화합물이 단독으로 사용되거나 또는 공지의 전자 수송층 물질이 혼합되어 사용되는 것을 포함할 수 있다.In one embodiment of the present application, the electron transport layer 15 functions to stably transport electrons injected from an electron injection electrode (cathode electrode 17), and the compound represented by Chemical Formula 1 is used alone. Or known mixtures of electron transport layers may be used.
본원의 일 구현예에 있어서, 상기 전자 수송층(15)으로서 상기 화학식 1로서 표시되는 화합물을 사용함으로써, 상기 화합물에 포함되는 포스핀 옥사이드 유닛에 의해 전자 수송 특성이 강해지며, 이에 따라 상기 유기 발광 소자의 저전압 및 고효율 특성을 달성할 수 있다. 더불어, 상기 포스핀 옥사이드 유닛에 의해 재결합 영역이 이동되어, 색좌표 x, y가 감소될 수 있다. 또한, 상기 포스핀 옥사이드 유닛이 공액 결합 길이의 증가를 방지하여, 높은 삼중항 에너지의 유지가 가능하다. In one embodiment of the present application, by using the compound represented by the formula (1) as the electron transport layer 15, the electron transport properties are enhanced by the phosphine oxide unit included in the compound, accordingly the organic light emitting device Low voltage and high efficiency characteristics can be achieved. In addition, the recombination region is moved by the phosphine oxide unit, so that color coordinates x and y may be reduced. In addition, the phosphine oxide unit prevents the increase in the conjugated bond length, it is possible to maintain a high triplet energy.
본원의 일 구현예에 있어서, 상기 전자 수송층(15) 상에 캐소드[캐소드 전극(17)]로부터 전자의 주입을 용이하게 하는 기능을 가지는 물질인 전자 주입층(EIL)(16)이 적층되는 것을 추가 포함할 수 있으나, 이에 제한되지 않을 수 있다. 예를 들어, 상기 전자 주입층(16) 물질로는 LiF, NaCl, CsF, Li2O, BaO, 및 이들의 조합들로 이루어진 군으로부터 선택되는 것을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the electron injection layer (EIL) 16 that is a material having a function of facilitating the injection of electrons from the cathode (cathode electrode 17) on the electron transport layer 15 is laminated It may further include, but may not be limited to this. For example, the electron injection layer 16 may be a material selected from the group consisting of LiF, NaCl, CsF, Li 2 O, BaO, and combinations thereof, but may not be limited thereto. .
더불어, 도시하지는 않았지만, 본원의 일 구현예에 있어서, 상기 발광층(14)과 상기 전자 수송층(15) 사이에 상기 화학식 1로서 표시되는 화합물을 정공 저지층으로서 추가 포함할 수 있으나, 이에 제한되지 않을 수 있다. 상기 화학식 1로서 표시되는 화합물을 정공 저지층으로서 사용함으로써 전자 수송층으로 정공이 새는 것을 방지하고 상기 정공이 발광층 내에 남아 유기발광소자의 효율이 증가될 수 있다.In addition, although not shown, in the exemplary embodiment of the present application, a compound represented by Chemical Formula 1 may be further included as the hole blocking layer between the emission layer 14 and the electron transport layer 15, but is not limited thereto. Can be. By using the compound represented by Formula 1 as a hole blocking layer, holes may be prevented from leaking to the electron transport layer, and the holes may remain in the light emitting layer to increase the efficiency of the organic light emitting device.
마지막으로, 상기 전자 주입층(16) 상에 캐소드 형성용 금속을 진공증착법 또는 스퍼터링법에 의해 형성하고 캐소드 전극(17)으로서 사용할 수 있다. 상기 캐소드 전극(17)은 리튬, 마그네슘, 알루미늄, 칼슘, 인듐, 은, 금, 및 이들의 조합들로 이루어진 군으로부터 선택되는 것을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. 또한, 상기 캐소드 전극(17)으로서 전면 발광소자를 수득하기 위하여 ITO, IZO, SnO2, 또는 ZnO를 사용한 투과형 캐소드를 사용할 수도 있으나, 이에 제한되지 않을 수 있다.Finally, the cathode forming metal can be formed on the electron injection layer 16 by vacuum deposition or sputtering and used as the cathode electrode 17. The cathode electrode 17 may include one selected from the group consisting of lithium, magnesium, aluminum, calcium, indium, silver, gold, and combinations thereof, but may not be limited thereto. In addition, a transmissive cathode using ITO, IZO, SnO 2 , or ZnO may be used as the cathode electrode 17 to obtain a front light emitting device, but may not be limited thereto.
본원의 일 구현예에 따른 상기 유기 발광 소자는 애노드, 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층, 및 캐소드 구조뿐만 아니라, 다양한 구조의 유기 발광 소자가 가능하며, 필요에 따라 1층 또는 2층의 중간층을 추가 형성하는 것도 가능하다.The organic light emitting device according to the embodiment of the present application is not only an anode, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injection layer, and a cathode structure, but also an organic light emitting device having a variety of structures, 1 It is also possible to form additional layers or intermediate layers of two layers.
본원의 일 구현예에 따라 형성되는 각 유기물층의 두께는 요구되는 정도에 따라 조절할 수 있으며, 바람직하게는 약 10 nm 내지 약 1,000 ㎚를 포함하는 것일 수 있으며, 더욱 바람직하게는 약 20 nm 내지 약 150 ㎚를 포함하는 것일 수 있다.The thickness of each organic material layer formed in accordance with one embodiment of the present application can be adjusted according to the required degree, preferably may include about 10 nm to about 1,000 nm, more preferably about 20 nm to about 150 It may be one containing nm.
