WO2016060332A1 - Organic optoelectronic device and display device - Google Patents
Organic optoelectronic device and display device Download PDFInfo
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- WO2016060332A1 WO2016060332A1 PCT/KR2014/012542 KR2014012542W WO2016060332A1 WO 2016060332 A1 WO2016060332 A1 WO 2016060332A1 KR 2014012542 W KR2014012542 W KR 2014012542W WO 2016060332 A1 WO2016060332 A1 WO 2016060332A1
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- 230000005693 optoelectronics Effects 0.000 title claims abstract description 37
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- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 34
- 229910052805 deuterium Inorganic materials 0.000 claims description 34
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- 125000000217 alkyl group Chemical group 0.000 claims description 25
- -1 dibenzofuranyl group Chemical group 0.000 claims description 24
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
Definitions
- An organic optoelectronic device and a display device An organic optoelectronic device and a display device.
- Organic optoelectric diodes are devices that can switch between electrical and optical energy.
- Organic optoelectronic devices can be divided into two types according to the principle of operation.
- One is an optoelectronic device in which an exciton formed by light energy is separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electrical energy.
- It is a light emitting device that generates light energy from electrical energy.
- Examples of the organic optoelectronic device is an organic photoelectric device, the organic light emitting cow "Here, an organic solar cell and an organic photosensitive drum (organic photo conductor drum) or the like.
- organic light emitting diodes have recently attracted much attention as demand for flat panel displays increases.
- the organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material.
- the organic light emitting device has a structure in which an organic layer is inserted between an anode and a cathode.
- the present invention is to provide a long life blue organic light emitting device to solve this problem.
- One embodiment provides an organic optoelectronic device capable of realizing high efficiency characteristics.
- Another embodiment provides a display device including the organic optoelectronic device.
- Z are each independently N, C or CR a ,
- At least one of Z is N,
- R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to CI0 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof, and L 1 is substituted or unsubstituted A phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
- nl to n3 are each independently 0 or 1
- Y 1 and Y 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof, and Ar la and Ar lb are substituted or unsubstituted A substituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
- R ′′ to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or a combination thereof ,
- X 1 is 0 or S
- R 17 and R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C 1 to C20 alkoxy group, substituted Or an unsubstituted C3 to C20 cycloalkoxy group, a substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstit
- Ar 2 and Ar 3 are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
- L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 An arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
- n4 to n6 are each independently an integer of any one of 0 to 3,
- Substituted of Formula 1 to 3 is at least one hydrogen is deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 To C30 alkyl group, C3 to C30
- a cycloalkyl group a C2 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group.
- a display device including the organic optoelectronic device is provided.
- FIG. 1 is a schematic cross-sectional view of an organic optoelectronic device according to an embodiment. ⁇ Description of the sign>
- organic layer 31 hole transport layer
- substituted means that at least one hydrogen in a substituent or compound is a deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C 1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 It means substituted by C1-C10 trifluoroalkyl group or cyano group, such as an alkoxy group, a flutoro group, and a trifluoromethyl group.
- C1 to C10 trifluoroalkyl group or cyano group such as heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group
- the substituted C6 to C30 aryl group can be fused to another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.
- hetero means one to three hetero atoms selected from the group consisting of ⁇ , ⁇ , S, P, and Si in one functional group, and the remainder is carbon unless otherwise defined.
- an "alkyl group” is aliphatic
- the alkyl group may be a "saturated alkyl group" "that does not contain any double or triple bonds.
- the alkyl group may be an alkyl group of C1 to C30. More specifically, the alkyl group
- a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, with methyl, ethyl, propyl, iso-propyl, ⁇ ⁇ butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nuclear group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means a practical skill.
- an "aryl group” refers to a substituent in which all elements of a cyclic substituent have a p-orbital, and these P-orbitals form a conjugate, and are monocyclic and polycyclic. Or fused ring polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.
- heteroaryl group means containing 1 to 3 heteroatoms selected from the group consisting of N, 0, S, P, and Si in the aryl group, and the rest are carbon.
- each ring may contain 1 to 3 heteroatoms.
- a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heteroaryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthra Senyl, substituted or unsubstituted
- Phenanthryl group substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted P-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted Or an unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group , Substituted or unsubstituted pyryl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or un
- Acridinyl group substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenanozinyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuranyl group , Substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazolyl group, or a combination thereof, but is not limited thereto.
- the hole characteristic refers to a characteristic capable of forming holes by donating electrons when an electric field is applied, and injecting holes formed at the anode into the light emitting layer having conductive properties along the HOMO level, and emitting layer. It is a characteristic that facilitates the movement of the hole formed in the anode and the movement in the light emitting layer.
- the electron characteristic refers to a characteristic that can receive electrons when an electric field is applied, and has a conductivity characteristic along the LUMO level, and injects electrons formed in the cathode into the light emitting layer, moves electrons formed in the light emitting layer to the cathode, and It means a property that facilitates movement.
- an organic optoelectronic device according to example embodiments is described.
- the organic optoelectronic device is not particularly limited as long as the device can switch electrical energy and light energy, and examples thereof include organic photoelectric devices, organic light emitting devices, organic solar cells, and organic photosensitive drums.
- an organic light emitting device which is an example of an organic optoelectronic device, is illustrated.
- the present invention is not limited thereto and may be similarly applied to other organic optoelectronic devices.
- an organic optoelectronic device according to an embodiment is positioned between an anode 10 and a cathode 20 facing each other, and between the anode 10 and the cathode 20.
- the anode 10 may be made of, for example, a conductor having a high hole function, for example, to facilitate hole injection, and may be made of a metal, a metal oxide, and / or a conductive polymer, for example.
- the anode 10 may be, for example, a metal such as nickel, platinum, vanadium, crumb, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide (ITO),
- Metal oxides such as indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO and A1 or Sn02 and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not limited.
- the cathode 20 may be made of a low work function conductor, for example, to facilitate electron injection, and may be made of metal, metal oxide and / or conductive polymer, for example.
- the cathode 20 is, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; Multilayer structure materials such as LiF / Al, Li02 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca.
- the present invention is not limited thereto.
- the organic layer 30 includes a hole transport layer 31, a light emitting layer 32, and a hole transport auxiliary layer 33 positioned between the hole transport layer 31 and the light emitting layer 32.
- the hole transport layer 31 is a layer for facilitating hole transfer from the anode 10 to the light emitting layer 32, and may be, for example, an amine compound, but is not limited thereto.
- the amine compound may include, for example, at least one aryl group and / or heteroaryl group.
- the amine compound may be represented by, for example, the following Chemical Formula a or Chemical Formula b, but is not limited thereto.
- Ar a to Ar g are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof ,
- At least one of Ar a to Ar c and at least one of Ar d to Ar g is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
- Ar h is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.
- the electron transport layer 34 is a layer for facilitating electron transfer from the cathode 20 to the light emitting layer 32.
- the electron transport layer 34 is an organic compound having an electron withdrawing group, and a metal compound that can accept electrons well. Or combinations thereof may be used.
- aluminum trihydroxyquinoline Alq 3
- 1,3,4-oxadiazole derivative 2- (4-biphenylyl-5-phenyl-1,3,4-oxa oxadiazole (2- (4-biphenylyl) -5 -phenyl-l, 3, 4 -oxadiazole, PBD)
- a quinoxaline derivative of 1, 3, 4 _ Tris [Ophenyl ⁇ 6 -trifluoromethyl) ternoxaline _ 2 monoyl] benzene (1 , 3 , 4 _ tris [(3 _ p enyl _ 6 _ trifluoromethyl) quino-xaline-2-yl] benzene, TPQ)
- naphthalen-2-yl -6- (naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline) may be used, but is not limited thereto.
- the electron transport layer may be an organometallic compound represented by the following general formula (C) alone or in combination with the electron transport layer material.
- Y is a portion in which any one selected from C, N, 0 and S is directly bonded to M to form a single bond, and a portion selected from C, N, 0 and S forms a coordination bond to M. It includes, and is a ligand chelated by the single bond and the coordination bond,
- M is an alkali metal, alkaline earth metal, aluminum (A1) or boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination with M,
- A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 20 carbon atoms
- the 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, 1 selected from the group consisting of hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron It means to be substituted with more than one substituent.
- Y may be the same or different and each independently from each other, but to be any one selected from the formula cl) through (c39> not limited thereto.
- R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 Heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted 'or unsubstituted C1 to C30 alkylamino group, substituted Or an unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C6 to C30 arylamino group, and a substituted or unsubstituted C6 to C30 arylsilyl group, and are connected to adjacent substituents with alky
- the light emitting layer 32 is an organic layer having a light emitting function.
- the light emitting layer 32 includes a host and a dopant.
- the host mainly has a function of promoting recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant has a function of efficiently emitting excitons obtained by recombination.
- the light emitting layer can include known hosts and dopants.
- Known hosts include, for example, Alq3, CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole)), 9,10-di (naphthalene-2- Yl) anthracene (ADN), TCTA, TPBI (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (l, 3,5-tris (N-phenylbenzimidazole-2-yl) benzene) ), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene), mCP, OXD-7 and the like can be used, but is not limited thereto.
- the dopant may be at least one of a fluorescent dopant and a phosphorescent dopant.
- the phosphorescent dopant may be an organometallic complex including 1] ", 1 ⁇ 03,1,,, 1 or a combination of two or more thereof, but is not limited thereto.
- blue dopants examples include F 2 Irpic, (F 2 ppy) 2 Ir (tmd), Ir (dfppz) 3 , ter-fluorene, 4,4′-bis (4-diphenylamino Styryl) biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butyl perylene (TBPe), DPVBi, pyrene derivatives (KR0525408, LG Electronics Co., Ltd.) and the like, but are not limited thereto. It is not.
- red dopants examples include, but are not limited to, PtOEP, Ir (piq) 3 , BtpIr, and the like.
- the content of the dopant is typically may be selected from the range of the light-emitting layer 100 weight 0/0 of about 0.01 to about 15 parts by weight 0 / per., And the like.
- the light emitting layer has a thickness of about 200 A to about 700 A.
- the electron transport auxiliary layer 35 includes a chaff U compound having relatively strong electronic properties and a second compound having relatively strong hole properties.
- the first compound is a compound having relatively strong electronic properties, and may be represented by the following Chemical Formula 1.
- Z are each independently N, C or CR a ,
- At least one of Z is N,
- R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof, and L 1 is substituted or unsubstituted A phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
- nl to n3 are each independently 0 or 1, and nl + n2 + n3 ⁇ l.
- the first compound may be represented by, for example, the following Chemical Formula 1-I or Chemical Formula l- ⁇ depending on the bonding position of the triphenylene group.
- ⁇ , ⁇ 1 to R ⁇ L 1 and nl to n3 are as described above.
- the first compound includes a triarylene group and a heteroaryl group containing at least one nitrogen atom. Since the first compound includes a ring containing at least one nitrogen, the first compound has a structure in which electrons are easily received when an electric field is applied, and thus an electron injection amount can be increased by 0. Accordingly, the organic optoelectronic device to which the first compound is applied is driven. The voltage can be lowered and the efficiency can also be improved.
- the first compound represented by Chemical Formula 1 has at least one kink structure around an arylene group and / or a heteroarylene group.
- the fold structure refers to a structure in which two connecting portions of the arylene group and / or the heteroarylene group do not form a straight structure.
- a structure in which two connecting portions of the arylene group and / or the heteroarylene group do not form a straight structure For example, in the case of phenylene, para-phenylene (p-) in which o-phenylene and meta phenylene in which the linking portions do not form a straight structure has the bending structure, and the linking portions form a straight structure. phenylene) does not have this bending structure.
- the bending structure is a linking group (L 1 ) and / or
- It may be formed around the arylene group / hetero arylene group.
- nl of Formula 1 is 0, that is, in a structure without a linking group (L 1 ), a fold structure can be formed around an arylene group / heteroarylene group, for example, a compound represented by the following formula la or lb have.
- a folding structure may be formed around the linking group (L 1 ), and for example, L 1 may be a substituted or unsubstituted phenylene group having a folding structure, or a substituted or unsubstituted structure. It may be a biphenylene group or a substituted or unsubstituted terphenylene group having a folding structure.
- L 1 may be, for example, a single bond or one selected from substituted or unsubstituted groups listed in Group 1 below. [Group i]
- substituted means that at least one hydrogen is deuterium, halogen, C1 to C20 alkyl group,
- C3 to C20 cycloalkyl group C1 to C20 alkoxy group, C3 to C20 cycloalkoxy group, C1 to C20 alkylthio group, C6 to C30 aralkyl group, C6 to C30 aryl group, C6 to C30 aryloxy group, C6 to C30 arylti Or a C2 to C30 heteroaryl group, a C2 to C30 amino group, a C3 to C30 silyl group, a cyano group, a nitro group, a hydroxyl group, or a carboxyl group.
- the compound 11 may preferably have at least two folding structures, for example, may have two to four folding structures.
- the first compound has the above-described imaging structure to properly charge
- the efficiency of the organic optoelectronic device to which the composition is applied can be improved.
- the compound 1 may be represented by, for example, any one of Formulas lc to It. [Formula Is] [Formula it]
- R 60 to R 77 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 ' ' to C30 heteroaryl group, substituted or unsubstituted amine group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C6 to C30
- Heteroarylamine groups substituted or unsubstituted C1 to C30 alkoxy groups, halogen groups, halogen-containing groups, cyano groups, hydroxyl groups, amino groups, nitro groups, carboxyl groups, ferrocenyl groups or combinations thereof.
- the first compound may be, for example, a compound listed in Group 2, but is not limited thereto.
- the second compound may be represented by the following Chemical Formula 2 , for example. 2]
- Y 1 and Y 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
- Ar la and Ar lb are substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or a combination thereof,
- R 1 1 to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or a combination thereof to be.
- Compound represented by the formula (2) is a compound having a relatively strong hole characteristics, it is included in the electron transport auxiliary layer with the C1 compound, the electron injection amount of the first compound can be adjusted, the light emitting layer and the electron transport auxiliary The stability of the device can be improved by preventing the accumulation of holes at the layer interface. Therefore, the luminous efficiency and lifespan characteristics of the organic optoelectronic device can be significantly improved.
- the second compound may be represented by at least one of, for example, the following Chemical Formula 2- 1 to Chemical Formula 2-VII, depending on the binding position of bicarbazole.
- the second compound has a structure in which two carbazolyl groups having a substituent are connected.
- Ar la and Ar lb of the second compound is a substituent having a hole or electronic properties, each independently a substituted or unsubstituted phenyl group, substituted or unsubstituted
- Biphenyl group substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted Benzothiophenyl group, substituted or unsubstituted
- Fluorenyl group substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted triphenylene group, substituted or Unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.
- the second compound may be represented by at least one of Formula 2-K to Formula 2-XI according to the properties of Ar la and Ar lb , for example.
- 2-K] [Formula 2- ⁇ ]
- 2- ⁇ ⁇ ] [Formula 2- ⁇ ⁇ ]
- ET, ET1, and ⁇ 2 are each independently a substituent having electronic properties, and ⁇ , ⁇ and ⁇ 2 are each independently substituents having hole characteristics.
- Substituents? ⁇ ', ⁇ , and? ⁇ 2''having electronic properties among Ar la and Ar lb of the second compound may be, for example, substituents represented by the following Chemical Formula A.
- Z are each independently N or CR k ,
- R k are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and at least one of X, A, and A2 is N Including,
- a and b are each independently 0 or 1.
- the substituent represented by Formula A may be, for example, one of the functional groups listed in Group 3 below. [Group 3]
- substituents' ⁇ '' ⁇ and “ ⁇ 2” having hole characteristics among Ar la and Ar lb of the second compound may be, for example, one of the functional groups listed in Group 4 below.
- the second compound may be selected from, for example, the compounds listed in Group 5 below, but is not limited thereto.
- One kind or two or more kinds of the second compound may be used.
- the electron transport auxiliary layer according to the exemplary embodiment of the present invention may simultaneously include a compound 11 having strong electronic properties and a second compound having strong hole properties.
- At least one of the first compound represented by Formula 1-1 or Formula 1- ⁇ and the second compound represented by Formulas 2-1 to 2-X I may be used together.
- At least one of the first compounds represented by formulas lc to it and at least one of the second compounds represented by formulas 2-IX to 2- 2-I may be used together.
- At least one of the compound 1 represented by formulas lc, Id, lg, and lh and at least one of the second compound represented by formulas 2-K to 2-X I may be used together.
- first compound represented by Chemical Formula lh and the second compound represented by Chemical Formula 2-X I may be used together.
- the first compound and the crab 2 compound may be included, for example, in a weight ratio of about 1:99 to 99: 1. Specifically, it may be included in a weight ratio of 10:90 to 90: 10,20: 80 to 80: 20,30: 70 to 70:30, and 40:60 to 60:40, most specifically, 50:50.
- the hole transport auxiliary layer 33 includes a third compound having good hole transporting properties, and by adjusting the hole injection characteristics by reducing the HOMO energy level difference between the hole transport layer 31 and the light emitting layer 32, the hole transport auxiliary Extinction of extinction caused by polaron at the interface is reduced by reducing the accumulation of holes at the interface between the layer 33 and the light emitting insect 32
- the quenching can be reduced. Accordingly, deterioration of the device may be reduced and the device may be stabilized to improve efficiency and lifespan.
- the third compound may be a compound represented by Formula 3 below.
- X 1 is 0 or S
- R 17 and R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C 1 to C20 alkoxy group, substituted Or an unsubstituted C3 to C20 cycloalkoxy group, a substituted or unsubstituted C 1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstit
- Ar 2 and Ar 3 are each independently a substituted or unsubstituted C6 to C30 aryl group Or a substituted or unsubstituted C2 to C30 heteroaryl group,
- L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
- n4 to n6 are each independently an integer of 0 to 3
- the third compound may be represented by, for example, the following Formula 3-I or Formula 3- ⁇ depending on the bonding position of the amine substituent.
- the third compound may be, for example, at least one of Formula 3-m to Formula 3-K.
- X 2 is 0, S, or CR c R d ,
- X 3 are each independently 0 or S
- R 19 to R 27 , R C , and R d are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 amino group, substituted or
- Ar 2 and Ar 3 are specifically, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or Unsubstituted anthracenyl group, substituted or unsubstituted Phenanthrenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted pyridinyl groups substituted or unsubstituted pyrimidinyl groups, Substituted or unsubstituted triazinyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group, substituted or un
- substituted or unsubstituted phenyl group substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl Groups, substituted or unsubstituted phenanthrenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted groups
- Dibenzofuranyl group substituted or unsubstituted dibenzothiophenyl group s, or a combination thereof.
- Y is 0, S, CR f R g , SiR h R i or NR j ,
- R e to R j are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted A C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group, or a combination thereof,
- substituted means that at least one hydrogen is deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, C1 to C30 Alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group or cyano group It means substituted.
- the third compound may be selected from, for example, a compound listed in Group 7, but is not limited thereto.
- a hole transport auxiliary layer comprising a third compound may be included at the same time.
- efficiency can be improved by adjusting the charge balance through the hole injection control ability of the hole transport auxiliary layer and the electron injection control ability of the electron transport auxiliary layer, and by applying the hole transport auxiliary layer and the electron transport auxiliary layer, By preventing charge from accumulating at each interface of the organic layer, deterioration of the device can be reduced, and the device can be stabilized to improve life.
- At least one of the second compounds represented by 2- 1 to formula 2-X I, and the third compound represented by formula 3- 1 to formula 3-K can be used together.
- At least one of the first compounds represented by formulas lc to u, at least one of the second compounds represented by formulas 2-K to 2-XI, and represented by formulas 3- ⁇ to 3-K The third compound can be used together.
- At least one of the first compounds represented by the formulas lc, Id, lg, and lh, at least one of the two compounds represented by the formulas 2-K to 2-XI, and the formula 3-VH, 3-, and the third compound represented by the formula 3-K can be used together.
- the first compound represented by the formula lh, the second compound represented by the formula 2-X I, and the third compound represented by the formula 3-W and the formula 3-VI may be used together.
