CN116332914A - Compound for organic electric element, organic electric element using the same, and electronic device using the same - Google Patents
Compound for organic electric element, organic electric element using the same, and electronic device using the same Download PDFInfo
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- CN116332914A CN116332914A CN202310372237.1A CN202310372237A CN116332914A CN 116332914 A CN116332914 A CN 116332914A CN 202310372237 A CN202310372237 A CN 202310372237A CN 116332914 A CN116332914 A CN 116332914A
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
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- SKLNPGGDKRKWKC-UHFFFAOYSA-N (2-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1Cl SKLNPGGDKRKWKC-UHFFFAOYSA-N 0.000 description 1
- RRCMGJCFMJBHQC-UHFFFAOYSA-N (2-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1Cl RRCMGJCFMJBHQC-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- CFPFMAGBHTVLCZ-UHFFFAOYSA-N (4-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(Cl)C=C1 CFPFMAGBHTVLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- XTLFKEOFTWLFPG-UHFFFAOYSA-N 1-bromo-2-ethylsulfanyl-3-iodobenzene Chemical compound BrC1=C(C(=CC=C1)I)SCC XTLFKEOFTWLFPG-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
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- NYPHKCKUTARNAQ-UHFFFAOYSA-N 4-bromo-1-ethylsulfanyl-2-iodobenzene Chemical compound BrC1=CC(=C(C=C1)SCC)I NYPHKCKUTARNAQ-UHFFFAOYSA-N 0.000 description 1
- UXIULWIJWDJDQD-UHFFFAOYSA-N 4-bromo-2-iodophenol Chemical compound OC1=CC=C(Br)C=C1I UXIULWIJWDJDQD-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
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- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
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- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
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- 239000011241 protective layer Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
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- 125000003003 spiro group Chemical group 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Abstract
The invention provides: novel mixtures capable of improving the luminous efficiency, stability and lifetime of the element; an organic electric element using the mixture; and an electronic device thereof.
Description
Technical Field
The present invention relates to a compound for an organic electric element, an organic electric element using the compound, and an electronic device thereof.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic electronic element using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer interposed therebetween. Here, in order to improve efficiency and stability of the organic electric element, the organic material layer is generally composed of a multi-layer structure which is composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, an electron injection layer, and the like.
Materials used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transporting material, such as a hole injecting material, a hole transporting material, an electron injecting material, and the like, according to their functions.
The properties of the bi-cyclic compound containing a heteroatom have a very large difference according to the material structure, and thus are applied to various layers as materials of organic electric elements. In particular, band gap (HOMO, LUMO), electric property, chemical property, and physical property are different according to the number and condensed position of rings and the type and arrangement of hetero atoms, and thus application development of layers of various organic electric elements using the compounds has been developed.
In a phosphorescent organic electric element using a phosphorescent dopant material, LUMO and HOMO energy levels of a host material have a great influence on efficiency and lifetime of the organic electric element, and depending on whether electron and hole injection in an emission layer, charge balance in the emission layer, and dopant quenching can be effectively controlled, it is possible to prevent a decrease in efficiency and lifetime due to light emission at an interface of a hole transport layer.
For fluorescent and phosphorescent host materials, we have recently studied to improve the efficiency and lifetime of organic electrical elements using TADF (thermally activated delayed fluorescence), exciplex, etc., and in particular, many studies have been made to determine the energy transfer method from the host material to the dopant material.
Although there are various methods for determining energy transfer in the emissive layer of TADF (thermally activated delayed fluorescence) and exciplex, it can be easily confirmed by PL lifetime (TRTP) measurement methods.
The TRTP (time resolved transient PL) measurement method is a method of observing the decay time after a pulsed light source is irradiated onto a subject film, and is a measurement method by which the energy transfer method can be determined by observing the energy transfer and emission delay time. The TRTP measurement is a measurement method capable of distinguishing fluorescence from phosphorescence, and an energy transfer method of a mixed host material, an exciplex energy transfer method, and a TADF energy transfer method.
As such, there are various factors that affect efficiency and lifetime depending on how energy is transferred from the host material to the dopant material.
Since the energy transfer method varies depending on the material, development of a stable and effective host material for an organic electric element has not been sufficiently conducted. Accordingly, there is a continuing need to develop new materials, and in particular, there is an urgent need to develop host materials for emissive layers.
Reference KR101170666B1 is used as prior art document.
Detailed description of the invention
Disclosure of Invention
The present invention has been made in order to solve the problems of phosphorescent host materials, and an object of the present invention is to provide a compound capable of controlling charge balance and improving efficiency and lifetime in an emission layer by controlling HOMO energy levels of host materials of phosphorescent emitter electronic elements including phosphorescent dopants, and an organic electronic element and an electronic device using the same.