본원의 일 구현예에 있어서, 상기 화학식 1로서 표시되는 화합물을 포함하는 유기물층은 상기 유기물층의 두께를 분자 단위로 조절할 수 있기 때문에 표면이 균일하며, 형태 안정성이 뛰어난 장점이 있다.In one embodiment of the present application, the organic material layer including the compound represented by the formula (1) has the advantage that the surface is uniform, excellent in shape stability because the thickness of the organic material layer can be adjusted in molecular units.
이하, 첨부된 도면을 참조하여 본원의 구현예 및 실시예를 상세히 설명한다. 그러나, 본원이 이러한 구현예 및 실시예와 도면에 제한되지 않을 수 있다.Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application; However, the present disclosure may not be limited to these embodiments, examples, and drawings.
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제조예Production Example
] ]
1. 중간체의 합성1. Synthesis of Intermediates
1-1. 중간체 1의 합성1-1. Synthesis of Intermediate 1
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
아르곤 분위기 또는 질소 분위기 하에서 250 mL 플라스크에 3,5-다이브로모피리딘 24 g, 100 mmol 을 THF 250 mL에 녹인 후 -78℃에서 n-BuLi(2.5M) 48 mL를 넣고 1시간 유지 후 다이페닐포스핀클로라이드 를 18 mL를 넣고 상온에서 12시간 교반하였다. 반응이 끝나면 MC 와 증류수로 3 회 추출하였다. 무수황산나트륨으로 수분을 제거한 후, 용매를 제거하여 고체를 수득하였다. 수득한 고체를 MC 와 H2O2 에 녹여 3 시간 동안 교반한 후, MC 와 증류수로 3 회 추출하였다. 이어서, 무수황산나트륨으로 수분을 제거한 후, hexane : MC (1:1)를 이동상으로 컬럼분리 하여 흰색 고체 25g을 수득하였다.Dissolve 24 g and 100 mmol of 3,5-dibromopyridine in 250 mL of THF in a 250 mL flask under argon or nitrogen atmosphere, add 48 mL of n- BuLi (2.5M) at -78 ° C, and hold for 1 hour. 18 mL of phosphine chloride was added thereto and stirred at room temperature for 12 hours. After the reaction was extracted three times with MC and distilled water. After water was removed with anhydrous sodium sulfate, the solvent was removed to obtain a solid. The obtained solid was dissolved in MC and H 2 O 2 , stirred for 3 hours, and then extracted three times with MC and distilled water. Subsequently, after removing moisture with anhydrous sodium sulfate, hexane: MC (1: 1) was column separated into a mobile phase to give 25 g of a white solid.
1-2. 중간체 2의 합성1-2. Synthesis of Intermediate 2
상기 중간체 1의 합성 방법과 동일한 방법을 사용하되, 3,5-다이브로모피리딘 대신 1-클로로-3-아이오도 벤젠을 사용하여 하기 화합물을 합성하였다:Using the same method as the synthesis method of Intermediate 1, the following compound was synthesized using 1-chloro-3-iodo benzene instead of 3,5-dibromopyridine:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-3. 중간체 3의 합성1-3. Synthesis of Intermediate 3
상기 중간체 1의 합성 방법과 동일한 방법을 사용하되, 3,5-다이브로모피리딘 대신 2-클로로-4-아이오도 벤젠을 사용하여 하기 화합물을 합성하였다:Using the same method as the synthesis method of Intermediate 1, the following compound was synthesized using 2-chloro-4-iodobenzene instead of 3,5-dibromopyridine:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-4. 중간체 4의 합성1-4. Synthesis of Intermediate 4
상기 중간체 1의 합성 방법과 동일한 방법을 사용하되, 3,5-다이브로모피리딘 대신 5-브로모-2-클로로피리딘을 사용하여 하기 화합물을 합성하였다:The following compounds were synthesized using the same method as the synthesis method of Intermediate 1 above, using 5-bromo-2-chloropyridine instead of 3,5-dibromopyridine:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-5. 중간체 5의 합성 1-5. Synthesis of Intermediate 5
아르곤 또는 질소 분위기 하에서, 250 mL 플라스크에, 1,3,5-트리브로모벤젠 24 g, 9,9-다이메틸플루오렌-2-보로닉산 25 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 2.5 g, 다이옥산 300 mL, 및 탄산나트륨 25 g을 물 100 mL에 용해한 것을 넣고, 환류하면서 24 시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 흰색 고체 2-(3,5-다이브로모페닐)-9,9-다이메틸플루오렌 23 g(67%)을 수득하였다.In an argon or nitrogen atmosphere, in a 250 mL flask, 24 g of 1,3,5-tribromobenzene, 25 g of 9,9-dimethylfluorene-2-boronic acid, tetrakis (triphenylphosphine) palladium ( 0) 2.5 g, dioxane 300 mL, and sodium carbonate 25 g dissolved in 100 mL of water were added, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to give 23 g (67%) of a white solid 2- (3,5-dibromophenyl) -9,9-dimethylfluorene.