- the hole transport auxiliary layer 35 may be applied on the hole transport layer in a thickness of 0.1 nm to 2 (). 0 nm by a deposition or inkjet process, for example, 0.2 nm to 10.0 nm, 0.3 nm to 5 nm, 0.3 nm to 2 nm. , 0.4 nm to 1,0 nm in thickness can be applied.
- the organic layer 30 may optionally include a hole injection layer (not shown) located between the anode 10 and the hole transport layer 31 and / or an electron injection layer located between the cathode 20 and the electron transport layer 34 ( Not shown).
- the organic light emitting diode described above may be applied to an organic light emitting diode display. [Form for implementation of invention]
- 9-phenyl-9H-carbazol-3-yl boronic acid (9-phenyl-9H-carbazol-3-yl boronic acid, -TCI) 10 g (34.83 mmol), 3-bromo-9-phenylcarbazole ( 3-bromo-9-phenylcarbazole, Aldrich), 11.77 g (38.31 mmol) and 14.44 g (104.49 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 0.80 g (0.7 mmmol) The suspension was suspended in 50 ml of distilled water and stirred under reflux for 12 hours.
- Intermediate M- was synthesized and purified in the same manner as in the synthesis of Intermediate M-5, except that 10 g (30.9 mmol) of Intermediate M-2 and 6.3 g (37.08 mmol, Aldrich) of 4-aminobiphenyl were used. 8 10.5 g (80%) were obtained.
- Table 1 was prepared from the starting material 1 and starting material 2 in the synthesis method of Synthesis Example 20, the product of the following table. The yield and LC-Mass values for the same are shown in the following [Table 1].
- Glass substrates coated with ⁇ (Indium tin oxide) to a thickness of 1500A were washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and then transferred to the plasma cleaner. The substrate was cleaned for 10 minutes by using an oxygen plasma, and then the substrate was transferred to a vacuum laminator.
- ⁇ Indium tin oxide
- the light emitting layer was formed by doping BD370 at a weight of 200 A using BH1 13 and BD370 sold by SFC as a blue fluorescent light emitting host and dopant on the hole transport auxiliary layer.
- an electron transport auxiliary layer having a thickness of 50 A was formed on the light emitting layer by vacuum deposition of Compound A-33 obtained in Synthesis Example 8 and Compound B-43 obtained in Synthesis Example 11.
- compound A-33 and compound B-43 were used in 1: 1 weight ratio.
- the organic light emitting device has a structure having six organic thin film layers, specifically
- Example 2 An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound H-1 1 obtained in Synthesis Example 22 instead of the compound H-2 for the hole transport auxiliary layer. Reference Example 1
- An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound C was deposited to a thickness of 750 people to form a hole transport layer, without forming a hole transport auxiliary layer. Comparative Example 1
- the current value flowing through the unit device was measured by using a current-voltmeter (Keithley 2400) while increasing the voltage from 0V to 10V, and the measured current value was divided by the area to obtain a result.
- the luminance was measured by using a luminance meter (Minolta Cs-IOOOA) while increasing the voltage from 0V to 10V to obtain a result. (3) Measurement of luminous efficiency
- the current efficiency (cd / ⁇ ) of the same current density (10 mA / cm 2 ) was calculated using the luminance, current density, and voltage measured from (1) and (2).
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Abstract
The present invention relates to an organic optoelectronic device, and a display device containing the organic optoelectronic device, the organic optoelectronic device comprising: an anode and a cathode facing each other; a light emitting layer positioned between the anode and the cathode; a hole transport layer positioned between the anode and the light emitting layer; a hole transport auxiliary layer positioned between the hole transport layer and the light emitting layer; an electron transport layer positioned between the cathode and the light emitting layer; and an electron transport auxiliary layer positioned between the electron transport layer and the light emitting layer, wherein the electron transport auxiliary layer comprises at least one type of first compound represented by the following chemical formula 1 and at least one type of second compound represented by the following chemical formula 2, and the hole transport auxiliary layer comprises at least one type of third compound represented by the following chemical formula 3. Chemical formulas 1-3 are the same as those defined in the specification.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
유기 광전자 소자 및 표시 장치 Organic optoelectronic devices and displays
【기술분야】 Technical Field
유기 광전자 소자 및 표시 장치에 관한 것이다. An organic optoelectronic device and a display device.
【배경기술】 Background Art
유기 광전자 '소자 (organic optoelectric diode)는 전기 에너지와 광 에너지를 상호 전환할 수 있는 소자이다. Organic optoelectric diodes are devices that can switch between electrical and optical energy.
유기 광전자 소자는 동작 원리에 따라 크게 두 가지로 나눌 수 있다. 하나는 광 에너지에 의해 형성된 액시톤 (exciton)이 전자와 정공으로 분리되고 상기 전자와 정공이 각각 다른 전극으로 전달되면서 전기 에너지를 발생하는 광전 소자이고, 다른 하나는 전극에 전압 또는 전류를 공급하여 전기 에너지로부터 광 에너지를 발생하는 발광 소자이다. Organic optoelectronic devices can be divided into two types according to the principle of operation. One is an optoelectronic device in which an exciton formed by light energy is separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electrical energy. It is a light emitting device that generates light energy from electrical energy.
유기 광전자 소자의 예로는 유기 광전 소자, 유기 발광 소'자, 유기 태양 전지 및 유기 감광체 드럼 (organic photo conductor drum) 등을 들 수 있다. Examples of the organic optoelectronic device is an organic photoelectric device, the organic light emitting cow "Here, an organic solar cell and an organic photosensitive drum (organic photo conductor drum) or the like.
이 중, 유기 발광 소자 (organic light emitting diode, OLED)는 근래 평판 표시 장치 (flat panel display device)의 수요 증가에 따라 크게 주목 받고 있다. 상기 유기 발광 소자는 유기 발광 재료에 전류를 가하여 전기 에너지를 빛으로 전환시키는 소자로서, 통상 양극 (anode)과 음극 (cathode) 사이에 유기 층이 삽입된 구조로 이루어져 있다. Among these, organic light emitting diodes (OLEDs) have recently attracted much attention as demand for flat panel displays increases. The organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material. The organic light emitting device has a structure in which an organic layer is inserted between an anode and a cathode.
장수명 풀 칼라 디스플레이의 가장 큰 문제가 되고 있는 요소 중의 하나는 청색유기발광소자의 수명이다. 따라서 장수명 청색유기발광소자의 개발을 위해 많은 연구가 진행되고 있는 중이다. 본 발명에서는 이러한 문제점을 해결하기 위해 장수명 청색유기발광소자를 제공하고자 한다ᅳ One of the biggest problems of long life full color display is the lifetime of the blue organic light emitting device. Therefore, a lot of research is being carried out for the development of long-life blue organic light emitting device. The present invention is to provide a long life blue organic light emitting device to solve this problem.
【발명의 상세한 설명】 [Detailed Description of the Invention]
【기술적 과제】 [Technical problem]
일 구현예는 고효율 특성을 구현할 수 있는 유기 광전자 소자를 제공한다. 다른 구현예는 상기 유기 광전자 소자를 포함하는 표시 장치를 제공한다. 【기술적 해결 방법】 One embodiment provides an organic optoelectronic device capable of realizing high efficiency characteristics. Another embodiment provides a display device including the organic optoelectronic device. [Technical solution]
일 구현예에 따르면， 서로 마주하는 애노드와 캐소드, 상기 애노드와 상기
캐소드 사이에 위치하는」발광층, 상기 애노드와 상기 발광층 사이에 위치하는 정공수송층, 상기 정공수송층과 상기 발광층 사이에 위치하는 정공수송보조층, 상기 캐소드와 상기 발광층 사이에 위치하는 전자수송층, 그리고 상기 전자수송층과 상기 발광층 사이에 위치하는 전자수송보조층을 포함하고， 상기 전자수송보조층은 하기 화학식 1로 표현되는 적어도 1종의 제 1 화합물과 하기 화학식 2로 표현되는 적어도 1종의 제 2 화합물을 포함하고, 상기 정공수송보조층은 하기 화학식 3으로 표현되는 적어도 1종의 제 3 화합물을 포함하는 유기 광전자 소자를 제공한다. According to one embodiment, the anode and the cathode facing each other, the anode and the A light emitting layer located between the cathode, a hole transport layer located between the anode and the light emitting layer, a hole transport auxiliary layer located between the hole transport layer and the light emitting layer, an electron transport layer located between the cathode and the light emitting layer, and the electrons An electron transport auxiliary layer positioned between the transport layer and the light emitting layer, wherein the electron transport auxiliary layer comprises at least one first compound represented by the following Chemical Formula 1 and at least one second compound represented by the following Chemical Formula 2. It includes, the hole transport auxiliary layer provides an organic optoelectronic device comprising at least one third compound represented by the formula (3).
[화학식 1] [Formula 1]
상기 화학식 1에서, In Chemical Formula 1,
Z는 각각 독립적으로 N, C 또는 CRa이고, Z are each independently N, C or CR a ,
Z 중 적어도 하나는 N 이고, At least one of Z is N,
R1 내지 R10 및 Ra는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 CI0 알킬기, 치환 또는 비치환된 C6 내지 C12 아릴기 또는 이들의 조합이고， L1은 치환 또는 비치환된 페닐렌기, 치환 또는 비치환된 바이페닐렌기 또는 치환 또는 비치환된 터페닐렌기이고, R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to CI0 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof, and L 1 is substituted or unsubstituted A phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
nl 내지 n3는 각각 독립적으로 0 또는 1이고, nl to n3 are each independently 0 or 1,
nl+n2+n3>l 이고, nl + n2 + n3> l,
[화학식 2] [Formula 2]
Y1 및 Y2는 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기 또는 이들의 조합이고, Arla 및 Arl b은 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기 또는 이들의 조합이고, Y 1 and Y 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof, and Ar la and Ar lb are substituted or unsubstituted A substituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
R" 내지 R16는 각각 독립적으로 수소， 중수소, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C50 아릴기， 치환 또는 비치환된 C2 내지 C50 헤테로아릴기 또는 이들의 조합이고, R ″ to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or a combination thereof ,
상기 화학식 3 에서， In Chemical Formula 3,
X1은 0 또는 S이고， X 1 is 0 or S,
R17 및 R18은 각각 독립적으로, 수소, 중수소, 할로겐, 치환 또는 비치환된 C1 내지 C20 알킬기， 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환또는 비치환된 C 1 내지 C20 알콕시기, 치환 또는 비치환된 C3 내지 C20 시클로알콕시기, 치환 또는 비치환된 C1 내지 C20 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기， 치환 또는 비치환된 C6 내지 C30 아릴티오기， 치환 또는 비치환된 C2 내지 C30 해테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실기 또는 카르복실기, 또는 이들의 조합이고, R 17 and R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C 1 to C20 alkoxy group, substituted Or an unsubstituted C3 to C20 cycloalkoxy group, a substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 Silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof,
Ar2 및 Ar3는 각각 독립적으로, 치환 또는 비치환된 C6 내지 C30 아릴기 또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴기이고， Ar 2 and Ar 3 are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
L2 내지 L4는 각각 독립적으로 단일결합, 치환 또는 비치환된 C6 내지 C30
아릴렌기, 치환 또는 비치환된 헤테로아릴렌기 또는 이들의 조합이고, L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 An arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
n4 내지 n6은 각각 독립적으로, 0 내지 3 중 어느 하나인 정수이고, n4 to n6 are each independently an integer of any one of 0 to 3,
상기 화학식 1 내지 3의 "치환 "은 적어도 하나의 수소가 중수소, 할로겐기， 히드록시기, 아미노기, 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기， 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 "Substituted" of Formula 1 to 3 is at least one hydrogen is deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 To C30 alkyl group, C3 to C30
시클로알킬기， C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기, 플루오로기, C1 내지 C 10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. It is substituted with a cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group. .
다른 구현예에 따르면, 상기 유기 광전자 소자를 포함하는 표시 장치를 제공한다. According to another embodiment, a display device including the organic optoelectronic device is provided.
【유리한 효과】 Advantageous Effects
고효율 유기 광전자 소자를 구현할 수 있다. High efficiency organic optoelectronic devices can be implemented.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 일 구현예에 따른 유기 광전자 소자를 개략적으로 도시한 단면도이다. <부호의 설명 > 1 is a schematic cross-sectional view of an organic optoelectronic device according to an embodiment. <Description of the sign>
10: 애노드 20: 캐소드 10: anode 20: cathode
30: 유기층 31 : 정공수송층 30: organic layer 31: hole transport layer
32: 발광층 33: 정공수송보조층 32: light emitting layer 33: hole transport auxiliary layer
34: 전자수송층 35: 전자수송보조층 34: electron transport layer 35: electron transport auxiliary layer
【발명의 실시를 위한 최선의 형태】 [Best form for implementation of the invention]
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 명세서에서 "치환 "이란 별도의 정의가 없는 한, 치환기 또는 화합물 중의 적어도 하나의 수소가 중수소, 할로겐기, 히드록시기, 아미노기, 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C 1 내지 C 10 알킬실릴기, C3 내지 C30 시클로알킬기, C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기, 플투오로기, 트리플루오로메틸기 등의 C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다.
또한 상기 치환된 할로겐기, 히드록시기， 아미노기, 치환 또는 비치환된 C1 내지 C20 아민기, 니트로기， 치환 또는 비치환된 C3 내지 C40 실릴기， C1 내지 C30 알킬기, C1 내지 C10 알킬실릴기, C3 내지 C30 시클로알킬기, C2 내지 C30 As used herein, unless otherwise defined, "substituted" means that at least one hydrogen in a substituent or compound is a deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C 1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 It means substituted by C1-C10 trifluoroalkyl group or cyano group, such as an alkoxy group, a flutoro group, and a trifluoromethyl group. In addition, the substituted halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C20 amine group, nitro group, substituted or unsubstituted C3 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30
헤테로시클로알킬기， C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기， C1 내지 C20 알콕시기, 플루오로기, 트리플루오로메틸기 등의 C1 내지 C10 트리플루오로알킬기 또는 시아노기 중 인접한 두 개의 치환기가 융합되어 고리를 형성할 수도 있다. 예를 들어, 상기 치환된 C6 내지 C30 아릴기는 인접한 또다른 치환된 C6 내지 C30 아릴기와 융합되어 치환 또는 비치환된 플루오렌 고리를 형성할 수 있다. Two adjacent substituents of C1 to C10 trifluoroalkyl group or cyano group such as heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group To form a ring. For example, the substituted C6 to C30 aryl group can be fused to another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.
본 명세서에서 "헤테로"란 별도의 정의가 없는 한, 하나의 작용기 내에 Ν, Ο, S, P 및 Si로 이루어진 군에서 선택되는 헤테로 원자를 1 내지 3개 함유하고, 나머지는 탄소인 것을 의미한다. In the present specification, "hetero" means one to three hetero atoms selected from the group consisting of Ν, Ο, S, P, and Si in one functional group, and the remainder is carbon unless otherwise defined. .
본 명세서에서 "알킬 (alkyl)기"란 별도의 정의가 없는 한, 지방족 As used herein, unless otherwise defined, an "alkyl group" is aliphatic
탄화수소기를 의미한다. 알킬기는 어떠한 이중결합이나 삼중결합을 포함하고 있지 않은 "포화 알킬 (saturated alkyl)기 ' '일 수 있다. It means a hydrocarbon group. The alkyl group may be a "saturated alkyl group" "that does not contain any double or triple bonds.
상기 알킬기는 C1 내지 C30인 알킬기일 수 있다. 보다 구체적으로 알킬기는 The alkyl group may be an alkyl group of C1 to C30. More specifically, the alkyl group
C1 내지 C20 알킬기 또는 C1 내지 C10 알킬기일 수도 있다. 예를 들어, C1 내지 C4 알킬기는 알킬쇄에 1 내지 4 개의 탄소원자가 포함되는 것을 의미하며， 메틸, 에틸， 프로필, 이소-프로필 , ηᅳ부틸， 이소-부틸， sec-부틸 및 t-부틸로 이루어진 군에서 선택됨을 나타낸다. It may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, with methyl, ethyl, propyl, iso-propyl, η ᅳ butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:
상기 알킬기는 구체적인 예를 들어 메틸기， 에틸기， 프로필기, 이소프로필기, 부틸기, 이소부틸기, t-부틸기, 펜틸기, 핵실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기， 시클로핵실기 등을 의미한다. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nuclear group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means a practical skill.
본 명세서에서 "아릴 (aryl)기''는 환형인 치환기의 모든 원소가 p-오비탈을 가지고 있으며, 이들 P-오비탈이 공액 (conjugation)을 형성하고 있는 치환기를 의미하고, 모노시클릭, 폴리시클릭 또는 융합 고리 폴리시클릭 (즉, 탄소원자들의 인접한 쌍들을 나눠 가지는 고리) 작용기를 포함한다. As used herein, an "aryl group" refers to a substituent in which all elements of a cyclic substituent have a p-orbital, and these P-orbitals form a conjugate, and are monocyclic and polycyclic. Or fused ring polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.
본 명세서에서 "헤테로아릴 (heteroaryl)기 "는 아릴기 내에 N, 0, S, P 및 Si로 이루어진 군에서 선택되는 헤테로 원자를 1 내지 3개 함유하고, 나머지는 탄소인 것을 의미한다. 상기 헤테로아릴기가 융합고리인 경우, 각각의 고리마다 상기 해테로 원자를 1 내지 3개 포함할 수 있다.
보다 구체적으로, 치환 또는 비치환된 C6 내지 C30 아릴기 및 /또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴기는, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 나프틸기， 치환 또는 비치환된 안트라세닐기， 치환 또는 비치환된 As used herein, "heteroaryl group" means containing 1 to 3 heteroatoms selected from the group consisting of N, 0, S, P, and Si in the aryl group, and the rest are carbon. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms. More specifically, a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heteroaryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthra Senyl, substituted or unsubstituted
페난트릴기, 치환 또는 비치환된 나프타세닐기, 치환 또는 비치환된 피레닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 P-터페닐기, 치환 또는 비치환된 m- 터페닐기, 치환 또는 비치환된 크리세닐기， 치환 또는 비치환된 트리페닐레닐기, 치환 또는 비치환된 페릴레닐기, 치환 또는 비치환된 인데닐기, 치환 또는 비치환된 퓨라닐기, 치환 또는 비치환된 티오페닐기, 치환 또는 비치환된 피를릴기, 치환 또는 비치환된 피라졸릴기, 치환 또는 비치환된 이미다졸일기, 치환 또는 비치환된 트리아졸일기, 치환 또는 비치환된 옥사졸일기, 치환 또는 비치환된 티아졸일기, 치환 또는 비치환된 옥사디아졸일기, 치환 또는 비치환된 티아디아졸일기, 치환 또는 비치환된 피리딜기, 치환 또는 비치환된 피리미디닐기, 치환 또는 비치환된 피라지닐기, 치환 또는 비치환된 트리아지닐기, 치환 또는 비치환된 벤조퓨라닐기， 치환 또는 비치환된 벤조티오페닐기, 치환 또는 비치환된 벤즈이미다졸일기, 치환 또는 비치환된 인돌일기, 치환 또는 비치환된 퀴놀리닐기, 치환 또는 비치환된 이소퀴놀리닐기, 치환 또는 비치환된 퀴나졸리닐기， 치환 또는 비치환된 Phenanthryl group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted P-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted Or an unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group , Substituted or unsubstituted pyryl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted Substituted thiazolyl group, substituted or unsubstituted oxadiazoleyl group, substituted or unsubstituted thiadiazoleyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group , Substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted Quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted
퀴녹살리닐기, 치환 또는 비치환된 나프티리디닐기, 치환 또는 비치환된 Quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted
벤즈옥사진일기， 치환 또는 비치환된 벤즈티아진일기, 치환 또는 비치환된 Benzoxazineyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted
아크리디닐기, 치환 또는 비치환된 페나진일기, 치환 또는 비치환된 페노티아진일기, 치환 또는 비치환된 페녹사진일기, 치환 또는 비치환된 플루오레닐기, 치환 또는 비치환된 디벤조퓨란일기, 치환 또는 비치환된 디벤조티오페닐기, 치환 또는 비치환된 카바졸일기 또는 이들의 조합일 수 있으나, 이에 제한되지는 않는다. Acridinyl group, substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenanozinyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuranyl group , Substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazolyl group, or a combination thereof, but is not limited thereto.