Technical proposal
In order to control efficient hole injection in the emissive layer of a phosphorescent emissive organic electrical element, by including a second host material in combination with a first host material as a major component, the energy barrier between the emissive layer and adjacent layers can be reduced and charge balance in the emissive layer maximized to provide high efficiency and high lifetime of the organic electrical element.
The present invention provides an organic electric element including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes an emission layer, wherein the emission layer is a phosphorescent emission layer and includes a first host compound represented by formula 1 and a second host compound represented by formula 2.
The invention also provides an organic electric element and an electronic device using the compound represented by the formula.
Effects of the invention
By using the mixture according to the present invention as a phosphorescent host material, high luminous efficiency and low driving voltage of an organic electric element can be achieved, and the lifetime of the device can be greatly improved.
Drawings
Fig. 1 is an example of an organic electroluminescent device according to the present invention.
100: organic electrical element, 110: substrate and method for manufacturing the same
120: first electrode (anode), 130: hole injection layer
140: hole transport layer, 141: buffer layer
150: emission layer, 151: emission assisting layer
160: electron transport layer, 170: electron injection layer
180: second electrode (cathode)
Detailed Description
Hereinafter, some embodiments of the present invention will be described in detail. In addition, in the following description of the present invention, a detailed description thereof will be omitted when known functions and configurations incorporated herein may make the subject matter of the present invention rather unclear.
Further, when describing the components of the present invention, terms such as first, second, A, B, (a), (b), and the like may be used herein. Each of these terms is not intended to limit the substance, order, or sequence of corresponding components, but is merely intended to distinguish the corresponding components from other components. It should be noted that if a component is described as being "connected," "coupled," or "connected" to another component, the component may be directly connected or coupled to the other component, but the other component may be "connected," "coupled," or "connected" between the components.
As used in the specification and the appended claims, the following are the meanings of the following terms, unless otherwise indicated.
The term "halo" or "halogen" as used herein includes fluoro, bromo, chloro or iodo unless otherwise indicated.
The term "alkyl" or "alkyl group" as used herein has a single bond of 1 to 60 carbon atoms, unless otherwise specified, and means a saturated aliphatic functionality, including a straight chain alkyl group, a branched alkyl group, a cycloalkyl group (alicyclic), a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a cycloalkyl group.
The term "haloalkyl" or "haloalkyl" as used herein includes alkyl groups substituted with halogen unless otherwise specified.
The term "heteroalkyl," as used herein, means an alkyl group in which one or more of the carbon atoms making up the alkyl group are replaced with a heteroatom, unless otherwise indicated.
The term "alkenyl" or "alkynyl" as used herein has a double or triple bond of 2 to 60 carbon atoms, unless otherwise specified, but is not limited thereto and includes straight or branched chain groups.
The term "cycloalkyl" as used herein means, unless otherwise specified, an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.
The term "alkoxy", "alkoxy group" or "alkyloxy group" as used herein means that an oxy group is attached to an alkyl group and has from 1 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.
The term "alkenyloxy", "alkenyloxy group" or "alkenyloxy group" as used herein means that an oxy group is attached to an alkenyl group and has 2 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.
The term "aryloxy group" or "aryloxy group" as used herein means that an oxy group is attached to an aryl group and has 6 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.
The term "aryl group" or "arylene group" as used herein has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto. Aryl or arylene groups herein mean monocyclic and polycyclic aromatic groups and may also be formed in combination with adjacent groups. Examples of "aryl groups" may include phenyl groups, biphenyl groups, fluorene groups, or spirofluorene groups.
The prefix "aryl" or "aryl" means a group substituted with an aryl group. For example, an arylalkyl group may be an alkyl group substituted with an aryl group, and an arylalkenyl group may be an alkenyl group substituted with an aryl group, with the aryl-substituted group having the number of carbon atoms as defined herein.
Furthermore, when the prefixes are named sequentially, this means that the substituents are listed in the order first described. For example, arylalkoxy means alkoxy substituted with aryl, alkoxycarbonyl means carbonyl substituted with alkoxy, and arylcarbonylalkenyl also means alkenyl substituted with arylcarbonyl, wherein arylcarbonyl may be carbonyl substituted with aryl.
The term "heteroalkyl," as used herein, means an alkyl group containing one or more heteroatoms, unless otherwise specified. The term "heteroaryl group" or "heteroarylene group" as used herein means a C2 to C60 aryl or arylene group containing one or more heteroatoms, but is not limited thereto, and includes at least one of monocyclic and polycyclic, and may also be formed in combination with an adjacent group, unless otherwise specified.