이어서, 아르곤 또는 질소분위기하에서, 250 mL 플라스크에, 상기에서 수득한 2-(3,5-다이브로모페닐)-9,9-다이메틸플루오렌 20 g, 반응물 5를 27 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 2.1 g, 다이옥산 300 mL, 및 탄산나트륨 20 g을 물 100 mL에 용해한 것을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 최종적으로 흰색 고체 20 g(71%)을 합성하였다:Subsequently, under argon or nitrogen atmosphere, in a 250 mL flask, 20 g of 2- (3,5-dibromophenyl) -9,9-dimethylfluorene obtained above, 27 g of reactant 5 and tetrakis (tri) 2.1 g of phenylphosphine) palladium (0), 300 mL of dioxane, and 20 g of sodium carbonate were added to 100 mL of water, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to finally synthesize 20 g (71%) of a white solid:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-6. 중간체 6의 합성1-6. Synthesis of Intermediate 6
상기 중간체 5의 합성 방법과 동일한 방법을 사용하되, 반응물 5 대신 반응물 1을 사용하여 하기 화합물을 합성하였다:Using the same method as the synthesis of Intermediate 5, Reactant 1 was used instead of Reactant 5 to synthesize the following compounds:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-7. 중간체 7의 합성1-7. Synthesis of Intermediate 7
상기 중간체 5의 합성 방법과 동일한 방법을 사용하되, 반응물 5 대신 반응물 2를 사용하여 하기 화합물을 합성하였다:Using the same method as the synthesis of Intermediate 5, Reactant 2 was used instead of Reactant 5 to synthesize the following compounds:
MS(EI) (m/z) [M+]MS (EI) (m / z) [M + ]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-8. 중간체 8의 합성1-8. Synthesis of Intermediate 8
아르곤 또는 질소분위기하에서, 250 mL 플라스크에, 1,3-다이브로모-9,9-다이메틸플루오렌 15 g, 반응물 2를 17 g, 테트라키스(트리페닐포스핀)팔라듐(0) 0.9 g, 다이옥산 150 mL, 및 탄산나트륨 14 g을 물 50 mL에 용해한 것을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 흰색 고체인 하기 화합물 12 g (66%)을 합성하였다:In an argon or nitrogen atmosphere, in a 250 mL flask, 15 g of 1,3-dibromo-9,9-dimethylfluorene, 17 g of reactant 2, 0.9 g of tetrakis (triphenylphosphine) palladium (0), 150 mL of dioxane and 14 g of sodium carbonate were dissolved in 50 mL of water, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to synthesize 12 g (66%) of the following compound as a white solid:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-9. 중간체 9의 합성1-9. Synthesis of Intermediate 9
상기 중간체 8의 합성 방법과 동일한 방법을 사용하되, 반응물 2 대신 반응물 1을 사용하여 하기 화합물을 합성하였다:Using the same method as the synthesis of Intermediate 8, Reactant 1 was used instead of Reactant 2 to synthesize the following compounds:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-10. 중간체 10의 합성1-10. Synthesis of Intermediate 10
아르곤 또는 질소분위기하에서, 250 mL 플라스크에, 3,5-다이브로모사이아노벤젠 17 g, 반응물 1 23 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 1.5 g, 다이옥산 150 mL, 및 탄산나트륨 16 g을 물 50 mL에 용해한 것을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 하기 화합물 13 g(65%)을 합성하였다:In an argon or nitrogen atmosphere, in a 250 mL flask, 17 g of 3,5-dibromocyanobenzene, 1 23 g of reactant, 1.5 g of tetrakis (triphenylphosphine) palladium (0), 150 mL of dioxane, and sodium carbonate 16 g was dissolved in 50 mL of water, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to synthesize 13 g (65%) of the following compound:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-11. 중간체 11의 합성1-11. Synthesis of Intermediate 11
아르곤 또는 질소 분위기 하에서, 250 mL 플라스크에, 4-(3,5-다이브로모페닐)사이아노벤젠 19.5 g, 반응물 1 22 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 1.7 g, 다이옥산 200 mL, 및 탄산나트륨 19 g을 물 70 mL에 용해한 것을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 하기 화합물 14.3 g(67%)을 합성하였다:In an argon or nitrogen atmosphere, in a 250 mL flask, 19.5 g of 4- (3,5-dibromophenyl) cyanobenzene, 22 g of reactant 1, 1.7 g of tetrakis (triphenylphosphine) palladium (0), 200 dioxane mL and 19 g of sodium carbonate dissolved in 70 mL of water were added, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to synthesize 14.3 g (67%) of the following compound:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-12. 중간체 12의 합성1-12. Synthesis of Intermediate 12
아르곤 또는 질소 분위기 하에서, 250 mL 플라스크에, 3-(3,5-다이브로모페닐)사이아노벤젠 19.5 g, 반응물 1 22 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 1.7 g, 다이옥산 200 mL, 및 탄산나트륨 19 g을 물 70 mL에 용해한 것을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 하기 화합물 15.1 g(69%)을 합성하였다:In an argon or nitrogen atmosphere, in a 250 mL flask, 19.5 g of 3- (3,5-dibromophenyl) cyanobenzene, 22 g of reactant 1, 1.7 g of tetrakis (triphenylphosphine) palladium (0), 200 dioxane mL and 19 g of sodium carbonate dissolved in 70 mL of water were added, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to synthesize 15.1 g (69%) of the following compound:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
1-13. 중간체 13의 합성1-13. Synthesis of Intermediate 13
1) 중간체 13-1의 합성1) Synthesis of Intermediate 13-1
아르곤 또는 질소 분위기 하에서, 250 mL 플라스크에, 2,7-다이브로-9,9-다이메틸-플루오렌 17 g, 반응물 2를 23 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 1.5 g, 다이옥산 150 mL, 및 탄산나트륨 16 g을 물 50 mL에 용해한 것을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 하기 중간체 13-1로서 표시되는 화합물 13 g(65%)을 합성하였다.In an argon or nitrogen atmosphere, in a 250 mL flask, 17 g of 2,7-dibro-9,9-dimethyl-fluorene, 23 g of reactant 2, 1.5 g of tetrakis (triphenylphosphine) palladium (0) , 150 mL of dioxane, and 16 g of sodium carbonate were dissolved in 50 mL of water, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized with toluene to synthesize 13 g (65%) of the compound represented as Intermediate 13-1.