본 명세서에서, 정공 특성이란, 전기장 (electric field)을 가했을 때 전자를 공여하여 정공을 형성할 수 있는 특성을 말하는 것으로 , HOMO 준위를 따라 전도 특성을 가져 양극에서 형성된 정공의 발광층으로의 주입, 발광층에서 형성된 정공의 양극으로의 이동 및 발광층에서의 이동을 용이하게 하는 특성을 의미한다ᅳ In the present specification, the hole characteristic refers to a characteristic capable of forming holes by donating electrons when an electric field is applied, and injecting holes formed at the anode into the light emitting layer having conductive properties along the HOMO level, and emitting layer. It is a characteristic that facilitates the movement of the hole formed in the anode and the movement in the light emitting layer.
또한 전자 특성이란, 전기장을 가했을 때 전자를 받을 수 있는 특성을 말하는 것으로, LUMO 준위를 따라 전도 특성을 가져 음극에서 형성된 전자의 발광층으로의 주입, 발광층에서 형성된 전자의 음극으로의 이동 및 발광층에서의 이동을 용이하게 하는 특성을 의미한다.
이하 일 구현예에 따른 유기 광전자 소자에 대하여 설명한다. In addition, the electron characteristic refers to a characteristic that can receive electrons when an electric field is applied, and has a conductivity characteristic along the LUMO level, and injects electrons formed in the cathode into the light emitting layer, moves electrons formed in the light emitting layer to the cathode, and It means a property that facilitates movement. Hereinafter, an organic optoelectronic device according to example embodiments is described.
상기 유기 광전자 소자는 전기 에너지와 광 에너지를 상호 전환할 수 있는 소자이면 특별히 한정되지 않으며， 예컨대 유기 광전 소자, 유기 발광 소자, 유기 태양 전지 및 유기 감광체 드럼 등을 들 수 있다. The organic optoelectronic device is not particularly limited as long as the device can switch electrical energy and light energy, and examples thereof include organic photoelectric devices, organic light emitting devices, organic solar cells, and organic photosensitive drums.
여기서는 유기 광전자 소자의 일 예인 유기 발광 소자를 예시적으로 Herein, an organic light emitting device, which is an example of an organic optoelectronic device, is illustrated.
설명하지만, 이에 한정되지 않고 다른 유기 광전자 소자에도 동일하게 적용될 수 있다. Although described, the present invention is not limited thereto and may be similarly applied to other organic optoelectronic devices.
도면에서 여러 층 및 영역을 명확하게 표현하기 위하여 두께를 확대하여 나타내었다. 명세서 전체를 통하여 유사한 부분에 대해서는 동일한 도면 부호를 붙였다. 층, 막, 영역, 판 등의 부분이 다른 부분 "위에" 있다고 할 때, 이는 다른 부분 "바로 위에" 있는 경우 뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 반대로 어떤 부분이 다른 부분 "바로 위에" 있다고 할 때에는 증간에 다른 부분이 없는 것을 뜻한다. In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like parts are designated by like reference numerals throughout the specification. When a portion of a layer, film, region, plate, etc. is said to be "on top" of another part, this includes not only when the other part is "right over" but also when there is another part in between. On the contrary, when a part is "just above" another part, it means that there is no other part between them.
도 1은 일 구현예에 따른 유기 광전자 소자를 개략적으로 도시한 단면도이다. 도 1을 참고하면, 일 구현예에 따른 유기 광전자 소자는 서로 마주하는 애노드 (10)와 캐소드 (20), 그리고 애노드 (10)와 캐소드 (20) 사이에 위치하는 1 is a schematic cross-sectional view of an organic optoelectronic device according to an embodiment. Referring to FIG. 1, an organic optoelectronic device according to an embodiment is positioned between an anode 10 and a cathode 20 facing each other, and between the anode 10 and the cathode 20.
유기층 (30)을 포함한다. And an organic layer 30.
애노드 (10)는 예컨대 정공 주입이 원활하도톡 일 함수가 높은 도전체로 만들어질 수 있^며, 예컨대 금속， 금속 산화물 및 /또는 도전성 고분자로 만들어질 수 있다. 애노드 (10)는 예컨대 니켈, 백금, 바나듐， 크름, 구리， 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물， 인듐산화물, 인듐주석산화물 (ITO), The anode 10 may be made of, for example, a conductor having a high hole function, for example, to facilitate hole injection, and may be made of a metal, a metal oxide, and / or a conductive polymer, for example. The anode 10 may be, for example, a metal such as nickel, platinum, vanadium, crumb, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide (ITO),
인듐아연산화물 (IZO)과 같은 금속 산화물; ZnO와 A1 또는 Sn02와 Sb와 같은 금속과 산화물의 조합; 폴리 (3-메틸티오펜), 폴리 (3,4- (에틸렌 -1 ,2- 디옥시)티오펜 )(polyehtylenedioxythiophene: PEDT), 폴리피를 및 폴리아닐린과 같은 도전성 고분자 등을 들 수 있으나, 이에 한정되는 것은 아니다. Metal oxides such as indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO and A1 or Sn02 and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not limited.
캐소드 (20)는 예컨대 전자 주입이 원활하도록 일 함수가 낮은 도전체로 만들어질 수 있으며, 예컨대 금속, 금속 산화물 및 /또는 도전성 고분자로 만들어질 수 있다. 캐소드 (20)는 예컨대 마그네슘, 칼슘， 나트륨, 칼륨， 타이타늄， 인듐， 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석， 납, 세슘, 바륨 등과 같은 금속 또는 이들의 합금; LiF/Al, Li02/Al, LiF/Ca, LiF/Al 및 BaF2/Ca과 같은 다층 구조 물질을 들 수
있으나, 이에 한정되는 것은 아니다. The cathode 20 may be made of a low work function conductor, for example, to facilitate electron injection, and may be made of metal, metal oxide and / or conductive polymer, for example. The cathode 20 is, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; Multilayer structure materials such as LiF / Al, Li02 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca. However, the present invention is not limited thereto.
유기층 (30)은 정공수송층 (31), 발광층 (32), 그리고 정공수송층 (31)과 발광층 (32) 사이에 위치하는 정공수송보조층 (33)을 포함한다. The organic layer 30 includes a hole transport layer 31, a light emitting layer 32, and a hole transport auxiliary layer 33 positioned between the hole transport layer 31 and the light emitting layer 32.
또한, 전자수송층 (34)， 그리고 전자수송층 (34)과 발광층 (32) 사이에 위치한 전자수송보조층 (35)을 포함한다. It also includes an electron transport layer 34 and an electron transport auxiliary layer 35 positioned between the electron transport layer 34 and the light emitting layer 32.
정공수송층 (31)은 애노드 (10)로부터 발광층 (32)으로 정공 전달을 용이하게 하기 위한 층으로, 예컨대 아민 화합물일 수 있으나 이에 한정되는 것은 아니다. 상기 아민 화합물은 예컨대 적어도 하나의 아릴기 및 /또는 헤테로아릴기를 포함할 수 있다. 상기 아민 화합물은 예컨대 하기 화학식 a또는 화학식 b로 표현될 수 있으나， 이에 한정되는 것은 아니다. The hole transport layer 31 is a layer for facilitating hole transfer from the anode 10 to the light emitting layer 32, and may be, for example, an amine compound, but is not limited thereto. The amine compound may include, for example, at least one aryl group and / or heteroaryl group. The amine compound may be represented by, for example, the following Chemical Formula a or Chemical Formula b, but is not limited thereto.
[화학식 a] [화학식 b]
[Formula a] [Formula b]
상기 화학식 a또는 화학식 b에서, In Chemical Formula a or Chemical Formula b,
Ara 내지 Arg는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기 또는 이들의 조합이고, Ar a to Ar g are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof ,
Ara 내지 Arc 중 적어도 하나 및 Ard 내지 Arg 중 적어도 하나는 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기 또는 이들의 조합이고, At least one of Ar a to Ar c and at least one of Ar d to Ar g is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
Arh는 단일결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기 또는 이들의 조합이다. Ar h is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.
전자수송층 (34)은 캐소드 (20)로부터 발광층 (32)으로 전자 전달을 용이하게 하기 위한 층으로， 전자 받개 작용기 (electron withdrawing group)를 보유하고 있는 유기화합물, 전자를 잘 수용할 수 있는 금속화합물, 또는 이들의 흔합물이 사용될 수 있다. 예컨대 전자수송층 재료로서 알루미늄 트리하이드록시퀴놀린 (alumi mi trihydroxyquinoline, Alq3), 1 ,3,4-옥사디아졸 유도체인 2-(4-바이페닐일 -5-페닐 -1 ,3,4- 옥사디아졸 (2-(4-biphenylyl)-5-phenyl-l,3,4-oxadiazole, PBD), 퀴녹살린 유도체인 1，3，4_
트리스 [O페닐ᅳ6-트리플루오로메틸)뀌녹살린 _2ᅳ일]벤젠 ( 1 ,3,4_tris[(3_penyl_6_ trifluoromethyl) quino-xaline-2-yl]benzene, TPQ), 트리아졸 유도체 및 트리아진 유도체인 8-(4_(4_ (나프탈렌 _2ᅵ일)ᅵ 6ᅵ (나프탈렌 _3_일) 3,5-트리아진 _2_일)페닐)퀴놀린 (8-(4_(4ᅳThe electron transport layer 34 is a layer for facilitating electron transfer from the cathode 20 to the light emitting layer 32. The electron transport layer 34 is an organic compound having an electron withdrawing group, and a metal compound that can accept electrons well. Or combinations thereof may be used. For example, as an electron transport layer material, aluminum trihydroxyquinoline (Alumi mi trihydroxyquinoline, Alq 3 ), 1,3,4-oxadiazole derivative 2- (4-biphenylyl-5-phenyl-1,3,4-oxa oxadiazole (2- (4-biphenylyl) -5 -phenyl-l, 3, 4 -oxadiazole, PBD), a quinoxaline derivative of 1, 3, 4 _ Tris [Ophenyl ᅳ 6 -trifluoromethyl) ternoxaline _ 2 monoyl] benzene (1 , 3 , 4 _ tris [(3 _ p enyl _ 6 _ trifluoromethyl) quino-xaline-2-yl] benzene, TPQ), Triazole derivatives and triazine derivatives 8- ( 4 _ ( 4 _ (naphthalene _ 2 ᅵ yl)) 6 ᅵ (naphthalene _ 3 _yl) 3,5-triazine _ 2 _yl) phenyl) quinoline (8- ( 4 _ (4 ᅳ
(naphthalen-2-yl)-6-(naphthalen-3-yl)-l ,3,5-triazin-2-yl)phenyl)quinoline) 등이 사용될 수 있으나, 이에 한정되는 것은 아니다. (naphthalen-2-yl) -6- (naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline) may be used, but is not limited thereto.
또한, 전자수송층은 하기 화학식 C로 표시되는 유기 금속 화합물이 단독 또는 상기 전자수송층 재료와 흔합으로 사용될 수 있다. In addition, the electron transport layer may be an organometallic compound represented by the following general formula (C) alone or in combination with the electron transport layer material.
[화학식 c]
[Formula c]
상기 화학식 c에서， In Chemical Formula c,
Y는 C, N, 0 및 S에서 선택되는 어느 하나가 상기 M에 직접 결합되어 단일결합을 이루는 부분과, C, N, 0 및 S에서 선택되는 어느 하나가 상기 M에 배위결합을 이루는 부분을 포함하며, 상기 단일결합과 배위결합에 의해 킬레이트된 리간드이고, Y is a portion in which any one selected from C, N, 0 and S is directly bonded to M to form a single bond, and a portion selected from C, N, 0 and S forms a coordination bond to M. It includes, and is a ligand chelated by the single bond and the coordination bond,
상기 M은 알카리 금속, 알카리 토금속, 알루미늄 (A1) 또는 붕소 (B)원자이고, 상기 OA는 상기 M과 단일결합 또는 배위결합 가능한 1가의 리간드로서, M is an alkali metal, alkaline earth metal, aluminum (A1) or boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination with M,
상기 0는 산소이며, 0 is oxygen,
A는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 5 내지 50의 아릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 20의 알키닐기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기， 치환 또는 비치환된 탄소수 5 내지 30의 시클로알케닐기 및 치환 또는 비치환된 이종 원자로 Ο, Ν또는 S를 갖는 탄소수 2 내지 50의 A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 20 carbon atoms An alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and a substituted or unsubstituted hetero atom having 2 to 50 carbon atoms having Ο, Ν or S
헤테로아릴기 중에서 선택되는 어느 하나이고, Any one selected from heteroaryl groups,
상기 Μ이 알카리 금속에서 선택되는 하나의 금속인 경우에는 m-l, n=0이고， 상기 M이 알카리 토금속에서 선택되는 하나의 금속인 경우에는 m=l , n=l이거나, 또는 m=2, n=0이고, When Μ is one metal selected from alkali metals, ml, n = 0, and when m is one metal selected from alkaline earth metals, m = l, n = l, or m = 2, n = 0,
상기 M이 붕소 또는 알루미늄인 경우에는 m = l 내지 3중 어느 하나이며 , η은 0 내지 2 중 어느 하나로서 m +n-3을 만족하며; When M is boron or aluminum, any one of m = l to 3, and η satisfies m + n-3 as any one of 0 to 2;
상기 '치환 또는 비치환된'에서의 '치환 '은 중수소, 시아노기, 할로겐기,
히드록시기, 니트로기 , 알킬기, 알콕시기， 알킬아미노기， 아릴아미노기, 헤테로 아릴아미노기, 알킬실릴기, 아릴실릴기, 아릴옥시기， 아릴기, 헤테로아릴기， 게르마늄, 인 및 보론으로 이루어진 군에서 선택된 1개 이상의 치환기로 치환되는 것을 의미한다. The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, 1 selected from the group consisting of hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron It means to be substituted with more than one substituent.
본 발명에서 Y는 각각 동일하거나 상이하며, 서로 독립적으로 하기 화학식 cl 내지 화학식 c39 로부터 선택되는 어느 하나일 수 있으나 > 이에 한정된 것은 아니다. And in the present invention, Y may be the same or different and each independently from each other, but to be any one selected from the formula cl) through (c39> not limited thereto.
[화학식 cl [화학식 c2] [화학식 c3] [화학식 c4] [화학식 c5] [Formula cl [Formula c2] [Formula c3] [Formula c4] [Formula c5]
[ c6] [화학식 c7] [화학식 c8] [화학식 c9] [화학식 clO] [c6] [Formula c7] [Formula c8] [Formula c9] [Formula clO]
[화학식 cl l] [화학식 cl2] [화학식 cl3] [화학식 cl4] [화학식 cl5] [Formula cl l] [Formula cl2] [Formula cl3] [Formula cl4] [Formula cl5]
[화학식 c21] [화학식 c22] [화학식 c23] [화학식 c24] [화학식 c25]
[Formula c21] [Formula c22] [Formula c23] [Formula c24] [Formula c25]
[화학식 c31] [화학식 c32] [화학식 c33] [화학식 c34] [화학식 c35]
[화학식 c36] [화학식 c37] [화학식 c38] [화학식 c39] [Formula c31] [Formula c32] [Formula c33] [Formula c34] [Formula c35] [Formula c36] [Formula c37] [Formula c38] [Formula c39]
상기 화학식 cl 내지 화학식 c39에서, In Chemical Formula cl to Chemical Formula c39,
R은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기， 치환 또는.비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 헤테로아릴기， 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 '또는 비치환된 C1 내지 C30 알킬아미노기, 치환 또는 비치환된 C1 내지 C30 알킬실릴기, 치환 또는 비치환된 C6 내지 C30 아릴아미노기 및 치환 또는 비치환된 C6 내지 C30 아릴실릴기 중에서 선택되고, 인접한 치환체와 알킬렌 또는 알케닐렌으로 연결되어 스피로고리 또는 융합고리를 형성할 수 있다. R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 Heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted 'or unsubstituted C1 to C30 alkylamino group, substituted Or an unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C6 to C30 arylamino group, and a substituted or unsubstituted C6 to C30 arylsilyl group, and are connected to adjacent substituents with alkylene or alkenylene to form a styro ring Alternatively, the fused ring may be formed.
발광층 (32)은 발광 기능을 갖는 유기층으로서, 도핑 시스템올 채용하는 경우, 호스트와 도편트를 포함하고 있다. 이때, 호스트는, 주로 전자와 정공의 재결합을 촉진하고, 여기자를 발광층 내에 가두는 기능을 가지며, 도펀트는, 재결합으로 얻어진 여기자를 효율적으로 발광시키는 기능을 갖는다. The light emitting layer 32 is an organic layer having a light emitting function. When the doping system is employed, the light emitting layer 32 includes a host and a dopant. At this time, the host mainly has a function of promoting recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant has a function of efficiently emitting excitons obtained by recombination.
발광층은 공지의 호스트 및 도편트를 포함할 수 있다. The light emitting layer can include known hosts and dopants.
공지의 호스트로는 예컨대, Alq3, CBP(4,4'-N,N'-디카바졸 -비페닐)， PVK (폴리 (n- 비닐카바졸)) , 9,10-디 (나프탈렌 -2-일)안트라센 (ADN), TCTA, TPBI(1,3,5-트리스 (N- 페닐벤즈이미다졸 -2-일)벤젠 (l,3,5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN(3- tert-부틸 -9,10-디 (나프트 -2-일) 안트라센), mCP, OXD-7 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.
OXD-7Known hosts include, for example, Alq3, CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole)), 9,10-di (naphthalene-2- Yl) anthracene (ADN), TCTA, TPBI (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (l, 3,5-tris (N-phenylbenzimidazole-2-yl) benzene) ), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene), mCP, OXD-7 and the like can be used, but is not limited thereto. OXD-7
상기 도편트는 형광 도편트 및 인광 도편트 중 적어도 하나일 수 있다. 상기 인광 도편트는,1]",1^03,1 , , ,1 또는 이들 중 2 이상의 조합을 포함한 유기 금속 착체일 수 있으나, 이에 한정되는 것은 아니다. The dopant may be at least one of a fluorescent dopant and a phosphorescent dopant. The phosphorescent dopant may be an organometallic complex including 1] ", 1 ^ 03,1,,, 1 or a combination of two or more thereof, but is not limited thereto.
공지된 청색 도편트의 예로는, F2Irpic, (F2ppy)2Ir(tmd), Ir(dfppz)3, ter- 플투오렌 (fluorene), 4,4'-비스 (4-디페닐아미노스티릴) 비페닐 (DPAVBi), 2,5,8,11-테트라- tert-부틸 페릴렌 (TBPe), DPVBi, 피렌 유도체 (KR0525408, 엘지전자 주식회사) 등을 들 수 있으나, 이.에 한정되는 것은 아니다. Examples of known blue dopants include F 2 Irpic, (F 2 ppy) 2 Ir (tmd), Ir (dfppz) 3 , ter-fluorene, 4,4′-bis (4-diphenylamino Styryl) biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butyl perylene (TBPe), DPVBi, pyrene derivatives (KR0525408, LG Electronics Co., Ltd.) and the like, but are not limited thereto. It is not.
lr(dfppz)3 lr (dfppz) 3
공지된 적색 도펀트의 예로는, PtOEP,Ir(piq)3,BtpIr등을 들 수 있으나, 이에 한정되는 것은 아니다. Examples of known red dopants include, but are not limited to, PtOEP, Ir (piq) 3 , BtpIr, and the like.
공지된 녹색 도편트의 예로는， Ir(ppy)3(ppy= 페닐피리딘)， Ir(ppy)2(acac), Ir(mpyp)3 등을 들 수 있으나, 이에 한정되는 것은 아니다. Examples of known green dopants include, but are not limited to, Ir (ppy) 3 (ppy = phenylpyridine), Ir (ppy) 2 (acac), Ir (mpyp) 3 , and the like.
3 lr(pPV)2(acac) lr(mpyp)3 3 lr (pPV) 2 (acac) lr (mpyp) 3
상기 발광층이 호스트 및 도편트를 포함하는 경우, 도펀트의 함량은 통상적으로 발광층 100중량0 /0 당 약 0.01 내지 약 15 중량0 /。의 범위에서 선택될 수 있으나, 이에 한정되는 것은 아니다. If said light emitting layer comprises a host and dopyeon agent, the content of the dopant is typically may be selected from the range of the light-emitting layer 100 weight 0/0 of about 0.01 to about 15 parts by weight 0 / per., And the like.
상기 발광층의 두께는 약 200 A 내지 약 700 A이다. The light emitting layer has a thickness of about 200 A to about 700 A.
전자수송보조층 (35)은 전자 특성이 상대적으로 강한 특성을 가지는 겨 U 화합물과 정공 특성이 상대적으로 강한 특성을 가지는 제 2 화합물을 포함한다.
상기 제 1 화합물은 전자 특성이 상대적으로 강한 특성을 가지는 화합물로, 하기 화학식 1로 표현될 수 있다ᅳ The electron transport auxiliary layer 35 includes a chaff U compound having relatively strong electronic properties and a second compound having relatively strong hole properties. The first compound is a compound having relatively strong electronic properties, and may be represented by the following Chemical Formula 1.
[화학식 1] [Formula 1]
상기 화학식 1에서, In Chemical Formula 1,
Z는 각각 독립적으로 N,C 또는 CRa이고, Z are each independently N, C or CR a ,
Z 중 적어도 하나는 N 이고, At least one of Z is N,
R1 내지 R10 및 Ra는 각각 독립적으로 수소， 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C12 아릴기 또는 이들의 조합이고, L1은 치환 또는 비치환된 페닐렌기, 치환 또는 비치환된 바이페닐렌기 또는 치환 또는 비치환된 터페닐렌기이고, R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof, and L 1 is substituted or unsubstituted A phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
nl 내지 n3는 각각 독립적으로 0 또는 1이고, nl+n2+n3≥l 이다. nl to n3 are each independently 0 or 1, and nl + n2 + n3 ≧ l.
상기 제 1 화합물은 트리페닐렌기의 결합 위치에 따라 예컨대 하기 화학식 1- I 또는 화학식 l - Π로 표현될 수 있다. The first compound may be represented by, for example, the following Chemical Formula 1-I or Chemical Formula l-Π depending on the bonding position of the triphenylene group.
1-1] [화학식 1- Π ] 1-1] [Formula 1- Π]
상기 화학식 1-1 또는 1- Π에서， Ζ, Ι 1 내지 R^ L1 및 nl 내지 n3는 전술한 바와 같다. In Formula 1-1 or 1--, Ζ, Ι 1 to R ^ L 1 and nl to n3 are as described above.
상기 제 1 화합물은 트리페닐렌기와 적어도 하나의 질소원자를 함유하는 헤테로아릴기를 포함한다. 상기 제 1 화합물은 적어도 하나의 질소를 함유하는 고리를 포함함으로써 전기장 인가 시 전자를 받기 쉬운 구조가 되어 전자 주입량0 증가될 수 있고, 이에 따라 상기 게 1 화합물을 적용한 유기 광전자 소자의 구동
전압을 낮출 수 있고, 또한 효율을 개선할 수 있다. The first compound includes a triarylene group and a heteroaryl group containing at least one nitrogen atom. Since the first compound includes a ring containing at least one nitrogen, the first compound has a structure in which electrons are easily received when an electric field is applied, and thus an electron injection amount can be increased by 0. Accordingly, the organic optoelectronic device to which the first compound is applied is driven. The voltage can be lowered and the efficiency can also be improved.
상기 화학식 1로 표현되는 제 1 화합물은 아릴렌기 및 /또는 헤테로아릴렌기를 중심으로 적어도 하나의 꺾임 (kink) 구조를 가진다. The first compound represented by Chemical Formula 1 has at least one kink structure around an arylene group and / or a heteroarylene group.
상기 꺾임 구조는 아릴렌기 및 /또는 해테로아릴렌기의 두 개의 연결 부분들이 직선 구조를 이루지 않는 구조를 말한다. 예컨대 페닐렌의 경우 연결 부분들이 직선 구조를 이루지 않는 올쏘 페닐렌 (o-phenylene)과 메타 페닐렌 (m- phenylene)이 상기 꺾임 구조를 가지며, 연결 부분들이 직선 구조를 이루는 파라 페닐렌 (p-phenylene)은 상기 꺾임 구조를 가지지 않는다. The fold structure refers to a structure in which two connecting portions of the arylene group and / or the heteroarylene group do not form a straight structure. For example, in the case of phenylene, para-phenylene (p-) in which o-phenylene and meta phenylene in which the linking portions do not form a straight structure has the bending structure, and the linking portions form a straight structure. phenylene) does not have this bending structure.
상기 화학식 1에서, 상기 꺾임 구조는 연결기 (L1) 및 /또는 In Formula 1, the bending structure is a linking group (L 1 ) and / or
아릴렌기 /헤테로아릴렌기를 중심으로 형성될 수 있다. It may be formed around the arylene group / hetero arylene group.
예컨대 상기 화학식 1의 nl이 0인 경우, 즉 연결기 (L1)가 없는 구조에서는 아릴렌기 /헤테로아릴렌기를 중심으로 꺾임 구조를 형성할 수 있고, 예컨대 하기 화학식 la또는 lb로 표현되는 화합물일 수 있다. For example, when nl of Formula 1 is 0, that is, in a structure without a linking group (L 1 ), a fold structure can be formed around an arylene group / heteroarylene group, for example, a compound represented by the following formula la or lb have.
[화학식 la] [화학식 lb] [Formula la] [Formula lb]
상기 화학식 la또는 lb에서 , Z, R' 내지 R10 은 전술한 바와 같다. In the formula la or lb, Z, R 'to R 10 are as described above.
예컨대 상기 화학식 1의 nl이 1인 경우에는 연결기 (L1)를 중심으로 꺾임 구조를 형성할 수 있고, 예컨대 L1은 꺾임 구조의 치환 또는 비치환된 페닐렌기, 꺾임 구조의 치환 또는 비치환된 바이페닐렌기 또는 꺾임 구조의 치환 또는 비치환된 터페닐렌기일 수 있다. For example, when nl of Formula 1 is 1, a folding structure may be formed around the linking group (L 1 ), and for example, L 1 may be a substituted or unsubstituted phenylene group having a folding structure, or a substituted or unsubstituted structure. It may be a biphenylene group or a substituted or unsubstituted terphenylene group having a folding structure.
상기 L1은 예컨대 단일결합이거나 하기 그룹 1에 나열된 치환 또는 비치환된 기에서 선택된 하나일 수 있다.
[그룹 i] L 1 may be, for example, a single bond or one selected from substituted or unsubstituted groups listed in Group 1 below. [Group i]
상기 그룹 1에서, In group 1 above,
*은 연결 지점이고, * Is the junction point,
여기서， "치환"은 적어도 하나의 수소가 중수소, 할로겐, C1 내지 C20 알킬기, Here, "substituted" means that at least one hydrogen is deuterium, halogen, C1 to C20 alkyl group,
C3 내지 C20 시클로알킬기, C1 내지 C20 알콕시기, C3 내지 C20 시클로알콕시기, C1 내지 C20 알킬티오기, C6 내지 C30 아르알킬기， C6 내지 C30 아릴기, C6 내지 C30 아릴옥시기, C6 내지 C30 아릴티오기, C2 내지 C30 헤테로아릴기， C2 내지 C30 아미노기, C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실기 또는 카르복실기로 치환된 것을 의미한다. C3 to C20 cycloalkyl group, C1 to C20 alkoxy group, C3 to C20 cycloalkoxy group, C1 to C20 alkylthio group, C6 to C30 aralkyl group, C6 to C30 aryl group, C6 to C30 aryloxy group, C6 to C30 arylti Or a C2 to C30 heteroaryl group, a C2 to C30 amino group, a C3 to C30 silyl group, a cyano group, a nitro group, a hydroxyl group, or a carboxyl group.
상기 거 1 1 화합물은 바람직하게는 적어도 두 개의 꺾임 구조를 가질 수 있으며, 예컨대 두 개 내지 네 개의 꺾임 구조를 가질 수 있다. The compound 11 may preferably have at least two folding structures, for example, may have two to four folding structures.
상기 제 1 화합물은 전술한 찍임 구조를 가짐으로써 전하를 적절히 The first compound has the above-described imaging structure to properly charge
구역화 (localization)하고 공액계의 흐름을 효과적으로 제어함으로써 상기 조성물을 적용한 유기 광전자 소자의 효율을 개선할 수 있다. By localizing and effectively controlling the flow of the conjugated system, the efficiency of the organic optoelectronic device to which the composition is applied can be improved.
상기 게 1 화합물은 예컨대 하기 화학식 lc 내지 It 중 어느 하나로 표현될 수 있다.
[화학식 Is] [화학식 it] The compound 1 may be represented by, for example, any one of Formulas lc to It. [Formula Is] [Formula it]
상기 화학식 ic 내지 it에서 In the above formulas ic to it
Z 및 R1 내지 R10는 각각 전술한 바와 같고， Z and R 1 to R 10 are the same as described above,
R60 내지 R77 은 각각 독립적으로 수소, 중수소， 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 ''내지 C30 헤테로아릴기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C6 내지 C30 R 60 to R 77 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 '' to C30 heteroaryl group, substituted or unsubstituted amine group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C6 to C30
헤테로아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 할로겐기, 할로겐 함유기, 시아노기, 히드록실기, 아미노기, 니트로기, 카르복실기， 페로세닐기 또는 이들의 조합이다. Heteroarylamine groups, substituted or unsubstituted C1 to C30 alkoxy groups, halogen groups, halogen-containing groups, cyano groups, hydroxyl groups, amino groups, nitro groups, carboxyl groups, ferrocenyl groups or combinations thereof.
상기 제 1 화합물은 예컨대 하기 그룹 2에 나열된 화합물일 수 있으나, 이에 한정되는 것은 아니다. The first compound may be, for example, a compound listed in Group 2, but is not limited thereto.
" [그룹 2] "[Group 2]
상기 제 1 화합물은 1종 또는 2종 이상이 사용될 수 있다ᅳ 상기 제 2 화합물은 예컨대 하기 화학식 2로 표현될 수 있다
2] One or two or more kinds of the first compound may be used. The second compound may be represented by the following Chemical Formula 2 , for example. 2]
상기 화학식 2에서, In Chemical Formula 2,
Y1 및 Y2는 각각 독립적으로, 단일 결합， 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기 또는 이들의 조합이고,Y 1 and Y 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
Arla 및 Arlb은 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기 또는 이들의 조합이고, Ar la and Ar lb are substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or a combination thereof,
R1 1 내지 R16는 각각 독립적으로 수소， 중수소, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C50 아릴기, 치환 또는 비치환된 C2 내지 C50 헤테로아릴기 또는 이들의 조합이다. R 1 1 to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or a combination thereof to be.
상기 화학식 2로 표현되는 화합물은 정공 특성이 상대적으로 강한 특성을 가지는 화합물로, 상기 게 1 화합물과 함께 전자수송보조층에 포함되어， 제 1 화합물의 전자 주입량을 조정할 수 있으며, 발광층과 전자수송보조층 계면에서 정공의 축적을 방지하여 소자의 안정성을 높일 수 있다. 따라서 유기 광전자 소자의 발광 효율 및 수명 특성을 현저히 개선시킬 수 있다. Compound represented by the formula (2) is a compound having a relatively strong hole characteristics, it is included in the electron transport auxiliary layer with the C1 compound, the electron injection amount of the first compound can be adjusted, the light emitting layer and the electron transport auxiliary The stability of the device can be improved by preventing the accumulation of holes at the layer interface. Therefore, the luminous efficiency and lifespan characteristics of the organic optoelectronic device can be significantly improved.
상기 제 2 화합물은 바이카바졸의 결합 위치에 따라 예컨대 하기 화학식 2- 1 내지 화학식 2-观 중 적어도 하나로 표현될 수 있다. The second compound may be represented by at least one of, for example, the following Chemical Formula 2- 1 to Chemical Formula 2-VII, depending on the binding position of bicarbazole.
[화학식 2- 1 ] [화학식 2- Π ] [Formula 2- 1] [Formula 2- Π]
[ - VI] [화학식 2-VD] [화학식 2-VI] [-VI] [Formula 2-VD] [Formula 2-VI]
상기 화학식 2- 1 내지 2-環에서, In the above formula 2- 1 to 2- 環,
Y1 및 Y2, Arla 및 Arlb, R" 내지 R16는 각각 전술한 바와 같다. Y 1 and Y 2 , Ar la and Ar lb , R ″ to R 16 are the same as described above.
상기 제 2 화합물은 치환기를 가진 두 개의 카바졸일기가 연결되어 있는 구조이다. The second compound has a structure in which two carbazolyl groups having a substituent are connected.
상기 제 2 화합물의 Arl a 및 Arlb는 정공 또는 전자 특성을 가지는 치환기로， 각각 독립적으로 예컨대 치환 또는 비치환된 페닐기, 치환 또는 비치환된 Ar la and Ar lb of the second compound is a substituent having a hole or electronic properties, each independently a substituted or unsubstituted phenyl group, substituted or unsubstituted
바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환또는 비치환된 안트라세닐기, 치환 또는 비치환된 카바졸일기, 치환 또는 비치환된 벤조퓨라닐기, 치환 또는 비치환된 벤조티오페닐기, 치환 또는 비치환된 Biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted Benzothiophenyl group, substituted or unsubstituted
플투오레닐기, 치환 또는 비치환된 피리딜기, 치환 또는 비치환된 피리미디닐기, 치환 또는 비치환된 피라지닐기, 치환 또는 비치환된 트리아지닐기, 치환 또는 비치환된 트리페닐렌기, 치환 또는 비치환된 디벤조퓨란일기, 치환 또는 비치환된 디벤조티오펜일기, 또는 이들의 조합일 수 있다. Fluorenyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted triphenylene group, substituted or Unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.
상기 제 2 화합물은 Arla 및 Arlb의 특성에 따라 예컨대 하기 화학식 2-K 내지 화학식 2- X I 중 적어도 하나로 표현될 수 있다.
2-K] [화학식 2- Χ ] [화학식 2- Χ Ι ] The second compound may be represented by at least one of Formula 2-K to Formula 2-XI according to the properties of Ar la and Ar lb , for example. 2-K] [Formula 2- Χ] [Formula 2- Χ Ι]
상기 화학식 2-Κ 내지 2- Χ I에서 In Chemical Formulas 2-Κ to 2-Χ I
Υ1 및 Υ2, 그리고 R11 내지 R16는 전술한 바와 같고, X 1 and X 2 , and R 11 to R 16 are as described above,
ET, ET1, 및 ΕΤ2는 각각 독립적으로 전자 특성을 가지는 치환기이고, ΗΤ, ΗΤΙ 및 ΗΤ2는 각각 독립적으로 정공 특성을 가지는 치환기이다. 상기 제 2 화합물의 Arla 및 Arlb 중 전자 특성을 가지는 치환기 ΈΓ', ΤΓ 및 ΈΤ2' '는 예컨대 하기 화학식 Α로 표현되는 치환기일 수 있다. ET, ET1, and ΕΤ2 are each independently a substituent having electronic properties, and ΗΤ, ΗΤΙ and ΗΤ2 are each independently substituents having hole characteristics. Substituents? Γ ', ΤΓ, and? Τ2''having electronic properties among Ar la and Ar lb of the second compound may be, for example, substituents represented by the following Chemical Formula A.
[화학식 A] [Formula A]
상기 화학식 A에서， In Chemical Formula A,
Z는 각각 독립적으로 N 또는 CRk 이고， Z are each independently N or CR k ,
A1 및 A2, 및 Rk는 각각 독립적으로 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기 또는 이들의 조합이고, 상기 Ζ, ΑΙ 및 Α2 중 적어도 하나는 Ν을 포함하고, A1 and A2, and R k are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and at least one of X, A, and A2 is N Including,
a 및 b는 각각 독립적으로 0 또는 1이다. a and b are each independently 0 or 1.
상기 화학식 A로 표현되는 치환기는 예컨대 하기 그룹 3에 나열된 작용기 중 하나일 수 있다.
[그룹 3] The substituent represented by Formula A may be, for example, one of the functional groups listed in Group 3 below. [Group 3]
또한, 상기 제 2 화합물의 Arla및 Arlb 중 정공 특성을 가지는 치환기 'ΉΓ' 'ΉΤΓ 및 "ΗΤ2 "는 예컨대 하기 그룹 4에 나열된 작용기 중 하나일 수 있다.Further, the substituents' ΉΓ '' ΉΤΓ and “ΗΤ2” having hole characteristics among Ar la and Ar lb of the second compound may be, for example, one of the functional groups listed in Group 4 below.
그룹 4] Group 4]
β'Ί;12 β-113 β'Ί; 12 β-113
상기 제 2 화합물은 1종 또는 2종 이상이 사용될 수 있다. One kind or two or more kinds of the second compound may be used.
본 발명의 일 구현예에 따른 전자수송보조층은 전자 특성이 강한 거 11 화합물과 정공 특성이 강한 제 2 화합물을 동시에 포함할 수 있다. The electron transport auxiliary layer according to the exemplary embodiment of the present invention may simultaneously include a compound 11 having strong electronic properties and a second compound having strong hole properties.
화학식 1로 표현되는 적어도 1종의 제 1 화합물과 화학식 2로 표현되는 적어도 1종의 게 2 화합물을 함께 사용함으로써, 소자의 효율 및 수명을 개선시킬 수 있다. By using at least one first compound represented by the formula (1) and at least one crab compound represented by the formula (2) together, the efficiency and lifetime of the device can be improved.
구체적으로, 화학식 1- 1 또는 화학식 1-Π로 표현되는 제 1 화합물과 화학식 2-1 내지 화학식 2-X I로 표현되는 제 2 화합물 중 적어도 하나를 함께 사용할 수 있다. Specifically, at least one of the first compound represented by Formula 1-1 or Formula 1-Π and the second compound represented by Formulas 2-1 to 2-X I may be used together.
더욱 구체적으로, 화학식 lc 내지 it로 표현되는 제 1 화합물 중 적어도 하나와 화학식 2-IX 내지 화학식 2-Χ I로 표현되는 제 2 화합물 중 적어도 하나를 함께 사용할 수 있다. More specifically, at least one of the first compounds represented by formulas lc to it and at least one of the second compounds represented by formulas 2-IX to 2- 2-I may be used together.
더욱 구체적으로, 화학식 lc, Id, lg, 및 lh로 표현되는 게 1 화합물 중 적어도 하나와 화학식 2-K 내지 화학식 2-X I로 표현되는 제 2 화합물 중 적어도 하나를 함께 사용할 수 있다ᅳ More specifically, at least one of the compound 1 represented by formulas lc, Id, lg, and lh and at least one of the second compound represented by formulas 2-K to 2-X I may be used together.
예컨대， 화학식 lh로 표현되는 제 1 화합물과 화학식 2-X I로 표현되는 제 2 화합물을 함께 사용할 수 있다. For example, the first compound represented by Chemical Formula lh and the second compound represented by Chemical Formula 2-X I may be used together.
전자수송보조층 (35)에서 상기 제 1 화합물과 상기 게 2 화합물은, 예컨대 약 1:99 내지 99:1의 중량비로 포함될 수 있다. 구체적으로, 10:90 내지 90:10,20:80 내지 80:20,30:70 내지 70:30, 그리고 40:60 내지 60:40, 가장 구체적으로, 50:50의 중량비로 포함될 수 있다. In the electron transport auxiliary layer 35, the first compound and the crab 2 compound may be included, for example, in a weight ratio of about 1:99 to 99: 1. Specifically, it may be included in a weight ratio of 10:90 to 90: 10,20: 80 to 80: 20,30: 70 to 70:30, and 40:60 to 60:40, most specifically, 50:50.