2) 중간체 13-2의 합성2) Synthesis of Intermediate 13-2
아르곤 또는 질소 분위기 하에서, 250 mL 플라스크에, 상기에서 수득한 중간체 13-1을 13 g, 비스(피나콜라토)다이보론 17 g, [1,1′-비스(다이페닐포스피노)페로센]다이클로로팔라듐(II) 0.5 g, 포타슘아세테이트 15 g, 및 다이옥산 130 mL을 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출한 결정을 여과 분리하였다. 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 하기 중간체 13-2로서 표시되는 화합물 12 g(83%)을 합성하였다:In an argon or nitrogen atmosphere, in a 250 mL flask, 13 g of Intermediate 13-1 obtained above, 17 g of bis (pinacolato) diboron, [1,1′-bis (diphenylphosphino) ferrocene] die 0.5 g of chloropalladium (II), 15 g of potassium acetate, and 130 mL of dioxane were added thereto, and the mixture was heated and stirred for 24 hours while refluxing. After the reaction was completed, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. The filtered crystals were recrystallized from toluene to synthesize 12 g (83%) of the compound represented as the following Intermediate 13-2:
1-14. 중간체 14의 합성1-14. Synthesis of Intermediate 14
1) 중간체 14-1의 합성1) Synthesis of Intermediate 14-1
상기 중간체 13-1의 합성 방법과 동일한 방법을 사용하되, 반응물 2 대신 반응물 1을 사용하여 하기 중간체 14-1로서 표시되는 화합물을 합성하였다.Using the same method as the synthesis of the intermediate 13-1, using the reactant 1 instead of reactant 2 to synthesize a compound represented by the following intermediate 14-1.
2) 중간체 14-2의 합성 2) Synthesis of Intermediate 14-2
상기 중간체 13-2의 합성 방법과 동일한 방법을 사용하되, 중간체 13-1 대신, 중간체 14-1을 사용하여 하기 중간체 14-2로서 표시되는 화합물을 합성하였다: Using the same method as the synthesis of Intermediate 13-2, instead of Intermediate 13-1, Intermediate 14-1 was used to synthesize the compound represented by Intermediate 14-2:
2. 반응물 2. Reactant
유기 발광 소자를 제조하기 위한 반응물로서 하기 반응물 1 내지 5를 사용하였다. The following reactants 1 to 5 were used as reactants for preparing the organic light emitting device.
[반응물 1][Reactant 1]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
[반응물 2][Reactant 2]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
[반응물 3][Reactant 3]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
[반응물 4][Reactant 4]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
[반응물 5][Reactant 5]
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
3. 화합물의 합성3. Synthesis of Compound
3-1. 화합물 1의 합성3-1. Synthesis of Compound 1
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
아르곤 또는 질소분위기하에서, 250 mL 플라스크에, 상기 중간체 1을 4.2 g, 상기 반응물 1을 6.8 g, 테트라키스(트라이페닐포스핀)팔라듐(0) 0.6 g을 다이옥산 50 mL에 녹이고, 탄산나트륨 7.6 g을 물 20 mL에 용해시킨 것을 추가한 후, 24 시간 동안 가열 교반하였다. 반응 후, 실온까지 냉각시켜 석출된 결정을 여과 분리하였다. 마지막으로, 이를 톨루엔으로 재결정하여 2.7 g(40%)의 화합물 1을 합성하였다.In an argon or nitrogen atmosphere, 4.2 g of the intermediate 1, 6.8 g of the reactant 1, 0.6 g of tetrakis (triphenylphosphine) palladium (0) were dissolved in 50 mL of dioxane and 7.6 g of sodium carbonate in a 250 mL flask. After dissolving in 20 mL of water, the mixture was heated and stirred for 24 hours. After the reaction, the mixture was cooled to room temperature and the precipitated crystals were separated by filtration. Finally, it was recrystallized with toluene to synthesize 2.7 g (40%) of Compound 1.
1H-NMR (CDCl3, 400MHz): δ7.46-7.50 (4H, m), 7.54-7.63 (10H, m), 7.69-7.74 (6H, m), 7.86 (1H, d), 8.04 (1H, d), 8.75-8.81 (6H, m)1 H-NMR (CDCl 3 , 400 MHz): δ 7.46-7.50 (4H, m), 7.54-7.63 (10H, m), 7.69-7.74 (6H, m), 7.86 (1H, d), 8.04 (1H, d), 8.75-8.81 (6H, m)
LC-MS Purityis 99.91 %, Rt=2.67min; MS Calcd.: 586.19; MS Found: 587.4[M].LC-MS Purityis 99.91%, Rt = 2.67 min; MS Calcd .: 586.19; MS Found: 587.4 [M].
3-2. 화합물 2의 합성3-2. Synthesis of Compound 2
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 중간체 1 대신 중간체 2를 사용하여 화합물 2를 합성하였다. Compound 2 was synthesized using the same method as Compound 1, but using Intermediate 2 instead of Intermediate 1.