상기 범위로 포함됨으로써 상기 두 화합물의 비율에 따라서 전자 주입 능력을 조절할 수 있어, 발광층의 전자수송능력과 균형을 맞춤으로써 발광층의 계면에서 전자가 축적되는 것을 방지할 수 있다.
또한， 발광층으로부터 넘어온 정공 및 /또는 엑시톤이 전자수송보조층 (35)으로 인해 발광층의 엑시톤의 에너지보다 더 낮은 에너지의 엑시톤으로 변환됨으로써 정공 및 /또는 발광층의 액시톤이 전자수송층 (34)에 미치는 영향을 최소화할 수 있다. 정공수송보조층 (33)은 정공 수송 톡성이 좋은 제 3 화합물을 포함하고, 정공수송층 (3 1)과 발광층 (32) 사이의 HOMO 에너지 레벨 차이를 줄임으로써 정공의 주입 특성을 조절하여 정공수송보조층 (33)과 발광충 (32)의 계면에서 정공이 축적되는 것을 감소시켜 계면에서 폴라론 (polaron)에 의한 엑시톤이 소멸되는 소광 By being included in the above range it is possible to adjust the electron injection ability according to the ratio of the two compounds, it is possible to prevent the accumulation of electrons at the interface of the light emitting layer by balancing the electron transport capacity of the light emitting layer. In addition, holes and / or excitons from the light emitting layer are converted into excitons of lower energy than those of the excitons of the light emitting layer due to the electron transport auxiliary layer 35 so that the axtone of the holes and / or light emitting layers may affect the electron transport layer 34. The impact can be minimized. The hole transport auxiliary layer 33 includes a third compound having good hole transporting properties, and by adjusting the hole injection characteristics by reducing the HOMO energy level difference between the hole transport layer 31 and the light emitting layer 32, the hole transport auxiliary Extinction of extinction caused by polaron at the interface is reduced by reducing the accumulation of holes at the interface between the layer 33 and the light emitting insect 32
현상 (quenching)을 줄일 수 있다. 이에 따라 소자의 열화현상이 감소하고 소자가 안정화되어 효율 및 수명을 개선할 수 있다. The quenching can be reduced. Accordingly, deterioration of the device may be reduced and the device may be stabilized to improve efficiency and lifespan.
상기 제 3 화합물은 하기 화학식 3으로 표현되는 화합물일 수 있다. The third compound may be a compound represented by Formula 3 below.
상기 화학식 3에서, In Chemical Formula 3,
X1은 0 또는 S이고, X 1 is 0 or S,
R17 및 R18은 각각 독립적으로, 수소, 중수소， 할로겐, 치환 또는 비치환된 C1 내지 C20 알킬기， 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C 1 내지 C20 알콕시기， 치환 또는 비치환된 C3 내지 C20 시클로알콕시기, 치환 또는 비치환된 C 1 내지 C20 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C6 내지 C30 아릴티오기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기， 치환 또는 비치환된 C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실기 또는 카르복실기, 또는 이들의 조합이고, R 17 and R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C 1 to C20 alkoxy group, substituted Or an unsubstituted C3 to C20 cycloalkoxy group, a substituted or unsubstituted C 1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 Silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof,
Ar2 및 Ar3는 각각 독립적으로， 치환 또는 비치환된 C6 내지 C30 아릴기
또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴기이고， Ar 2 and Ar 3 are each independently a substituted or unsubstituted C6 to C30 aryl group Or a substituted or unsubstituted C2 to C30 heteroaryl group,
L2 내지 L4는 각각 독립적으로 단일결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 헤테로아릴렌기 또는 이들의 조합이고, L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
. n4 내지 n6은 각각 독립적으로, 0 내지 3 증 어느 하나인 정수이고, . n4 to n6 are each independently an integer of 0 to 3,
상기 제 3 화합물은 아민 치환기의 결합 위치에 따라 예컨대 하기 화학식 3- I 또는 화학식 3-Π로 표현될 수 있다. The third compound may be represented by, for example, the following Formula 3-I or Formula 3-Π depending on the bonding position of the amine substituent.
[화학식 3-1] [화학식 3-Π [Formula 3-1] [Formula 3-Π
상기 화학식 3-1 및 화학식 ^！！에서,：^1,!^7,!^,^2, ^3,! 내지 L4, 및 n4 내지 n6는 전술한 바와 같다. In the above Chemical Formula 3-1 and Chemical Formula ^ ！！,: ^ 1 ,! ^ 7 ,! ^, ^ 2 , ^ 3 ,! To L 4 , and n4 to n6 are as described above.
상기 제 3 화합물은 예컨대 하기 화학식 3-m내지 화학식 3-K중 적어도 하나일 수 있다. The third compound may be, for example, at least one of Formula 3-m to Formula 3-K.
[화학식 3-m] [화학식 3-IV][화학식 3-V] [Formula 3-m] [Formula 3-IV] [Formula 3-V]
상기 화학식 3-ΠΙ 내지 화학식 3-K에서, Χ', Ι 17 및 R18, L2 내지 L4, 및 η4 내지 n6는 전술한 바와 같고, In the above Formula 3-ΠΙ to Formula 3-K, Χ ', Ι 17 and R 18 , L 2 to L 4 , and η4 to n6 are as described above,
X2는 0, S, 또는 CRcRd이고, X 2 is 0, S, or CR c R d ,
X3은 각각 독립적으로 0 또는 S이고, X 3 are each independently 0 or S,
R19 내지 R27, RC, 및 Rd 각각 독립적으로, 수소, 중수소, 할로겐, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C1 내지 C20 알콕시기， 치환 또는 비치환된 C3 내지 C20 시클로알콕시기, 치환 또는 비치환된 C1 내지 C20 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C6 내지 C30 아릴티오기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C1 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실기 또는 카르복실기, 또는 이들의 조합이고, R 19 to R 27 , R C , and R d are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof,
Ar2 및 Ar3는 구체적으로, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 쿼터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 안트라세닐기, 치환 또는 비치환된
페난트렌일기, 치환 또는 비치환된 피렌일기 (pyrenyl), 치환 또는 비치환된 트리페닐렌기, 치환 또는 비치환된 플루오레닐기, 치환 또는 비치환된 피리디닐기 치환 또는 비치환된 피리미디닐기, 치환 또는 비치환된 트리아지닐기, 치환 또는 비치환된 카바졸일기, 치환 또는 비치환된 디벤조퓨라닐기, 치환 또는 비치환된 디벤조티오페닐기, 또는 이들의 조합일 수 있고, Ar 2 and Ar 3 are specifically, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or Unsubstituted anthracenyl group, substituted or unsubstituted Phenanthrenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted pyridinyl groups substituted or unsubstituted pyrimidinyl groups, Substituted or unsubstituted triazinyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,
더욱 구체적으로, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 쿼터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 안트라세닐기, 치환 또는 비치환된 페난트렌일기, 치환 또는 비치환된 피렌일기 (pyrenyl), 치환 또는 비치환된 트리페닐렌기, 치환 또는 비치환된 플루오레닐기, 치환 또는 비치환된 More specifically, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl Groups, substituted or unsubstituted phenanthrenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted groups
디벤조퓨라닐기， 치환 또는 비치환된 디벤조티오페닐기 s 또는 이들의 조합일 수 있다. Dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group s, or a combination thereof.
예컨대, 하기 그룹 6에 나열된 작용기 중 하나일 수 있다. For example, it may be one of the functional groups listed in group 6 below.
[그룹 6] [Group 6]
Y는 0, S, CRfRg, SiRhRi 또는 NRj이고, Y is 0, S, CR f R g , SiR h R i or NR j ,
*은' 연결 지점이고, * Is a "connection point,
Re 내지 Rj는 각각 독립적으로, 수소, 중수소， 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아르알킬기， 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 또는 이들의 조합이고, R e to R j are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted A C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group, or a combination thereof,
여기서 "치환''은 적어도 하나의 수소가 중수소, 할로겐기, 히드톡시기, 아미노기, 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기, C2 내지 C30 헤테로시클로알킬기， C6 내지 C30 아릴기, C2 내지 C30 해테로아릴기, C1 내지 C20 알콕시기, 플루오로기, C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. Wherein “substituted” means that at least one hydrogen is deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, C1 to C30 Alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group or cyano group It means substituted.
상기 제 3 화합물은 예컨대 하기 그룹 7에 나열된 화합물에서 선택될 수 있으나, 이에 한정되는 것은 아니다. The third compound may be selected from, for example, a compound listed in Group 7, but is not limited thereto.
[그룹 7] [Group 7]
이들을 함께 사용함으로써, 정공수송보조층의 정공 주입 조절 능력과 전자수송보조층의 전자 주입 조절 능력을 통해 전하 밸런스를 조정하여 효율을 개선시킬 수 있으며, 정공수송보조층과 전자수송보조층을 적용해 유기층의 각 계면에서 전하가 축적되는 것을 방지하여 소자의 열화현상이 감소하고, 소자가 안정화되어 수명을 개선시킬 수 있다. By using them together, efficiency can be improved by adjusting the charge balance through the hole injection control ability of the hole transport auxiliary layer and the electron injection control ability of the electron transport auxiliary layer, and by applying the hole transport auxiliary layer and the electron transport auxiliary layer, By preventing charge from accumulating at each interface of the organic layer, deterioration of the device can be reduced, and the device can be stabilized to improve life.
구체적으로, 화학식 1- 1 또는 화학식 l- Π로 표현되는 제 1 화합물과 화학식 Specifically, the first compound and the formula represented by the formula 1-1 or formula l- Π
2- 1 내지 화학식 2- X I로 표현되는 제 2 화합물 중 적어도 하나, 그리고 화학식 3- 1 내지 화학식 3-K로 표현되는 제 3 화합물을 함께 사용할 수 있다. At least one of the second compounds represented by 2- 1 to formula 2-X I, and the third compound represented by formula 3- 1 to formula 3-K can be used together.
더욱 구체적으로, 화학식 lc 내지 u로 표현되는 제 1 화합물 중 적어도 하나, 화학식 2-K 내지 화학식 2- X I로 표현되는 제 2 화합물 중 적어도 하나, 그리고 화학식 3-ΠΙ 내지 화학식 3-K로 표현되는 제 3 화합물을 함께 사용할 수 있다. More specifically, at least one of the first compounds represented by formulas lc to u, at least one of the second compounds represented by formulas 2-K to 2-XI, and represented by formulas 3-ΠΙ to 3-K The third compound can be used together.
더욱 구체적으로, 화학식 lc, Id, lg, 및 lh로 표현되는 제 1 화합물 증 적어도 ᅳ하나, 화학식 2-K 내지 화학식 2- X I로 표현되는 게 2 화합물 중 적어도 하나, 그리고 화학식 3-VH, 화학식 3- ， 및 화학식 3-K로 표현되는 제 3 화합물을 함께 사용할 수 있다. More specifically, at least one of the first compounds represented by the formulas lc, Id, lg, and lh, at least one of the two compounds represented by the formulas 2-K to 2-XI, and the formula 3-VH, 3-, and the third compound represented by the formula 3-K can be used together.
예컨대, 화학식 lh로 표현되는 게 1 화합물, 화학식 2- X I로 표현되는 제 2 화합물, 그리고 화학식 3-W 및 화학식 3-VI로 표현되는 제 3 화합물을 함께 사용할 수 있다. For example, the first compound represented by the formula lh, the second compound represented by the formula 2-X I, and the third compound represented by the formula 3-W and the formula 3-VI may be used together.
정공수송보조층 (35)은 증착 또는 잉크젯 공정으로 0.1 nm 내지 2().0 nm의 두께로 정공수송층 위에 도포 가능하며, 예컨대 0.2 nm 내지 10.0 nm, 0.3 nm 내지 5 nm, 0.3 nm 내지 2 nm, 0.4 nm 내지 1,0 nm의 두께 둥으로 도포 가능하다. 유기층 (30)은 선택적으로 애노드 (10)와 정공수송층 (31) 사이에 위치하는 정공주입층 (도시하지 않음) 및 /또는 캐소드 (20)와 전자수송층 (34) 사이에 위치하는 전자주입층 (도시하지 않음)을 더 포함할 수 있다. The hole transport auxiliary layer 35 may be applied on the hole transport layer in a thickness of 0.1 nm to 2 (). 0 nm by a deposition or inkjet process, for example, 0.2 nm to 10.0 nm, 0.3 nm to 5 nm, 0.3 nm to 2 nm. , 0.4 nm to 1,0 nm in thickness can be applied. The organic layer 30 may optionally include a hole injection layer (not shown) located between the anode 10 and the hole transport layer 31 and / or an electron injection layer located between the cathode 20 and the electron transport layer 34 ( Not shown).
상술한 유기 발광 소자는 유기 발광 표시 장치에 적용될 수 있다.
【발명의 실시를 위한 형태】 The organic light emitting diode described above may be applied to an organic light emitting diode display. [Form for implementation of invention]
이하에서는 본 발명의 구체적인 실시예들을 제시한다. 다만, 하기에 기재된 실시예들은 본 발명을 구체적으로 예시하거나 설명하기 위한 것에 불과하며, 이로서 본 발명이 제한되어서는 아니된다. 제 1 화합물의 합성 The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto. Synthesis of First Compound
합성예 1: 중간체 Ϊ-1의 합성 Synthesis Example 1 Synthesis of Intermediate VIII-1
[반웅식 1]
질소 환경에서 2-브로모트리페닐렌(2- 0010 }?1^ 1∞^71：1)100§(3261«1^1)을 디메틸포름아미드((1^^1^1"01"0^11^6,0 )11 ᅵᅵ 녹인 후, 여기에 [Banungsik 1] In a nitrogen environment, 2-bromotriphenylene (2- 0010}? 1 ^ 1∞ ^ 71: 1) 100§ (3261 «1 ^ 1) was converted to dimethylformamide ((1 ^^ 1 ^ 1 " 01 " 0 ^ 11 ^ 6,0) 11 ᅵ ᅵ After melting
비스 (피나콜라토)디보론 (bis(pinacolato)diboron, Aldrich) 99.2 g (391 mmol)와 (Ι,Γ- 비스 (디페닐포스핀)디클로로팔라듐 (II)((U'-bis(diphenylphosphme) 99.2 g (391 mmol) of bis (pinacolato) diboron (Aldrich) and (Ι, Γ- bis (diphenylphosphine) dichloropalladium (II) ((U'-bis (diphenylphosphme)
ferrocene)dichloropalladium(II)) 2.66 g (3.26 mmol) 그리고 포타슴아세테이트 (potassium acetate) 80 g (815 mmol)을 넣고 150 °C에서 5시간 동안 가열하여 환류시켰다. 반웅 완료 후 반응액에 물을 넣고 흔합물을 필터한 후， 진공오븐에서 건조하였다. 이렇게 얻어진 잔사를 컬럼 크로마토그래피 (flash column chromatography)로 분리 정제하여 화합물 1-1113g(98%)을 얻었다. 2.66 g (3.26 mmol) of ferrocene) dichloropalladium (II)) and 80 g (815 mmol) of potassium acetate were added and refluxed at 150 ° C. for 5 hours. After completion of reaction, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining a compound 1-1113 g (98%).
HRMS (70 eV, EI+): m/z calcd for C24H23B02: 354.1791, found: 354 HRMS (70 eV, EI +): m / z calcd for C24H23B02: 354.1791, found: 354
Elemental Analysis: C, 81 %; H, 7 % 합성예 2: 중간체 1-2의 합성 Elemental Analysis: C, 81%; H, 7% Synthesis Example 2 Synthesis of Intermediate 1-2
반응식 2] Scheme 2]
질소 환경에서 2-브로모트리페닐렌 (2-bromotriphenylene, TCI)32.7g(107
mmol)을 테트라하이드로퓨란 (tetrahydrof ran, THF) 0.3 L에 녹인 후, 여기에 3- 클로로페닐보론산 (3-chlorophenyl boronic acid, TCI) (20 g, 128 mmol)와 32.7 g (107 bromotriphenylene, TCI) in a nitrogen environment mmol) was dissolved in 0.3 L of tetrahydrofuran (THF), followed by 3-chlorophenyl boronic acid (TCI) (20 g, 128 mmol).
테트라키스 (트리페닐포스핀)팔라듐 (tetrakis(tdphenylphosphine)palladium) 1.23 g (1.07 mmol)을 넣고 교반시켰다. 물에 포화된 포타슴카보네이트 36.8 g (267 mmol)을 넣고 80 °C에서 24시간 동안 가열하여 환류시켰다. 반웅 완료 후 반웅액에 물을 넣고 디클로로메탄 (dichloromethane, DCM)로 추출한 다음 무수 MgS04로 수분을 제거한 후: 필터하고 감압 농축하였다ᅳ 이렇게 얻어진 잔사를 컬럼 크로마토그래피로 분리 정제하여 화합물 1-2 22.6 g (63 %)을 얻었다. 1.23 g (1.07 mmol) of tetrakis (tdphenylphosphine) palladium was added and stirred. 36.8 g (267 mmol) of potassium carbonate saturated in water was added thereto, and the mixture was heated and refluxed at 80 ° C. for 24 hours. After completion of reaction, water was added to the reaction solution and extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgS04 : filtered and concentrated under reduced pressure. (63%) was obtained.
HRMS (70 eV, EI+): m/z calcd for C24H15C1: 338.0862, found: 338 HRMS (70 eV, EI +): m / z calcd for C24H15C1: 338.0862, found: 338
Elemental Analysis: C, 85 %; H, 5 % 합성예 3: 중간체 1-3의 합성 Elemental Analysis: C, 85%; H, 5% Synthesis Example 3 Synthesis of Intermediate 1-3
중간체 1-1의 합성방법과 동일한 방법으로 합성, 정제하여 화합물 I-3 18.6 g (65 %)을 얻었다. 18.6 g (65%) of Compound I-3 was obtained by synthesis and purification in the same manner as in the synthesis of Intermediate 1-1.
HRMS (70 eV, EI+): m/z calcd for C30H27BO2: 430.2104, found: 430 HRMS (70 eV, EI +): m / z calcd for C30H27BO2: 430.2104, found: 430
Elemental Analysis: C, 84 %; H, 6 % 합성예 4: 중간체 1-4의 합성 Elemental Analysis: C, 84%; H, 6% Synthesis Example 4 Synthesis of Intermediate 1-4
[반응식 4]
질소 환경에서 상기 화합물 1-1 100 g (282 mmol)을 테트라하이드로퓨란 (THF) 1 L에 녹인 후, 여기에 1-브로모 -2-아이오도벤젠 (l-bromo-2-iodobenzene, Aldrich) 95.9 g (339mmol)와 테트라키스 (트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine) palladium) 3.26 g (2.82 mmol)을 넣고 교반시켰다. 물에 포화된 포타슘카보네이트 9그 4 g (705
mmol)을 넣고 80 °C에서 53시간 동안 가열하여 환류시켰다. 반웅 완료 후 반웅액에 물올 넣고 디클로로메탄 (DCM)으로 추출한 다음 무수 MgS04로 수분올 제거한 후, 필터하고 감압 농축하였다. 이렇게 얻어진 잔사를 컬럼 크로마토그래피로 분리 정제하여 화합물 1-4 95.1 g (88 %)를 얻었다. Scheme 4 Dissolve 100 g (282 mmol) of the compound 1-1 in 1 L of tetrahydrofuran (THF) in a nitrogen environment, and then add 1-bromo-2-iodobenzene (Aldrich). 95.9 g (3 3 9 mmol) and 3.26 g (2.82 mmol) of tetrakis (triphenylphosphine) palladium were added and stirred. 4 g of potassium carbonate saturated in water (705 mmol) was added and heated to reflux for 53 hours at 80 ° C. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS04, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through column chromatography, obtaining 95.1 g (88%) of Compound 1-4.
HRMS (70 eV, EI+): m/z calcd for C24H15Br: 382.0357, found: 382 HRMS (70 eV, EI +): m / z calcd for C 24 H 15 Br: 382.0357, found: 382
Elemental Analysis: C, 75 %; H, 4 % 합성예 5: 중간체 1-5의 합성 Elemental Analysis: C, 75%; H, 4% Synthesis Example 5 Synthesis of Intermediate 1-5
[반웅식 5] [Bungungsik 5]
중간체 1-1의 합성방법과 동일한 방법으로 합성, 정제하여 화합물 1-5 74.8 g (74 %)을 얻었다. Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1-1 to give 74.8 g (74%) of Compound 1-5.
HRMS (70 eV, EI+): m/z calcd for C30H27BO2: 430.2104, found: 430 HRMS (70 eV, EI +): m / z calcd for C30H27BO2: 430.2104, found: 430
Elemental Analysis: C, 84 %; H, 6 % 합성예 6: 중간체 1-6의 합성 Elemental Analysis: C, 84%; H, 6% Synthesis Example 6 Synthesis of Intermediate 1-6
반웅식 6] Banungsik 6]
33
중간체 1-4의 합성방법과 동일한 방법으로 합성, 정제하여 화합물 1-6 42.6 g (80 %)을 얻었다. 42.6 g (80%) of Compound 1-6 was obtained by synthesis and purification in the same manner as in the synthesis of Intermediate 1-4.
HRMS (70 eV, EI+): m/z calcd for C30H19Br: 458.0670, found: 458. HRMS (70 eV, EI < + >): m / z calcd for C 30 H 19 Br: 458.0670, found: 458 .
Elemental Analysis: C, 78 %; H, 4 % 합성예 Ί: 중간체 1-7의 합성
[반웅식 7]
Elemental Analysis: C, 78%; H, 4% Synthesis Example iii: Synthesis of Intermediate 1-7 [Bungungsik 7]
증간체 1-1의 합성방법과 동일한 방법으로 합성， 정제하여 화합물 1-7 34 g (77 %)을 얻었다. 34 g (77%) of Compound 1-7 was obtained by synthesis and purification in the same manner as in the synthesis of Intermediate 1-1.
HRMS (70 eV, EI+): m/z calcd for C36H31B02: 506.2417, found: 506 HRMS (70 eV, EI +): m / z calcd for C36H31B02: 506.2417, found: 506
Elemental Analysis: C, 85 %; H, 6 % 합성예 8: 화합물 A-33의 합성 Elemental Analysis: C, 85%; H, 6% Synthesis Example 8 Synthesis of Compound A-33
반응식 8] Scheme 8]
질소 환경에서 상기 화합물 I -7 20 g (39.5 mmol)을 테트라하이드로퓨란 (THF) 0.2 L에 녹인 후, 여기에 2-클로로 -4,6-디페닐 -1,3,5-트리아진 p-chloro-^^diphenyl-HS- triazine, TCI) 10.6 g (39.5 mmol)와 In a nitrogen environment, 20 g (39.5 mmol) of the compound I-7 was dissolved in 0.2 L of tetrahydrofuran (THF), followed by 2-chloro-4,6-diphenyl-1,3,5-triazine p- chloro-^^ diphenyl-HS- triazine, TCI) 10.6 g (39.5 mmol)
테트라키스 (트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine)palladium) 0.46 g (0.4 mmol)을 넣고 교반시켰다. 물에 포화된 포타슴카보네이트 13.6 g (98.8 mmol)을 넣고 80 °C에서 23시간 동안 가열하여 환류시켰다. 반웅 완료 후 반웅액에 물을 넣고 디클로로메탄 (DCM)으로 추출한 다음 무수 MgS04로 수분을 제거한 후， 필터하고 감압 농축하였다. 이렇게 얻어진 잔사를 컬럼 크로마토그래피로 분리 정제하여 상기 화합물 A-33 17.9 g (74 %)을 얻었다. 0.46 g (0.4 mmol) of tetrakis (triphenylphosphine) palladium was added and stirred. 13.6 g (98.8 mmol) of potassium carbonate saturated in water was added thereto, and the mixture was heated and refluxed at 80 ° C. for 23 hours. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS04, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through column chromatography, obtaining 17.9 g (74%) of the compound A-33.
HRMS (70 eV, EI+): m/z calcd for C45H29N3: 61 1.2361 , found: 61 1 HRMS (70 eV, EI +): m / z calcd for C45H29N3: 61 1.2361, found: 61 1
Elemental Analysis: C, 88 %; H, 5 % 제 2 화합물의 합성 Elemental Analysis: C, 88%; H, synthesis of 5% second compound
합성예 9: 화합물 B-10의 합성
[반응식 9] Synthesis Example 9: Synthesis of Compound B-10 Scheme 9
제 1 단계: 화합물 A의 합성 First Step: Synthesis of Compound A
2-Benzalacetophenone 140.4 g (674 mmol), 피리딘염화합물 199.04 g (808.77 mmol); 암모늄아세테이트 415.6 g (5391 mmol)을 메탄을 (1720 ml)에 현탁시킨 후, 1 10°C에서 2시간 동안 환류 교반하였다. 반웅 후, 생성물을 증류수에 침전시켜 고체를 140.4 g (674 mmol) of 2-Benzalacetophenone, 199.04 g (808.77 mmol) of pyridine salt ; 415.6 g (5391 mmol) of ammonium acetate were suspended in methane (1720 ml) and then stirred at reflux at 1 10 ° C for 2 hours. After reaction, the product was precipitated in distilled water to give a solid.
형성시키고, 생성된 고체를 필터하여 화합물 A를 106 g (64 %) 수득하였다. Formed and the resulting solid was filtered to yield 106 g (64%) of compound A.
제 2 단계: 화합물 B의 합성 Second Step: Synthesis of Compound B
화합물 (A) 100 g (405.67 mmol)과 P205 172.74 g (1217 mmol), TBAB 196.17 g (608.5 mmol)를 모두 넣고, 클로로벤젠에 현탁시킨 후， 140 °C에서 14시간 동안 환류
교반하였다. 반응 후 용매를 제거하고, 디클로로메탄과 증류수로 추출한 유기층을 실리카겔 필터하고, 얻은 유기층을 150ml까지 제거한 후 메탄을을 부어 침전물을 형성하고， 생성된 고형물올 필터하여 화합물 B를 89 g (71 %) 수득하였다. 100 g (405.67 mmol) of Compound (A), 172.74 g (1217 mmol) of P 2 0 5 , and 196.17 g (608.5 mmol) of TBAB were added thereto, suspended in chlorobenzene and refluxed at 140 ° C. for 14 hours. Stirred. After the reaction, the solvent was removed, the organic layer extracted with dichloromethane and distilled water was filtered through silica gel, the obtained organic layer was removed to 150 ml, and methane was poured to form a precipitate. The resulting solid was filtered to give 89 g (71%) of compound B Obtained.
제 3 단계: 화합물 J의 합성 Third Step: Synthesis of Compound J
9-페닐 -9H-카바졸 -3-일 보론산 (9-phenyl-9H-carbazol-3-yl boronic acid, -TCI) 10 g 10 g of 9-phenyl-9H-carbazol-3-yl boronic acid (9-phenyl-9H-carbazol-3-yl boronic acid, -TCI)
(34.83 mmol), 3-브로모카바졸 (3-bromocarbazole, Aldrich), 1 1.77 g (38.31 mmol) 및 (34.83 mmol), 3-bromocarbazole (Aldrich), 1 1.77 g (38.31 mmol) and
탄산칼륨 14.44 g (104.49 mmol), 테트라키스- (트리페닐포스핀)팔라듐 (0) 0.80 g (0.7 mmmol) 을 를루엔 140 ml, 증류수 50 ml에 현탁시킨 후 12 시간 동안 환류 14.44 g (104.49 mmol) of potassium carbonate, 0.80 g (0.7 mmmol) of tetrakis- (triphenylphosphine) palladium (0) were suspended in 140 ml of toluene and 50 ml of distilled water and refluxed for 12 hours.
교반하였다. 이어서 디클로로메탄과 증류수로 추출하고 유기층을 실리카겔 필터한다. 이어서 반웅 종결 후 반웅물에 메탄을에 부어 생기는 고형물을 필터 한 다음， 고형물을 다시 클로로밴젠에 녹여 활성탄과 무수황산마그네슘을 넣어 교반한다. Stirred. Subsequently, the mixture was extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. Subsequently, after the completion of the reaction, the solid produced by pouring methane into the reaction product was filtered, and then the solid was dissolved in chlorovanzen and stirred with activated carbon and anhydrous magnesium sulfate.
용액을 필터한 다음 클로로벤젠과 메탄을을 이용해 재결정하여 화합물 J, 22.6 g (68 %)을 얻었다. The solution was filtered and then recrystallized with chlorobenzene and methane to give compound J, 22.6 g (68%).
HRMS (70 eV, EI+): m/z calcd for C30H20N2: 408.16, found: 408 HRMS (70 eV, EI +): m / z calcd for C 30 H 20 N 2: 408.16, found: 408
Elemental Analysis: C, 88 %; H, 5 % 제 4 단계: 화합물 B-10의 합성 Elemental Analysis: C, 88%; H, 5% Step 4: Synthesis of Compound B-10
화합물 J로 표시되는 화합물 22.42 g (54.88 mmol), 2-브로모 -4,6- 다이페닐피리딘 (2-bromo-4,6-diphenylpyridine, 화합물 B 20.43g(65.85 mmol) 및 22.42 g (54.88 mmol) of the compound represented by compound J, 2-bromo-4,6-diphenylpyridine (2-bromo-4,6-diphenylpyridine, Compound B 20.43 g (65.85 mmol), and
터셔리부특시나트륨 7.92 g (82.32 mmol)을 를루엔 400ml 녹인 후， 팔라듐 Dissolve 400 ml of toluene in 7.92 g (82.32 mmol) of tertiary sodium specialty, palladium
다이벤질리덴아민 1.65 g (1.65 mmol) 과 터셔리부틸인 1.78 g (4.39 mmol)을 적가한다. 반웅용액을 질소기류하에서 12 시간 동안 1 10 °C로 가열하여 교반하였다. 반응 종결 후 반응물에 메탄올을 부어 생기는 고형물을 필터 한 다음, 고형물을 다시 1.65 g (1.65 mmol) of dibenzylideneamine and 1.78 g (4.39 mmol) of tertiary butyl are added dropwise. The semi-aqueous solution was heated and stirred at 1 10 ° C for 12 hours under a nitrogen stream. After completion of the reaction, the solids produced by pouring methanol into the reactants were filtered, and the solids again
클로로벤젠에 녹여 활성탄과 무수황산마그네슘을 넣어 교반한다. 용액을 필터한 다음 클로로벤젠과 메탄올을 이용해 재결정 하여 화합물 B-10, 28.10g (80 %)을 얻었다. Dissolve in chlorobenzene, add activated carbon and anhydrous magnesium sulfate, and stir. The solution was filtered and recrystallized with chlorobenzene and methanol to obtain compound B-10, 28.10g (80%).
HRMS (70 eV, EI+): m/z calcd for C47H31N3: 637.25, found: 637 HRMS (70 eV, EI +): m / z calcd for C47H31N3: 637.25, found: 637
Elemental Analysis: C, 89 %; H, 5 % 합성예 10: 화합물 B-31의 합성
Elemental Analysis: C, 89%; H, 5% Synthesis Example 10 Synthesis of Compound B-31
9-페닐 -9H-카바졸 -3-일 보론산 (9-phenyl-9H-carbazol-3-yl boronic acid, -TCI) 10 g (34.83 mmol), 3-브로모 -9-페닐카바졸 (3-bromo-9-phenylcarbazole, Aldrich), 11.77 g (38.31 mmol) 및 탄산칼륨 14.44 g (104.49 mmol), 테트라키스- (트리페닐포스핀)팔라듐 (0) 0.80 g (0.7 mmmol) 을 를루엔 140 ml, 증류수 50 ml에 현탁시킨 후 12 시간 동안 환류 교반하였다. 이어서 디클로로메탄과 증류수로 추출하고 유기층을 실리카겔 필터한다ᅳ 이어서 유기 용액을 제거하고 핵산:디클로로메탄 = 7:3(v/v) 으로 실리카 겔 컬럼하여 생성물 고체를 디클로로메탄과 n-핵산으로 재결정하여 화합물 B-31 13.8 g (92 %)을 얻었다. 9-phenyl-9H-carbazol-3-yl boronic acid (9-phenyl-9H-carbazol-3-yl boronic acid, -TCI) 10 g (34.83 mmol), 3-bromo-9-phenylcarbazole ( 3-bromo-9-phenylcarbazole, Aldrich), 11.77 g (38.31 mmol) and 14.44 g (104.49 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 0.80 g (0.7 mmmol) The suspension was suspended in 50 ml of distilled water and stirred under reflux for 12 hours. Then, the mixture was extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. Then, the organic solution was removed and the silica gel column was purified by nucleic acid: dichloromethane = 7: 3 (v / v) to recrystallize the product solid with dichloromethane and n -nucleic acid. 13.8 g (92%) of compound B-31 were obtained.
H MS (70 eV, EI+): m/z calcd for C36H24N2: 484.19, found: 484 H MS (70 eV, EI +): m / z calcd for C36H24N2: 484.19, found: 484
Elemental Analysis: C, 89 %; H, 5 % 합성예 11: 화합물 B-43의 합성
Elemental Analysis: C, 89%; H, 5% Synthesis Example 11: Synthesis of Compound B-43
제 1 단계: 화합물 K의 합성 First Step: Synthesis of Compound K
화합물 B-10의 합성 방법과 동일한 방법으로, 정제하여 화합물 K20g(900/0)을 수득하였다.
제 2 단계: 화합물 L의 합성 By the same method as the compound B-10, was purified to give the compound K20g (90 0/0). Second Step: Synthesis of Compound L
화합물 K 20g (62.6 mmol)을 DMF (200 ml)에 현탁시킨 후, NBS 12.93 g (72.67 mmol)을 조금씩 첨가하고, 12 시간 동안 환류 교반하였다. 증류수를 넣고 반웅 종결시킨 후， 디클로로메탄으로 추출하여 얻은 유기층을 실리카겔 필터한다. 이어서 유기 용액을 제거하고 핵산:디클로로메탄 = 7:3(ν/ν) 으로 실리카 겔 컬럼하여 생성물 고체를 디클로로메탄과 η-핵산으로 재결정하여 화합물 L 22.4 g (90 %)을 얻었다. 제 3 단계: 화합물 N의 합성 20 g (62.6 mmol) of compound K was suspended in DMF (200 ml), then 12.93 g (72.67 mmol) of NBS were added in portions and stirred at reflux for 12 hours. After distilled water was added and reaction was terminated, the organic layer obtained by extraction with dichloromethane was filtered through a silica gel filter. The organic solution was then removed and silica gel column with nucleic acid: dichloromethane = 7 : 3 (v / v) to recrystallize the product solid with dichloromethane and η-nucleic acid to give compound L 22.4 g (90%). Third Step: Synthesis of Compound N
증간체 1-1의 합성 방법과 동일한 방법으로, 정제하여 화합물 N 22.5 g (90 0/0)을 수득하였다. 제 4 단계: 화합물 B-43의 합성 By the same method as the method of increasing Simplified 1-1 was purified to give the compound N 22.5 g (90 0/0 ). Fourth Step: Synthesis of Compound B-43
화합물 N 10 g (34.83 mmol), 9-[U'-바이페닐-4-일]-3-브로모-9H-카바졸(9-[l,Γ- Biphenyl-4-yl]-3-bromo-9H-carbazole, TCI), 11.77 g (38.31 mmol) 및 탄산칼륨 14.44 g (104.49 mmol), 테트라키스- (트리페닐포스핀)팔라듐 (0) 0.80 g (0.7 mmmol) 을 틀루엔 140 ml, 증류수 50 ml에 현탁시킨 후 12 시간 동안 환류 교반하였다. 이어서 디클로로메탄과 n-핵산으로 재결정하여 화합물 B-43 18.7g (92 %)을 얻었다. Compound N 10 g (34.83 mmol), 9- [U'-biphenyl-4-yl] -3-bromo-9H-carbazole (9- [l, Γ- Biphenyl-4-yl] -3-bromo -9H-carbazole, TCI), 11.77 g (38.31 mmol) and 14.44 g (104.49 mmol) of potassium carbonate, 0.80 g (0.7 mmmol) of tetrakis- (triphenylphosphine) palladium (0) 140 ml of toluene, distilled water It was suspended in 50 ml and stirred at reflux for 12 hours. Then recrystallized with dichloromethane and n-nucleic acid to give 18.7g (92%) of Compound B-43.
HRMS (70 eV, EI+): m/z calcd for C48H32N2: 636.26, found: 636 HRMS (70 eV, EI +): m / z calcd for C48H32N2: 636.26, found: 636
Elemental Analysis: C, 91 %; H, 5 % 제 3 화합물의 합성 Elemental Analysis: C, 91%; H, synthesis of 5% tertiary compound
합성예 12: 중간체 M-1의 합성 Synthesis Example 12 Synthesis of Intermediate M-1
[반응식 12] Scheme 12
M-1 중간체 i_4의 합성방법과 동일한 방법으로 합성하되, 반웅용매를 틀루엔으로 하고， 12시간 환류시킨 후, 정제하여 중간체 M-1 27 g (89 %)을 수득하였다. But synthesized in the same method as in the method of intermediate M-1 i_ 4, then the solvent banung a frame toluene and refluxed for 12 hours, and purified to give the intermediate M-1 27 g (89% ).
LC-Mass (이론치： 322.00 g/mol, 측정치 : M+ = 322.09 g/mol, M+2 = 324.04 g/mol)
합성예 13: 증간체 M-2의 합성 LC-Mass (Theoretical value: 322.00 g / mol, Measured value: M + = 322.09 g / mol, M + 2 = 324.04 g / mol) Synthesis Example 13 Synthesis of Intermediate M-2
[반웅식 13] [Banungsik 13]
M-2 M-2
상기 중간체 M-1의 합성방법과 동일한 방법으로 합성, 정제하여 중간체 M-2 29 g (91 %)을 수득하였다. Synthesis and purification were carried out in the same manner as the synthesis of Intermediate M-1 to obtain 29 g (91%) of Intermediate M-2.
LC-Mass (이론치： 337.98 g/mol, 측정치 : M+ = 338.04 g/mol, M+2 = 340.1 1 g/mol) 합성예 14: 중간체 M-3의 합성 LC-Mass (Theoretical value: 337.98 g / mol, Measured value: M + = 338.04 g / mol, M + 2 = 340.1 1 g / mol) Synthesis Example 14 Synthesis of Intermediate M-3
[반응식 14] Scheme 14
상기 증간체 M-1의 합성방법과 동일한 방법으로 합성, 정제하여 중간체 M-3 23.9 g (91 %)을 수득하였다. Synthesis and purification were carried out in the same manner as the synthesis of Intermediate M-1 to obtain 23.9 g (91%) of intermediate M-3.
LC-Mass (이론치： 278.05 g/mol, 측정치 : M+ = 278.12 g/mol, M+2 = 280.13 g/mol) 합성예 15: 중간체 M-4의 합성 LC-Mass (Theoretical value: 278.05 g / mol, Measured value: M + = 278.12 g / mol, M + 2 = 280.13 g / mol) Synthesis Example 15 Synthesis of Intermediate M-4
[반응식 15] Scheme 15
중간체 M-1의 합성방법과 동일한 방법으로 합성, 정제하여 중간체 M-4 25.6 g (92 %)을 수득하였다. Synthesis and purification were carried out in the same manner as the synthesis of Intermediate M-1 to obtain 25.6 g (92%) of Intermediate M-4.