MS Calcd.: 585.20; MS Found: 586.4[M].MS Calcd .: 585.20; MS Found: 586.4 [M].
3-3. 화합물 3의 합성3-3. Synthesis of Compound 3
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 반응물 1 대신 반응물 2를 사용하여 화합물 3을 합성하였다. Compound 3 was synthesized using the same method as compound 1, but using reactant 2 instead of reactant 1.
MS Calcd.: 586.19; MS Found: 587.4[M].MS Calcd .: 586.19; MS Found: 587.4 [M].
3-4. 화합물 4의 합성3-4. Synthesis of Compound 4
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 반응물 1 대신 반응물 2를 사용하였고, 중간체 1 대신 중간체 2를 사용하여 화합물 4를 합성하였다. Compound 4 was synthesized using the same method as compound 1, but using reactant 2 instead of reactant 1, and using intermediate 2 instead of intermediate 1.
MS Calcd.: 585.20; MS Found: 586.4[M].MS Calcd .: 585.20; MS Found: 586.4 [M].
3-5. 화합물 5의 합성3-5. Synthesis of Compound 5
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 반응물 1 대신 반응물 3을 사용하였고, 중간체 1 대신 중간체 2를 사용하여 화합물5 를 합성하였다.Using the same method as compound 1, reactant 3 was used instead of reactant 1, and compound 5 was synthesized using intermediate 2 instead of intermediate 1.
MS Calcd.: 580.20; MS Found: 581.4[M].MS Calcd .: 580.20; MS Found: 581.4 [M].
3-6. 화합물 6의 합성3-6. Synthesis of Compound 6
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 반응물 1 대신 반응물 3을 사용하여 화합물 6을 합성하였다. Compound 6 was synthesized using the same method as compound 1, but using reactant 3 instead of reactant 1.
MS Calcd.: 581.19; MS Found: 582.4[M].MS Calcd .: 581.19; MS Found: 582.4 [M].
3-7. 화합물 7의 합성3-7. Synthesis of Compound 7
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 반응물 1 대신 반응물 4를 사용하였고, 중간체 1 대신 중간체 2를 사용하여 화합물 7을 합성하였다. Compound 7 was synthesized using the same method as compound 1, but using reactant 4 instead of reactant 1, and using intermediate 2 instead of intermediate 1.
MS Calcd.: 580.20; MS Found: 581.4[M].MS Calcd .: 580.20; MS Found: 581.4 [M].
3-8. 화합물 8의 합성3-8. Synthesis of Compound 8
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 1과 동일한 방법을 이용하되, 반응물 1 대신 반응물 4를 사용하여 화합물 8 을 합성하였다. Compound 8 was synthesized using the same method as compound 1, but using reactant 4 instead of reactant 1.
MS Calcd.: 581.19; MS Found: 582.4[M].MS Calcd .: 581.19; MS Found: 582.4 [M].
3-9. 화합물 9의 합성3-9. Synthesis of Compound 9
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
아르곤 또는 질소 분위기 하에서 500 mL 플라스크에 중간체 5 27.3 g 다이페닐포스핀옥사이드 30 g, 무수인산칼륨 41 g, 다이클로로(1,3-(비스다이페닐포스피노)프로펜)니켈(Ⅱ) 3.25 g, 및 다이옥산 250 mL를 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 더이상 진행되지 않으면, 실온까지 냉각시켜 증류수 200 mL 를 넣고, MC 30 mL로 3회 추출하였다. 이어서, 무수황산나트륨으로 수분을 제거한 후, 헥산:에틸아세테이트(1:1)를 이동상으로 컬럼 분리하여 흰색 고체 화합물인, 화합물 9를 20 g(50%)을 합성하였다.30 g of intermediate 5 27.3 g diphenylphosphine oxide in a 500 mL flask under argon or nitrogen atmosphere, 41 g of anhydrous potassium phosphate, dichloro (1,3- (bisdiphenylphosphino) propene) nickel (II) 3.25 g , And 250 mL of dioxane were added and heated and stirred for 24 hours while refluxing. When the reaction no longer proceeded, the mixture was cooled to room temperature, distilled water 200 mL was added, and extracted three times with 30 mL of MC. Subsequently, water was removed with anhydrous sodium sulfate, and then hexane: ethyl acetate (1: 1) was column separated into a mobile phase to synthesize 20 g (50%) of compound 9 as a white solid compound.
MS Calcd.: 701.79 ; MS Found: 701.26[M].MS Calcd .: 701.79; MS Found: 701.26 [M].
3-10. 화합물 10의 합성3-10. Synthesis of Compound 10
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물9의 합성 방법과 동일한 방법을 이용하되, 중간체 5 대신 중간체 6을 사용하여 화합물 10을 합성하였다. Compound 10 was synthesized using the same method as the synthesis method of compound 9, using Intermediate 6 instead of Intermediate 5.
MS Calcd.: 777.89 ; MS Found: 777.29[M]. MS Calcd .: 777.89; MS Found: 777.29 [M].
3-11. 화합물 11의 합성3-11. Synthesis of Compound 11
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 9의 합성 방법과 동일한 방법을 이용하되, 중간체 5 대신 중간체 7을 사용하여 화합물 11을 합성하였다. Compound 11 was synthesized in the same manner as in the synthesis of Compound 9, using Intermediate 7 instead of Intermediate 5.
MS Calcd.: 777.89 ; MS Found: 777.29[M].MS Calcd .: 777.89; MS Found: 777.29 [M].