LC-Mass (이론치： 294.03 g/mol, 측정치： M+ = 294.16 g/mol, M+2 = 296.13 g/mol) 합성예 16: 중간체 M-5의 합성
[반웅식 16] LC-Mass (Theoretical value: 294.03 g / mol, Measured value: M + = 294.16 g / mol, M + 2 = 296.13 g / mol) Synthesis Example 16: Synthesis of Intermediate M-5 [Banungsik 16]
등근바닥플라스크에 중간체 M-1 10 g (30.9 mmol)과 4-아미노바이페닐 6.3 g (37.08 mmol, Aldrich), 소디움 t-부톡사이드 5.35 g (55.6 mmol)을 넣고 틀루엔 155 ml을 가하여 용해시켰다ᅳ 여기에 Pd(dba)2 0.178 g (0.31 mmol)과 트리 -터셔리- 부틸포스핀 0.125 g (0.62 mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반시켰다. 반웅 종료 후 에틸아세테이트과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다ᅳ 생성물을 n- 핵산 /디클로로메탄 (7:3 부피비)로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-5 9.92 g (78 %)을 수득하였다. 10 g (30.9 mmol) of intermediate M-1, 6.3 g (37.08 mmol, Aldrich) and 5.35 g (55.6 mmol) of sodium t-butoxide were added to the back bottom flask, and 155 ml of toluene was added to dissolve it. ᅳ 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were added thereto, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. Banung end The organic layer was dried and then extracted with ethyl ahseteyiteugwa distilled over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to eu product n - nucleic acid / dichloromethane (7: 3 by volume) was purified by column chromatography on silica gel to the desired compounds 9.92 g (78%) of phosphorus intermediate M-5 was obtained.
LC-Mass (이론치: 411.16 g/mol, 측정치: M+ = 411.21 g/mol) 합성예 17: 중간체 M-6의 합성 LC-Mass (Theoretical value: 411.16 g / mol, Measured value: M + = 411.21 g / mol) Synthesis Example 17 Synthesis of Intermediate M-6
[반웅식 17] [Banungsik 17]
중간체 M-2 10 g (30.9 mmol)와 2-아미노 -9，9'-다이메틸플루오렌 10 g (30.9 mmol) of intermediate M-2 and 2-amino-9,9'-dimethylfluorene
6.3 g (37.08 mmol, TCI)을 사용한 것을 제외하고는， 상기 증간체 M-5의 합성방법과 동일한 방법으로 합성, 정제하여 중간체 M-6 1 1 g (76 %)을 수득하였다. Except for using 6.3 g (37.08 mmol, TCI), was synthesized and purified in the same manner as the synthesis of Intermediate M-5 to give 1 g (76%) of intermediate M-6.
LC-Mass (이론치： 467.17 g/mol, 측정치： M+ = 467.23 g/mol) 합성예 18: 중간체 M-7의 합성
[반웅식 18] LC-Mass (Theoretical value: 467.17 g / mol, Measured value: M + = 467.23 g / mol) Synthesis Example 18: Synthesis of Intermediate M-7 [Banungsik 18]
중간체 M-4 10 g (30.9 mmol)와 4-아미노바이페닐 6.3 g (37.08 mmol, Aldrich)을 사용한 것을 제외하고는, 상기 중간체 M-5의 합성방법과 동일한 방법으로 합성， 정제하여 중간체 M-7 10.6 g (80 %)을 수득하였다. Intermediate M- was synthesized and purified in the same manner as in the synthesis of Intermediate M-5, except that 10 g (30.9 mmol) of Intermediate M-4 and 6.3 g (37.08 mmol, Aldrich) of 4-aminobiphenyl were used. 7 10.6 g (80%) was obtained.
LC-Mass (이론치： 427.14 g/mol, 측정치： M+ = 427.19 g/mol) 합성예 19: 중간체 M-8의 합성 LC-Mass (Theoretical value: 427.14 g / mol, Measured value: M + = 427.19 g / mol) Synthesis Example 19: Synthesis of Intermediate M-8
[반웅식 19] [Banungsik 19]
중간체 M-2 10 g (30.9 mmol)와 4-아미노바이페닐 6.3 g (37.08 mmol, Aldrich)을 사용한 것을 제외하고는, 상기 중간체 M-5의 합성방법과 동일한 방법으로 합성, 정제하여 중간체 M-8 10.5 g (80 %)을 수득하였다. Intermediate M- was synthesized and purified in the same manner as in the synthesis of Intermediate M-5, except that 10 g (30.9 mmol) of Intermediate M-2 and 6.3 g (37.08 mmol, Aldrich) of 4-aminobiphenyl were used. 8 10.5 g (80%) were obtained.
LC-Mass (이론치： 427.14 g/mol, 측정치 : M+ = 427.20 g/mol) 합성예 20: 화합물 H-1의 합성 LC-Mass (Theoretical value: 427.14 g / mol, Measured value: M + = 427.20 g / mol) Synthesis Example 20: Synthesis of Compound H-1
[반웅식 20] [Banungsik 20]
155 ml을 가하여 용해시켰다. 여기에 Pd(dba)2 0.53 g (0.928 mmol)과 트리 -터셔리- 부틸포스핀 으 38 g (1.86 mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반시켰다. 반응 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슴 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n- 핵산 /다클로로메탄 (8:2 부피비)로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-1 13.7 g (90 %)을 수득하였다. 155 ml was added to dissolve. 0.53 g (0.928 mmol) of Pd (dba) 2 and 38 g (1.86 mmol) of tri-tertiary-butylphosphine were sequentially added thereto, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n -nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.7 g (90%) of the title compound H-1.
LC-Mass (이론치： 653.24 g/mol, 측정치 : M+ = 653.31 g/mol) 합성예 21 내지 31: 화합물의 합성 LC-Mass (Theoretical value: 653.24 g / mol, Measured value: M + = 653.31 g / mol) Synthesis Examples 21 to 31 Synthesis of Compound
하기 [표 1]의 출발물질 1 및 출발물질 2를 위 합성예 20의 합성법으로 하기 표의.생성물을 제조하였으며, 이에 대한 수율 및 LC-Mass 값은 하기 [표 1]과 같다. Table 1 was prepared from the starting material 1 and starting material 2 in the synthesis method of Synthesis Example 20, the product of the following table. The yield and LC-Mass values for the same are shown in the following [Table 1].
[표 1] TABLE 1
실시예 1 Example 1
ΠΌ (Indium tin oxide)가 1500A의 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음
산소 플라즈마를 이용하여 상기 기판을 10분간 세정 한 후 진공 층착기로 기판을 이송하였다. 이렇게 준비된 ΠΌ 투명 전극을 양극으로 사용하여 ΠΌ 기판 상부에 Ν4,Ν4'-디페닐 -Ν4,Ν4'-비스 (9-페닐 -9Η-카바졸 -3-일)바이페닐 -4，4'-디아민 (Ν4,Ν4'- diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-V A)를 진공 증착하여 700A두께의 정공 주입층을 형성하고 상기 정공 주입층 상부에 Glass substrates coated with ΠΌ (Indium tin oxide) to a thickness of 1500A were washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and then transferred to the plasma cleaner. The substrate was cleaned for 10 minutes by using an oxygen plasma, and then the substrate was transferred to a vacuum laminator. Using the prepared ΠΌ transparent electrode as an anode, Ν4, Ν4'-diphenyl -Ν4, Ν4'-bis (9-phenyl-9Η-carbazol-3-yl) biphenyl-4,4'- Diamine (Ν4, Ν4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-V A) was vacuum deposited to form a hole injection layer having a thickness of 700 A and the hole injection layer At the top
1，4,5，8，9,1 1-핵사아자트리페닐렌 -핵사카보니트릴 (1 ,4,5,8,9, 11 -hexaazatriphenylene- hexacarbonitrile, HAT-CN)(화합물 B)를 50 A의 두께로 증착한 후 , N- (바이페닐 -4-일) - 9,9-디메틸 -N-(4-(9-페닐 -9H-카바졸 -3-일)페닐) -9H-플루오렌 -2-아민 (N-(biphenyl-4-yl)-9,9- dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-am^ C)를 1,4,5,8,9,1 1-nucleated azatriphenylene-nuxacarbonitrile (1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile, HAT-CN) (Compound B) After deposition to a thickness of N- (biphenyl-4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluorene 2-amine (N- (biphenyl-4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-am ^ C)
700A의 두께로 증착하여 정공수송층을 형성하였다. 정공수송층 상부에 합성예 21에서 얻어진 화합물 H-2을 진공 증착으로 50 A 두께의 정공수송보조층을 Depositing a thickness of 700A to form a hole transport layer. Compound H-2 obtained in Synthesis Example 21 was vacuum deposited on the hole transport layer to form a hole transport auxiliary layer having a thickness of 50 A.
형성하였다. 이어서 상기 정공수송보조층 상부에 청색형광 발광 호스트 및 도편트로 SFC사에서 판매하는 BH1 13과 BD370을 사용하여 BD370을 5wt%로 도핑하여 200 A의 두께로 증착하여 발광층을 형성하였다. 이어서 상기 발광층 상부에 합성예 8에서 얻어진 화합물 A-33 및 합성예 11에서 얻어진 화합물 B-43을 진공 증착으로 50 A 두께의 전자수송보조층을 형성하였다. 여기서 화합물 A-33과 화합물 B-43은 1 : 1 중량비로 사용되었다. Formed. Subsequently, the light emitting layer was formed by doping BD370 at a weight of 200 A using BH1 13 and BD370 sold by SFC as a blue fluorescent light emitting host and dopant on the hole transport auxiliary layer. Subsequently, an electron transport auxiliary layer having a thickness of 50 A was formed on the light emitting layer by vacuum deposition of Compound A-33 obtained in Synthesis Example 8 and Compound B-43 obtained in Synthesis Example 11. Here, compound A-33 and compound B-43 were used in 1: 1 weight ratio.
이어서 상기 전자수송보조층 상부에 8-(4-(4- (나프탈렌 -2-일) -6- (나프탈렌 -3-일) - I ,3,5-트리아진 -2-일)페닐)퀴놀린 (8-(4-(4-(naphthalen-2-yl)-6-(naphthalen-3-yl)-l,3,5-triazin- 2-yl)phenyl)quinoline) (화합물 E)와 Liq(8-hydroxyquinolatolithium)를 동시에 1 : 1 비율로 진공 증착하여 310 A 두께의 전자수송층을 형성하고 상기 전자수송층 상부에 Liq 15 A과 A1 1200 A을 순차적으로 진공 증착하여 음극을 형성함으로써 유기발광소자를 제작하였다. Subsequent to the electron transport layer upper secondary 8- (4- (4- (naphthalen-2-yl) -6- (naphthalen-3-yl) - I, 3, 5 - triazine-2-yl) phenyl) quinoline (8- ( 4- ( 4- (naphthalen-2-yl) -6- (naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline) (Compound E) and Liq ( 8-hydroxyquinolatolithium) was simultaneously vacuum deposited in a 1: 1 ratio to form an electron transport layer having a thickness of 310 A, and an organic light emitting device was formed by sequentially vacuum depositing Liq 15 A and A1 1200 A on the electron transport layer. It was.
상기 유기발광소자는 6층의 유기 박막층을 가지는 구조로 되어 있으며， 구체적으로 The organic light emitting device has a structure having six organic thin film layers, specifically
ITO/A(700A)/B(50A)/C(700A)/정공수송보조층 [H-2(50 A)]/ ITO / A (700A) / B (50A) / C (700A) / Hole Transport Auxiliary Layer [H-2 (50A)] /
EML[BH1 13:BD370(95:5wt%)](200A)/ 전자수송보조층 [A-33 :B-43=1 : 1(50 A)/ EML [BH1 13: BD370 (95: 5wt%)] (200A) / electron transport auxiliary layer [A-33: B-43 = 1: 1 (50A) /
E: Liq= 1： 1 (300 A )/ Liq( 15 A )/Al( 1200 A )≤1 구조로 제작하였다. 실시예 2
정공수송보조층에 화합물 H-2 대신 합성예 22에서 얻어진 화합물 H-1 1을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기발광소자를 제작하였다. 참고예 1 E: Liq = 1: 1 (300 A) / Liq (15 A) / Al (1200 A) was produced in a structure. Example 2 An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound H-1 1 obtained in Synthesis Example 22 instead of the compound H-2 for the hole transport auxiliary layer. Reference Example 1
정공수송보조층을 형성하지 않고, 화합물 C를 750人의 두께로 증착하여 정공수송층을 형성한 것을 제외하고는 실시예 1과 동일한 방법으로 유기발광소자를 제작하였다. 비교예 1 An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound C was deposited to a thickness of 750 people to form a hole transport layer, without forming a hole transport auxiliary layer. Comparative Example 1
정공수송보조층올 형성하지 않고, 화합물 C를 750 A의 두께로 증착하여 형성하고, 전자수송보조층을 형성하지 않고, 전자수송층에 화합물 E:Liq=l : l(310A) 대신 화합물 E:Liq=l : l (360A) 증착한 것올 제외하고는 실시예 1과 동일한 방법으로 유기발광소자를 제작하였다. 비교예 2 Compound C was formed by evaporating to a thickness of 750 A without forming a hole transport auxiliary layer, and compound E: Liq = instead of compound E: Liq = l: l (310A) in the electron transport layer without forming an electron transport auxiliary layer. l: l (360A) An organic light emitting diode was manufactured according to the same method as Example 1 except for depositing. Comparative Example 2
전자수송보조층을 형성하지 않고， 전자수송층에 화합물 E:Liq=l : l(310A) 대신 화합물 E:Liq=l : l(360 A) 증착한 것을 제외하고는 실시예 1과 동일한 방법으로 유기발광소자를 제작하였다. The same method as in Example 1 was carried out except that the electron transport auxiliary layer was not formed and the compound E: Liq = l: l (360 A) was deposited on the electron transport layer instead of the compound E: Liq = l: l (310A). A light emitting device was manufactured.
실시예 1, 실시예 2， 참고예 1 , 비교예 1 및 비교예 2에 따른 유기발광소자의 발광효율 및 수명올 평가하였다. The luminous efficiency and lifetime of the organic light emitting diode according to Example 1, Example 2, Reference Example 1, Comparative Example 1 and Comparative Example 2 were evaluated.
구체적인 측정방법은 하기와 같고, 그 결과는 표 2와 같다. Specific measurement methods are as follows, and the results are shown in Table 2.
(1) 전압변화에 따른 전류밀도의 변화 측정 (1) Measurement of change of current density according to voltage change
제조된 유기발광소자에 대해, 전압올 0V 부터 10V까지 상승시키면서 전류- 전압계 (Keithley 2400)를 이용하여 단위소자에 흐르는 전류값을 측정하고, 측정된 전류값을 면적으로 나누어 결과를 얻었다. With respect to the manufactured organic light emitting device, the current value flowing through the unit device was measured by using a current-voltmeter (Keithley 2400) while increasing the voltage from 0V to 10V, and the measured current value was divided by the area to obtain a result.
(2) 전압변화에 따른 휘도변화 측정 (2) Measurement of luminance change according to voltage change
제조된 유기발광소자에 대해, 전압을 0V 부터 10V까지 상승시키면서 휘도계 (Minolta Cs-IOOOA)를 이용하여 그 때의 휘도를 측정하여 결과를 얻었다.
(3) 발광효율 측정 For the manufactured organic light emitting device, the luminance was measured by using a luminance meter (Minolta Cs-IOOOA) while increasing the voltage from 0V to 10V to obtain a result. (3) Measurement of luminous efficiency
상기 (1) 및 (2)로부터 측정된 휘도와 전류밀도 및 전압을 이용하여 동일 전류밀도 (lO mA/cm2)의 전류 효율 (cd/Α) 을 계산하였다. The current efficiency (cd / Α) of the same current density (10 mA / cm 2 ) was calculated using the luminance, current density, and voltage measured from (1) and (2).
(4) 수명 측정 (4) life measurement
휘도 (cd/m2)를 750 cd/m2로 유지하고 전류 효율 (cd/A)이 97%로 감소하는 시간을 측정하여 결과를 얻었다. The results were obtained by measuring the time at which the luminance (cd / m 2) was maintained at 750 cd / m 2 and the current efficiency (cd / A) decreased to 97%.
[표 2] TABLE 2
Claims
[화학식 1] [Formula 1]
상기 화학식 1에서, . In Formula 1 above, .
Z는 각각 독립적으로 N, C 또는 CRa이고， Z is each independently N, C or CR a ,
Z 중 적어도 하나는 N 이고, At least one of Z is N,
R1 내지 R10 및 Ra는 각각 독립적으로 수소， 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C12 아릴기 또는 이돌의 조합이고， R 1 to R 10 and R a are each independently a combination of hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or idole,
L1은 치환 또는 비치환된 페닐렌기, 치환 또는 비치환된 바이페닐렌기 또는 치환 또는 비치환된 터페닐렌기이고, L 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
nl 내지 n3는 각각 독립적으로 0 또는 1이고, nl to n3 are each independently 0 or 1,
nl+n2+n3>l 이고,
nl+n2+n3>l,
상기 화학식 2에서, In Formula 2,
Y1 및 Y2는 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C2 내지 C30 해테로아릴렌기 또는 이들의 조합이고, Y 1 and Y 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
Arla 및 Arlb은 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기 또는 이들의 조합이고,Ar la and Ar lb are a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
" 내지 R16는 각각 독립적으로 수소， 증수소， 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C50 아릴기, 치환 또는 비치환된 C2 내지 C50 헤 로아릴기 또는 이들의 조합이고, " to R 16 are each independently hydrogen, increased hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heroyl group, or a combination thereof. ,
상기 화학식 3 에서， In Formula 3 above,
X1은 0 또는 S이고, X 1 is 0 or S,
17 및 R18은 각각 독립적으로, 수소， 증수소, 할로겐, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C3 내지 C20 시클로알킬기， 치환 또는 비치환된 C1 내지 C20 알콕시기, 치환 또는 비치환된 C3 내지 C20 시클로알콕시기， 치환 또는 비치환된 C1 내지 C20 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C6 내지
C30 아릴옥시기, 치환 또는 비치환된 C6 내지 C30 아릴티오기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실기 또는 카르복실기, 또는 이들의 조합이고, 1 7 and R 18 are each independently hydrogen, increased hydrogen, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted Or unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, A cyano group, a nitro group, a hydroxyl group, or a carboxyl group, or a combination thereof,
Ar2 및 Ar3는 각각 독립적으로, 치환 또는 비치환된 C6 내지 C30 아릴기 '또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴기이고, Ar 2 and Ar 3 are each independently a substituted or unsubstituted C6 to C30 aryl group ' or a substituted or unsubstituted C2 to C30 heteroaryl group,
L2 내지 L4는 각각 독립적으로 단일결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 해테로아릴렌기 또는 이들의 조합이고, L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
n4 내지 n6은 각각 독립적으로, 0 내지 3 중 어느 하나인 정수이고, 상기 화학식 1 내지 3의 "치환''은 적어도 하나의 수소가 중수소, 할로겐기, 히드록시기, 아미노기, 치환 또는 비치환된 C 1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 n4 to n6 are each independently an integer of 0 to 3, and "substitution'' in the formulas 1 to 3 means that at least one hydrogen is deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C 1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30
시클로알킬기, C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기, 플루오로기, C1 내지 C 10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. It means substituted with cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group or cyano group. .