3-12. 화합물 12의 합성3-12. Synthesis of Compound 12
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
아르곤 또는 질소 분위기 하에서 500 mL 플라스크에 중간체 8을 10 g, 다이페닐포스핀옥사이드 12 g, 무수인산칼륨 11 g, 다이클로로(1,3-(비스다이페닐포스피노)프로펜)니켈(Ⅱ) 0.8 g, 및 다이옥산 100 mL를 넣고, 환류하면서 24시간 동안 가열 교반하였다. 반응이 더이상 진행되지 않으면, 실온까지 냉각시켜 증류수 200 mL를 넣고, MC 30 mL로 3회 추출하였다. 무수황산나트륨으로 수분을 제거한 후, 헥산:에틸아세테이트(1:1)를 이동상으로 컬럼 분리하여 흰색 고체 화합물인, 화합물 12를 10 g(51%) 합성하였다.10 g of Intermediate 8, 12 g of diphenylphosphine oxide, 11 g of anhydrous potassium phosphate, dichloro (1,3- (bisdiphenylphosphino) propene) nickel (II) in a 500 mL flask under argon or nitrogen atmosphere 0.8 g, and 100 mL of dioxane were added and heated and stirred for 24 hours while refluxing. If the reaction did not proceed anymore, cooled to room temperature, distilled water 200mL, and extracted three times with 30mL MC. After water was removed with anhydrous sodium sulfate, hexane: ethyl acetate (1: 1) was column separated into a mobile phase to synthesize 10 g (51%) of a compound 12 as a white solid compound.
MS Calcd.: 701.79 ; MS Found: 701.26[M].MS Calcd .: 701.79; MS Found: 701.26 [M].
3-13. 화합물 13의 합성3-13. Synthesis of Compound 13
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 12의 합성 방법과 동일한 방법을 이용하되, 중간체 8 대신 중간체 9를 사용하여 화합물 13을 합성하였다. Compound 13 was synthesized using the same method as the synthesis method of compound 12, using Intermediate 9 instead of Intermediate 8.
MS Calcd.: 701.79 ; MS Found: 701.26[M].MS Calcd .: 701.79; MS Found: 701.26 [M].
3-14. 화합물 14의 합성3-14. Synthesis of Compound 14
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 12의 합성 방법과 동일한 방법을 이용하되, 중간체 8 대신 중간체 10을 사용하여 화합물 14를 합성하였다. Compound 14 was synthesized using the same method as the synthesis method of compound 12, using Intermediate 10 instead of Intermediate 8.
MS Calcd.: 610.64 ; MS Found: 610.19[M].MS Calcd .: 610.64; MS Found: 610.19 [M].
3-15. 화합물 15의 합성3-15. Synthesis of Compound 15
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 12의 합성 방법과 동일한 방법을 이용하되, 중간체 8 대신 중간체 11을 사용하여 화합물 15를 합성하였다. Compound 15 was synthesized using the same method as the synthesis method of compound 12, using Intermediate 11 instead of Intermediate 8.
MS Calcd.: 686.74 ; MS Found: 686.22[M].MS Calcd .: 686.74; MS Found: 686.22 [M].
3-16. 화합물 16의 합성3-16. Synthesis of Compound 16
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 12의 합성 방법과 동일한 방법을 이용하되, 중간체 8 대신 중간체 12를 사용하여 화합물 16을 합성하였다. Compound 16 was synthesized in the same manner as in the synthesis of Compound 12, using Intermediate 12 instead of Intermediate 8.
MS Calcd.: 686.74 ; MS Found: 686.22[M].MS Calcd .: 686.74; MS Found: 686.22 [M].
3-17. 화합물 17의 합성3-17. Synthesis of Compound 17
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
아르곤 또는 질소 분위기 하에서, 250 mL 플라스크에, 중간체 13-2를 12 g, 상기 중간체 2를 9.4 g, 및 테트라키스(트라이페닐포스핀)팔라듐(0) 0.9 g을 다이옥산 120 mL에 녹이고, 탄산나트륨 11 g을 물 40 mL에 용해시킨 것을 추가한 후, 24 시간 동안 가열 교반하였다. 반응이 끝나면, 실온까지 냉각시켜 석출된 결정을 여과 분리하였다. 마지막으로, 상기 여과 분리된 결정을 톨루엔으로 재결정화하여 화합물 17을 8 g(49%) 합성하였다. In an argon or nitrogen atmosphere, in a 250 mL flask, 12 g of Intermediate 13-2, 9.4 g of Intermediate 2, and 0.9 g of tetrakis (triphenylphosphine) palladium (0) were dissolved in 120 mL of dioxane, sodium carbonate 11 After adding g dissolved in 40 mL of water, the mixture was heated and stirred for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, and the precipitated crystals were separated by filtration. Finally, the filtered crystals were recrystallized with toluene to synthesize 8 g (49%) of compound 17.
MS Calcd.: 610.64 ; MS Found: 610.19[M].MS Calcd .: 610.64; MS Found: 610.19 [M].
3-18. 화합물 18의 합성3-18. Synthesis of Compound 18
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
화합물 17의 합성 방법과 동일한 방법을 이용하되, 중간체 13-2 대신 중간체 14-2를 사용하여 화합물 18을 합성하였다.Compound 18 was synthesized in the same manner as in the synthesis of Compound 17, using Intermediate 14-2 instead of Intermediate 13-2.
MS Calcd.: 610.64 ; MS Found: 610.19[M].MS Calcd .: 610.64; MS Found: 610.19 [M].