【청구항 2】 【Claim 2】
제 1항에서, In paragraph 1:
상기 제 1 화합물은 하기 화학식 1- 1 또는 화학식 1- Π로 표현되는 유기 광전자 소자: The first compound is an organic optoelectronic device represented by the following Chemical Formula 1-1 or Chemical Formula 1-Π:
1- 1 [화학식 1- Π ] 1- 1 [Formula 1- Π]
상기 화학식 1- 1 및 1 - Π에서, In the above formulas 1-1 and 1-Π,
Z는 각각 독립적으로 N, C 또는 CRa이고, Z is each independently N, C or CR a ,
Z 중 적어도 하나는 N 이고, At least one of Z is N,
R1 내지 R10 및 Ra는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C 12 아릴기 또는 이들의 조합이고，
L1은 치환 또는 비치환된 페닐렌기, 치환 또는 비치환된 바이페닐렌기 또는 치환 또는 비치환된 터페닐렌기이고, R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof, L 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
nl 내지 n3는 각각 독립적으로 0 또는 1이고, nl to n3 are each independently 0 or 1,
nl+n2+n3>l ·이고, nl+n2+n3>l · ,
여기서, "치환' '은 적어도 하나의 수소가 중수소, 할로겐기, 히드록시기, 아미노기, 차환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기, C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기, 플루오로기, C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. Here, “substituted” means that at least one hydrogen is deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group. , C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group or cyano group. means that
【청구항 3 ] [Claim 3]
제 1항에서, In paragraph 1:
상기 제 1 화합물은 하기 그룹 2에 나열된 화합물 중 적어도 하나인 유기 광전자 소자: An organic optoelectronic device wherein the first compound is at least one of the compounds listed in Group 2:
[그룹 2] - A A- [Group 2] - A A-
【청구항 4】 【Claim 4】
제 1항에서, In paragraph 1:
상기 제 2 화합물은 하기 화학식 2-K 내지 2- X I 중 적어도 하나로 표현되는 유기 광전자 소자: The second compound is an organic optoelectronic device represented by at least one of the following formulas 2-K to 2-X I:
상기 화학식 2-Κ 내지 2- X I에서 In the above formulas 2-Κ to 2-
Υ' 및 Υ2는 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기 , 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기 또는 이들의 조합이고, Υ' and Υ 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
R" 내지 R16는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C20 알킬기， 치환 또는 비치환된 C6 내지 C50 아릴기, 치환 또는 비치환된 C2 내^ C50 헤테로아릴기 또는 이들의 조합이고, R" to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2^C50 heteroaryl group, or a combination thereof. ego,
상기 ΕΤ, ΕΤΙ, 및 ΕΤ2는 각각 독립적으로 하기 그룹 3에 나열된 치환 또는 비치환된 기에서 선택되고, Wherein ΕΤ, ΕΤΙ, and ΕΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 3 below,
상기 ΗΤ, Η Ί, 및 ΗΤ2는 각각 독립적으로 하기 그룹 4에 나열된 치환 또는 비치환된 기에서 선택되는 유기 광전자 소자:
그룹 3] wherein ΗΤ, Η Ί, and ΗΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 4: Group 3]
상기 그룹 3 및 4에서 *은 연결 지점이다ᅳ In groups 3 and 4 above, * is a connection point.
【청구항 5】 【Claim 5】
제 1항에 있어서, According to clause 1,
상기 제 2 화합물은 하기 그룹 5에 나열된 화합물에서 선택되는 소자： The second compound is an element selected from the compounds listed in Group 5:
[그룹 5] [Group 5]
【청구항 6] [Claim 6]
제 i항에서, In clause i:
상기 전자수송보조층은, The electron transport auxiliary layer is,
하기 화학식 1-1 및 1-Π로 표현되는 제 1 화합물 중 적어도 1종; 및 하기 화학식 2-K 내지 2-X I로 표현되는 제 2 화합물 중 적어도 1종을 포함하는 유기 광전자 소자:
[화학식 1-1] 화학식 1-Π] At least one of the first compounds represented by the following formulas 1-1 and 1-Π; And an organic optoelectronic device comprising at least one of the second compounds represented by the following formulas 2-K to 2-XI: [Formula 1-1] Formula 1-Π]
상기 화학식 1- I 및. l-Π에서, The formula 1-I and . In l-Π,
Z는 각각 독립적으로 N 또는 CRa이고, Z is each independently N or CR a ,
Z 중 적어도 하나는 N 이고， At least one of Z is N,
R1 내지 R10 및 Ra는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C12 아릴기 또는 이들의 조합이고, R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof,
L1은 치환 또는 비치환된 페닐렌기， 치환 또는 비치환된 바이페닐렌기 또는 치환 또는 비치환된 터페닐렌기이고, L 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group,
nl 내지 n3는 각각 독립적으로 0 또는 1이고, nl to n3 are each independently 0 or 1,
nl+n2+n3>l 이고, nl+n2+n3>l,
-Κ] [화학식 2-Χ] [화학식 2-Χ I] -Κ] [Formula 2-Χ] [Formula 2-Χ I]
상기 화학식 2-Κ 내지 2-Χ I에서 In the above formulas 2-Κ to 2-Χ I
Υ1 및 Υ2는 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기 또는 이들의 조합이고, Υ 1 and Υ 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
R11 내지 R16는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C50 아릴기, 치환 또는 비치환된 C2 내지 C50 헤테로아릴기 또는 이들의 조합이고, R 11 to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or a combination thereof. ,
상기 ΕΤ,ΕΤΙ, 및 ΕΤ2는 각각 독립적으로 하기 그룹 3에 나열된 치환 또는 비치환된 기에서 선택되고, Wherein ΕΤ, ΕΤΙ, and ΕΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 3 below,
상기 ΗΤ,Η Ί, 및 ΗΤ2는 각각 독립적으로 하기 그룹 4에 나열된 치환 또는
비치환된 기에서 선택되고 The ΗΤ, Η Ί, and ΗΤ2 are each independently a substitution listed in Group 4 below, or is selected from an unsubstituted group
[그룹 3] [Group 3]
여기서 "치환"은 적어도 하나의 수소가 중수소, 할로겐기, 히드톡시기, 아미노기, 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기, C2 내지 C30
헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기， 플루오로기, C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. Here, “substitution” means that at least one hydrogen is deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group. , C3 to C30 cycloalkyl group, C2 to C30 It means substituted with a heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group, or cyano group.
【청구항 7】 【Claim 7】
제 6항에서, In paragraph 6:
상기 전자수송보조층은, The electron transport auxiliary layer is,
상기 화학식 1- 1로 표현되는 제 1 화합물; 및 A first compound represented by Formula 1-1; and
상기 화학식 2- X I로 표현되는 제 2 화합물을 포함하는 유기 광전자 소자. An organic optoelectronic device comprising a second compound represented by Formula 2-XI.
【청구항 8】 【Claim 8】
제 1항에서, In paragraph 1:
상기 제 3 화합물은 하기 화학식 3- 1 또는 화학식 3- Π로 표현되는 유기 광전자 소자: The third compound is an organic optoelectronic device represented by the following Chemical Formula 3-1 or Chemical Formula 3-Π:
화학식 3- 1 ] [화학식 Formula 3-1] [Formula 3-1] [Formula 3-1]
상기 화학식 3- 1 및 화학식 3- Π에서 In Formula 3-1 and Formula 3-Π
X1은 0 또는 S이고, X 1 is 0 or S,
R17 및 R18은 각각 독립적으로, 수소, 중수소, 할로겐, 치환 또는 비치환된 C1 내지 C20 알킬기， 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C1 내지 C20 알콕시기, 치환 또는 비치환된 C3 내지 C20 시클로알콕시기, 치환 또는 비치환된 C1 내지 C20 알킬티오기 , 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C6 내지 C30 아릴티오기, 치환 또는 비치환된 C2 내지 C30 해테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기， 시아노기, 니트로기, 히드톡실기 또는 카르복실기, 또는 이들의 조합이고,
Ar2 및 Ar3는 각각 독립적으로, 치환 또는 비치환된 C6 내지 C30 아릴기 또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴기이고, R 17 and R 18 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or Unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof, Ar 2 and Ar 3 are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
L2 내지 L4는 각각 독립적으로 단일결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 헤테로아릴렌기 또는 이들의 조합이고， L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
n4 내지 n6는 각각 독립적으로, 0 내지 3 중 어느 하나인 정수이고, 여기서 "치환 "은 적어도 하나의 수소가 중수소, 할로겐기， 히드록시기, 아미노기， 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기， C2 내지 C30 헤테로시클로알킬'기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기， C1 내지 C20 알콕시기， 플루오로기， C1 내지 C10 트리폴루오로알킬기 또는 시아노기로 치환된 것을 의미한다. n4 to n6 are each independently an integer from 0 to 3, where "substitution" means that at least one hydrogen is deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, or a nitro group. , substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl ' group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group. , It means substituted with a fluoro group, a C1 to C10 tripoluoroalkyl group, or a cyano group.
【청구항 9) 【Claim 9)
제 1항에서, In paragraph 1:
상기 제 3 화합물은 하기 화학식 3-ΠΙ 내지 화학식 3-K 중 적어도 하나로 표현되는 유기 광전자 소자: The third compound is an organic optoelectronic device represented by at least one of the following formulas 3-ΠΙ to formula 3-K:
3-m] [화학식 3-IV] [화학식 3- V] 3-m] [Formula 3-IV] [Formula 3-V]
[화학식 3-VI] [화학식 3-νΠ] [화학
[Formula 3-VI] [Formula 3-νΠ] [Chemistry
-K] -K]
상기 화학식 3-ffl 내지 화학식 3-K에서, In Formula 3-ffl to Formula 3-K,
X1 및 X3은 각각 독립적으로 0 또는 S이고, X 1 and X 3 are each independently 0 or S,
X2는 0, S, 또는 CRcRd이고, X 2 is 0, S, or CR c R d ,
R17 내지 R27, RC, 및 Rd 각각 독립적으로, 수소, 중수소, 할로겐, 치환 또는 비치환된 C 1 내지 C20 알킬기， 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C1 내지 C20 알콕시기, 치환 또는 비치환된 C3 내지 C20 시클로알콕시기, 치환 또는 비치환된 C1 내지 C20 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기， 치환 또는 비치환된 C6 내지 C30 아릴티오기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실 7 또는 카르복실기, 또는 이들의 조합이고, R 17 to R 27 , R C , and R d each independently, hydrogen, deuterium, halogen, substituted or unsubstituted C 1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group. , substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted A ringed C3 to C30 silyl group, cyano group, nitro group, hydroxyl 7 or carboxyl group, or a combination thereof,
Ar2 및 Ar3는 각각 독립적으로， 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 Ar 2 and Ar 3 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted group.
쿼터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 안트라세닐기, 치환 또는 비치환된 페난:트렌일기, 치환 또는 비치환된 피렌일기 (pyrenyl), 치환 또는 비치환된 트리페닐렌기, 치환 또는 비치환된 플루오레닐기， 치환 또는 비치환된 디벤조퓨라닐기, 치환 또는 비치환된 디벤조티오페닐기, 또는 이들의 조합이고,Quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenan:trenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted triphenylene group, A substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,
L2 내지 L4는 각각 독립적으로 단일결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 해테로아릴렌기 또는 이들의 조합이고, L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
n4 내지 n6은 각각 독립적으로, 0 내지 3 중 어느 하나인 정수이고, 여기서 "치환 "은 적어도 하나의 수소가 중수소, 할로겐기, 히드록시기,
아미노기, 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기, C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기, 풀루오로기, C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. n4 to n6 are each independently an integer of 0 to 3, where "substitution" means that at least one hydrogen is deuterium, halogen group, hydroxy group, Amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group. , C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group, or cyano group.
【청구항 10] [Claim 10]
제 1항에서, In paragraph 1:
상기 화학식 3의 Ar2 및 Ar3는 각각 독립적으로, 하기 그룹 6에 나열된 치환 또는 비치환된 기에서 선택된 하나인 유기 광전자 소자: Ar 2 and Ar 3 of Formula 3 are each independently selected from the substituted or unsubstituted groups listed in Group 6:
그룹 6] Group 6]
상기 그룹 6에서, In group 6 above,
Y는 0, S, CRfRg, SiRhR' 또는 NRj이고, Y is 0, S, CR f R g , SiR h R' or NR j ,
*은 연결 지점이고, * is the connection point,
Re 내지 Rj는 각각 독립적으로， 수소, 중수소, 치환 또는 비치환된 C1 내
C20 알킬기, 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기， 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 또는 이들의 조합이고, R e to R j are each independently hydrogen, deuterium, substituted or unsubstituted C1. C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or An unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group, or a combination thereof,
여기서 "치환 "은 적어도 하나의 수소가 증수소, 할로겐기, 히드록시기, 아미노기， 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기, C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 해테로아릴기, C1 내지 C20 알콕시기, 플루오로기, C1 내지 C10 트리플투오로알킬기 또는 시아노기로 치환된 것올 의미한다. Here, “substitution” means that at least one hydrogen is hydrogen, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, Substituted with a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group. It means everything.
【청구항 11】 【Claim 11】
제 1항에서, In paragraph 1:
상기 전자수송보조층은, 하기 화학식 1- 1 및 1- Π로 표현되는 제 1 화합물 중 적어도 1종; 및 하기 화학식 2-K 내지 2- X I로 표현되는 제 2 화합물 중 적어도 1종을 포함하고， The electron transport auxiliary layer includes at least one of the first compounds represented by the following formulas 1-1 and 1-Π; And at least one of the second compounds represented by the following formulas 2-K to 2-X I,
상기 정공수송보조층은, 하기 화학식 3-ΙΠ 내지 화학식 3-K로 표현되는 제 3 화합물 중 적어도 1종을 포함하는 유기 광전자 소자: The hole transport auxiliary layer is an organic optoelectronic device comprising at least one of the third compounds represented by the following formulas 3-ΙΠ to 3-K:
1- 1 ] [화학식 ι- π ] 1- 1 ] [Formula ι- π ]
상기 화학식 1- 1 및 1- Π에서, In the above formulas 1-1 and 1-Π,
Z는 각각 독립적으로 N 또는 CRa이고, Z is each independently N or CR a ,
Z 중 적어도 하나는 N 이고, At least one of Z is N,
R1 내지 R10 및 Ra는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C12 아릴기 또는 이들의 조합이고, R 1 to R 10 and R a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof,
L1은 치환 또는 비치환된 페닐렌기, 치환 또는 비치환된 바이페닐렌기 또는 치환 또는 비치환된 터페닐렌기이고,
nl 내지 n3는 각각 독립적으로 0 또는 1이고, L 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group, nl to n3 are each independently 0 or 1,
nl+n2+n3>l 이고， nl+n2+n3>l,
2-K] [화학식 2- X ] [화학식 2- X I ] 2-K] [Formula 2-X] [Formula 2-X I]
상기 화학식 2-K 내지 2- X I에서 In the above formulas 2-K to 2-
Y1 및 Y2는 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기 또는 이들의 조합이고， Y 1 and Y 2 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
R" 내지 R16는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C50 아릴기, 치환 또는 비치환된 C2 내 C50 헤테로아릴기 또는 이들의 조합이고, R" to R 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or a combination thereof. ,
상기 ΕΤ, ΕΤΊ, 및 ΕΤ2는 각각 독립적으로 하기 그룹 3에 나열된 치환 또는 비치환된 기에서 선택되고, Wherein ΕΤ, ΕΤΊ, and ΕΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 3 below,
상기 ΗΤ, ΗΤΙ, 및 ΗΤ2는 각각 독립적으로 하기 그룹 4에 나열된 치환 또는 비치환된 기에서 선택되고, .
Wherein ΗΤ, ΗΤΙ, and ΗΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 4 below.
[그룹 3]
[Group 3]
[그룹 4] [Group 4]
상기 그룹 3 및 4에서 *은 연결 지점이고,
-m] [화학식 3-IV] [화학식 3-V] In groups 3 and 4 above, * is a connection point, -m] [Formula 3-IV] [Formula 3-V]
-VI] [화학식 3-W] [화학식 3-VI] -VI] [Formula 3-W] [Formula 3-VI]
상기 화학식 3-ΙΠ 내지 화학식 3-K에서, In Formula 3-ΙΠ to Formula 3-K,
X1 및 X3은 각각 독립적으로 0 또는 S이고， X 1 and X 3 are each independently 0 or S,
X2는 0, S, 또는 CRcRd이고, X 2 is 0, S, or CR c R d ,
R17 내지 R27, RC, 및 Rd 각각 독립적으로, 수소, 중수소, 할로겐， 치환 또는 비치환된 C1 내지 C20 알킬기， 치환 또는 비치환된 C3 내지 C20 시클로알킬기, 치환 또는 비치환된 C1 내지 C20 알콕시기, 치환 또는 비치환된 C3 내지 C20 시클로알콕시기, 치환 또는 비치환된 C1 내지 C20 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아르알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C6 내지 C30 아릴티오기,
치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 아미노기, 치환 또는 비치환된 C3 내지 C30 실릴기, 시아노기, 니트로기, 히드록실기 또는 카르복실기, 또는 이들의 조합이고, R 17 to R 27 , R C , and R d each independently, hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, A substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group, a cyano group, a nitro group, a hydroxyl group or a carboxyl group, or a combination thereof. ,
Ar2 및 Ar3는 각각 독립적으로, 치환 또는 비치환된 페닐기, 치환또는 비치환된 바,이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 Ar 2 and Ar 3 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted phenyl group.
쿼터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 안트라세닐기, 치환 또는 비치환된 페난트렌일기, 치환또는 비치환된 피렌일기 (pyrenyl), 치환또는 비치환된 트리페닐렌기， 치환 또는 비치환된 플루오레닐기， 치환 또는 비치환된 디벤조퓨라닐기, 치환 또는 비치환된 디벤조티오페닐기, 또는 이들의 조합이고,Quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted pyrenyl group (pyrenyl), substituted or unsubstituted triphenylene group, substituted Or an unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,
L2 내지 L4는 각각 독립적으로 단일결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 헤테로아릴렌기 또는 이들의 조합이고, L 2 to L 4 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof,
n4 내지 n6은각각 독립적으로, 0 내지 3 증 어느 하나인 정수이고, 여기서 "치환' '은 적어도 하나의 수소가 중수소, 할로겐기, 히드록시기, 아미노기 , 치환 또는 비치환된 C1 내지 C30 아민기， 니트로기 , 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C3 내지 C30 시클로알킬기, C2 내지 C30 헤테로시클로알킬기, C6 내지 C30 아릴기, C2 내지 C30 헤테로아릴기, C1 내지 C20 알콕시기, 풀루오로기, C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. . n4 to n6 are each independently an integer from 0 to 3, where "substituted" means that at least one hydrogen is deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro Group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, It means substituted with a fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group.
【청구항 12】 【Claim 12】
제 1 1항에서, In paragraph 1 1:
상기 전자수송보조층은, 상기 화학식 1- 1로 표현되는 제 1 화합물, 및 상기 화학식 2- X I로 표현되는 제 2 화합물을 포함하고, The electron transport auxiliary layer includes a first compound represented by Formula 1-1, and a second compound represented by Formula 2-
상기 정공수송보조층은， 상기 화학식 3-νΠ, 화학식 3-VHI, 및 화학식 3-Κ로 표현되는 제 3 화합물 중 적어도 하나를 포함하는 유기 광전자 소자. The hole transport auxiliary layer is an organic optoelectronic device comprising at least one of the third compounds represented by Formula 3-νΠ, Formula 3-VHI, and Formula 3-Κ.
【청구항 13 ] [Claim 13]
거) 1항에서, o) In paragraph 1,
상기 정공수송보조충은 상기 정공수송층과 상기 발광층에 각각 접해있고, 상기 전자수송보조층은 상기 전자수송층과 상기 발광층에 각각 접해있는 유기 광전자 소자. The hole transport auxiliary layer is in contact with the hole transport layer and the light-emitting layer, respectively, and the electron transport auxiliary layer is in contact with the electron transport layer and the light-emitting layer, respectively. An organic optoelectronic device.
【청구항 14】
제 1항에서, 【Claim 14】 In paragraph 1:
상기 발광층은 형광 도편트를 더 포함하는 유기 광전자 소자. The light-emitting layer is an organic optoelectronic device further comprising a fluorescent dopant.
【청구항 15] [Claim 15]
제 1항 내지 제 14항 중 어느 한 항에 따론 유기 광전자 소자를 포함하는 표시 장치.
A display device comprising an organic optoelectronic device according to any one of claims 1 to 14.
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| KR1020140139143A KR101825541B1 (en) | 2014-10-15 | 2014-10-15 | Organic optoelectric device and display device |
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Also Published As
| Publication number | Publication date |
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| CN107075359A (en) | 2017-08-18 |
| KR20160044299A (en) | 2016-04-25 |
| KR101825541B1 (en) | 2018-02-05 |
| CN107075359B (en) | 2020-04-21 |
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