4. 유기 발광 소자의 제조4. Fabrication of Organic Light-Emitting Device
도 1에 기재된 구조에 따라 본 실시예에 따른 유기 발광 소자를 제조하였다. 상기 유기 발광 소자는 아래로부터 애노드 전극[(정공주입전극(11)]/정공 주입층(12)/정공 수송층(13)/발광층(14)/전자 수송층(15)/ 캐소드 전극[전자주입전극(17)] 순으로 적층하였다.According to the structure described in FIG. 1, an organic light emitting device according to the present embodiment was manufactured. The organic light emitting device is composed of an anode electrode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transport layer 15 / cathode electrode [electron injection electrode 17)] in order.
본 실시예 및 비교예의 정공 주입층(12), 정공 수송층(13), 발광층(14), 및 전자 수송층(15)으로서 하기와 같은 물질을 사용하였다:The following materials were used as the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of this example and the comparative example:
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
[[
실시예Example
]]
실시예Example
1 One
인듐틴옥사이드(ITO)가 1500 Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필알코올, 아세톤, 또는 메탄올 등의 용제를 이용하여 초음파 세척을 하고 건조시켰다. 이어서, 플라즈마 세정기로 이송시킨 다음, 산소 플라즈마를 이용하여 상기 기판을 5 분 동안 세정하였다. 그 후, ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공 주입층으로서 HT01 600Å, 정공 수송층으로서 Ref.4, 250 Å를 제막하였다. 이어서, 발광층으로서 BH01:BD01를 5%로 도핑하여 250 Å 두께로 제막하였다. 이어서, 전자 수송층으로서 상기 제조된 화합물 1과 Liq을 1:1비율로 하여 300 Å 두께로 제막한 후, LiF 10 Å, 알루미늄(Al) 1,000 Å를 제막하고, 상기 소자를 글로브 박스에서 밀봉(encapsulation)함으로써 유기 발광 소자를 제조하였다.The glass substrate coated with the indium tin oxide (ITO) thin film having a thickness of 1500 Å was washed with distilled water ultrasonically. After the distilled water was washed, ultrasonic washing with a solvent such as isopropyl alcohol, acetone, or methanol was dried and dried. The substrate was then transferred to a plasma scrubber and then the substrate was cleaned for 5 minutes using an oxygen plasma. Subsequently, HT01 600 kV as a hole injection layer and Ref. 4 and 250 kV as a hole transport layer were formed into a film using a thermal evaporator on the ITO substrate. Next, BH01: BD01 was doped at 5% as a light emitting layer to form a film having a thickness of 250 kHz. Subsequently, as the electron transporting layer, the prepared compound 1 and Liq were formed into a film having a thickness of 300 μs at a 1: 1 ratio, and then LiF 10 μs and aluminum (Al) 1,000 μs were formed and the device was encapsulated in a glove box. An organic light emitting device was manufactured by
실시예Example
2 내지 2 to
실시예Example
18 18
실시예 1과 동일한 방법을 이용하여 유기 발광 소자를 제작하였으며, 이때 전자 수송층을 각각 상기 제조된 화합물 2 내지 18을 사용하여 제막한 유기 발광 소자를 제작하였다.An organic light emitting device was manufactured in the same manner as in Example 1, where an organic light emitting device in which an electron transporting layer was formed using the prepared compounds 2 to 18, respectively.
비교예Comparative example
1 One
상기 실시예 1과 동일한 방법을 이용하되, 전자 수송층으로서 상기 화합물 1 대신 ET-01을 사용하여 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Example 1, but using ET-01 instead of Compound 1 as an electron transporting layer.
유기 발광 소자의 성능평가Performance evaluation of organic light emitting device
키슬리 2400 소스 메져먼트 유닛(Kiethley 2400 source measurement unit)으로 전압을 인가하여 전자 및 정공을 주입하고, 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 실시예 및 비교예의 유기 발광 소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건하에 측정하여 평가하였으며, 그 결과를 하기 표 1에 나타내었다.Apply a voltage to the Keithley 2400 source measurement unit to inject electrons and holes, and use the Konica Minolta Spectroradiometer (CS-2000) to measure the luminance when light is emitted. By measuring, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, the results are shown in Table 1 below.
[규칙 제91조에 의한 정정 15.03.2017]
[Correction under Article 91 of the Rule 15.03.2017]
상기 표 1을 통해 확인할 수 있는 바와 같이, 본 실시예에 따른 유기 발광 소자는 비교예에 비하여 물성이 향상되었음을 확인할 수 있었다.As can be seen through Table 1, the organic light emitting device according to the present embodiment was confirmed that the physical properties compared to the comparative example.
구체적으로, 도 2 내지 5는 각각 상기 실시예 6에 따른 유기 발광 소자의 전류 밀도 특성, 전류 효율 특성, 전계 발광 스펙트럼, 수명을 나타낸 그래프이다.2 to 5 are graphs showing current density characteristics, current efficiency characteristics, electroluminescence spectra, and lifetime of the organic light emitting diode according to Example 6, respectively.
상기 도 2 내지 도 5에서 확인할 수 있는 바와 같이, 상기 실시예 6에 따른 유기 발광 소자의 경우, 우수한 전류 밀도, 전류 효율, 전계 발광 스펙트럼, 및 장 시간 안정성을 달성하는 것을 확인할 수 있었다.2 to 5, in the case of the organic light emitting device according to Example 6, it was confirmed that excellent current density, current efficiency, electroluminescence spectrum, and long time stability were achieved.
또한, 도 6 내지 9는 각각 상기 실시예 8에 따른 유기 발광 소자의 전류 밀도 특성, 전류 효율 특성, 전계 발광 스펙트럼, 수명을 나타낸 그래프이다.6 to 9 are graphs showing current density characteristics, current efficiency characteristics, electroluminescence spectra, and lifetime of the organic light emitting diode according to Example 8, respectively.
상기 도 6 내지 도 9에서 확인할 수 있는 바와 같이, 상기 실시예 8에 따른 유기 발광 소자의 경우, 우수한 전류 밀도, 전류 효율, 전계 발광 스펙트럼, 및 장 시간 안정성을 달성하는 것을 확인할 수 있었다.6 to 9, in the organic light emitting diode according to Example 8, it was confirmed that excellent current density, current efficiency, electroluminescence spectrum, and long time stability were achieved.
전술한 본원의 설명은 예시를 위한 것이며, 본원이 속하는 기술분야의 통상의 지식을 가진 자는 본원의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다.The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본원의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본원의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.
[부호의 설명][Description of the code]
10 : 기판10: substrate
11 : 애노드 전극11: anode electrode
12 : 정공 주입층12: hole injection layer
13 : 정공 수송층13: hole transport layer
14 : 발광층14: light emitting layer
15 : 전자 수송층15: electron transport layer
16: 전자 주입층16: electron injection layer
17: 캐소드 전극17: cathode electrode
Claims (7)
- [규칙 제91조에 의한 정정 15.03.2017]
하기 화학식 1로서 표시되는, 화합물:
[화학식 1]
상기 화학식 1 중,
R1 내지 R2은, 각각 독립적으로, 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50 의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고,
X는 치환 또는 비치환된 CR3 또는 N이고,
R3는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기이고,
L은 치환 또는 비치환된 C6 내지 C30의 아릴렌 또는 C3 내지 C20의 헤테로 아릴렌기이고,
Z는 N 또는 CR3이고,
R1은 주변 아릴의 α 탄소(반복단위 m의 α 탄소 또는 R2의 α 탄소)와 고리를 형성할 수 있고,
m 및 n은 각각 독립적으로, 0 내지 2의 정수이며,
단, X가 모두 CR3일 때, n은 0이 아님.
[Correction under Article 91 of the Rule 15.03.2017]
Compound represented by the following formula (1):
[Formula 1]
In Formula 1,
R 1 to R 2 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group, or substituted or unsubstituted C 2 to C 50 hetero An aryl group,
X is substituted or unsubstituted CR 3 or N,
R 3 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group, or substituted or unsubstituted C 2 to C 50 hetero aryl group,
L is a substituted or unsubstituted C6 to C 30 arylene or C 3 to C 20 hetero arylene group,
Z is N or CR 3 ,
R 1 may form a ring with α carbon of the surrounding aryl (α carbon of repeating unit m or α carbon of R 2 ),
m and n are each independently an integer of 0 to 2,
However, when X is CR 3 , n is not 0.
- [규칙 제91조에 의한 정정 15.03.2017]
제 1 항에 있어서,
상기 R1 내지 R3 각각은 하기 치환기로부터 독립적으로 선택되는 것을 포함하는, 화합물:
상기 화학식들 중, -*는 결합부위이고, Y는 각각 독립적으로, C, N, 또는 CR4이고, R4는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기임.
[Correction under Article 91 of the Rule 15.03.2017]
The method of claim 1,
Wherein each of R 1 to R 3 is independently selected from the following substituents:
In the above formulas,-* is a bonding site, Y is each independently, C, N, or CR 4 , R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 hetero aryl group.
- [규칙 제91조에 의한 정정 15.03.2017]
제 1 항에 있어서,
상기 L은 하기 치환기로부터 선택되는 것인, 화합물:
상기 화학식들 중, -*는 결합부위이고, Y는 각각 독립적으로, C, N, 또는 CR4이고, R4는 수소, 중수소, 할로겐, 니트로기, 니트릴기, 치환 또는 비치환된 C6 내지 C50의 아릴기, 또는 치환 또는 비치환된 C2 내지 C50의 헤테로 아릴기임.
[Correction under Article 91 of the Rule 15.03.2017]
The method of claim 1,
Wherein L is selected from the following substituents:
In the above formulas,-* is a bonding site, Y is each independently, C, N, or CR 4 , R 4 is hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C 6 to C 50 aryl group or substituted or unsubstituted C 2 to C 50 hetero aryl group.
- [규칙 제91조에 의한 정정 15.03.2017]
제 1 항에 있어서,
하기 화학식들 중 어느 하나로 표시되는 것을 포함하는, 화합물:
[Correction under Article 91 of the Rule 15.03.2017]
The method of claim 1,
Compounds, including those represented by any of the following formulas:
- 제 1 항에 있어서,The method of claim 1,상기 화학식 1로서 표시되는 화합물은 전자 수송 물질인 것인, 화합물. Compound represented by Formula 1 is an electron transport material, compound.
- 애노드 전극, 캐소드 전극 사이에 형성된 제 1 항 내지 제 5 항 중 어느 한 항에 따른 화합물을 함유하는 1 층 이상의 유기물층을 포함하는, 유기 발광 소자.An organic light-emitting device comprising at least one organic material layer containing a compound according to any one of claims 1 to 5 formed between an anode electrode and a cathode electrode.
- 제 6 항에 있어서,The method of claim 6,상기 유기물층은 전자 수송층 또는 정공 저지층인 것인, 유기 발광 소자.The organic layer is an organic light emitting device that is an electron transport layer or a hole blocking layer.
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