The term "heterocyclic group" as used herein contains one or more heteroatoms, has from 2 to 60 carbon atoms, unless otherwise specified, but is not limited to, including any of monocyclic and polycyclic, and may include heteroalicyclic and/or heteroaromatic rings. In addition, it is also possible to combine with adjacent groups to form heterocyclic groups.
The term "heteroatom" as used herein means at least one of N, O, S, P or Si unless otherwise specified.
Furthermore, the term "heterocyclic group" may include SO-containing groups 2 Instead of the carbon ring constituting the ring. For example, "heterocyclic group" includes the following compounds.
The term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term "aliphatic ring" as used herein means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, unless otherwise specified.
The term "ring" as used herein means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, or a condensed ring formed by a combination thereof, and includes saturated or unsaturated rings, unless otherwise specified.
In addition to the hetero compounds mentioned above, other hetero compounds or groups include, but are not limited to, one or more heteroatoms.
The term "carbonyl" as used herein, unless otherwise specified, is represented by-COR ', wherein R' may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination of these.
The term "ether" as used herein, unless otherwise specified, is represented by-R-O-R ', wherein R or R' may independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination of these.
The term "substituted or unsubstituted" as used herein means that the substituent is substituted with at least one substituent including, but not limited to, deuterium, hydrogen, halogen, amino groups, nitrile groups, nitro groups, C, unless otherwise specified 1 -C 20 Alkyl group, C 1 -C 20 Alkoxy groups, C 1 -C 20 Alkyl amine group, C 1 -C 20 Alkyl thiophene group, C 6 -C 20 Arylthiophene group, C 2 -C 20 Alkenyl group, C 2 -C 20 Alkynyl radicals, C 3 -C 20 Cycloalkyl radicals, C 6 -C 20 Aryl group, C substituted with deuterium 6 -C 20 Aryl group, C 8 -C 20 An arylalkenyl group, a silane group, a boron group, a germanium group, andC 2 -C 20 a heterocyclic group.
Unless explicitly stated otherwise, the formulae used in the present invention as used herein apply in the same manner as defined for substituents according to the definition of the index of the following formulae.
Here, when a is an integer of 0, this means the substituent R 1 Not present, that is, when a is 0, this means that all hydrogen is bound to carbon forming a benzene ring, and in this case, display of hydrogen bound to carbon may be omitted, and chemical formula or compound may be described.
When a is an integer of 1, a substituent R 1 Is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, they are respectively bonded as follows, wherein R 1 May be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, but the symbol of hydrogen bonded to the carbon forming the benzene ring is omitted.
Hereinafter, a compound according to aspects of the present invention and an organic electrical element including the compound will be described.
The present invention provides an organic electric element comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer comprises an emission layer, wherein the emission layer comprises a first host compound represented by formula 1 and a second host compound represented by formula 2 as the phosphorescent emission layer.
{ in the formulae 1 and 2,
1)Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 and Ar is a group 7 Each independently selected from hydrogen; deuterium; halogen; c (C) 6 -C 60 An aryl group; fluorenyl groups; c comprising at least one heteroatom in O, N, S, si, P 2 -C 60 A heterocyclic group; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; c (C) 1 -C 50 An alkyl group; c (C) 2 -C 20 An alkenyl group; c (C) 2 -C 20 An alkynyl group; c (C) 1 -C 30 An alkoxy group; c (C) 6 -C 30 An aryloxy group; and-L' -N (R) a )(R b ) The method comprises the steps of carrying out a first treatment on the surface of the And Ar is 1 And Ar is a group 2 Or Ar 3 And Ar is a group 4 May be combined with each other to form a ring,
2) Wherein L' is selected from single bonds; c (C) 6 -C 60 An arylene group; fluorenylene groups; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; and C 2 -C 60 Heterocycle, and R a And R is b Each independently selected from C 6 -C 60 An aryl group; fluorenyl groups; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; and C containing at least one heteroatom of O, N, S, si and P 2 -C 60 A heterocyclic group which is a heterocyclic group,
3)L 1 、L 2 、L 3 、L 4 and L 5 Independently selected from single bonds; c (C) 6 -C 60 An arylene group; fluorenylene groups; or C containing at least one heteroatom of O, N, S, si and P 2 -C 60 A heteroarylene group;
4)X 1 is O or S, and is preferably selected from the group consisting of,
5) Ring A and ring B are independently C 6 -C 60 An aryl group; or C 2 -C 20 A heterocyclic group which is a heterocyclic group,
6)X 2 is a single bond, N-L 6 -Ar 7 O, S or CR' R ",
wherein R 'and R' are independently hydrogen; c (C) 6 -C 60 An aryl group; fluorenyl groups; c (C) 3 -C 60 A heterocyclic group; or C 1 -C 50 An alkyl group; r 'and R' may combine with each other to form a spiro ring,
7) x is an integer from 0 to 4, y is an integer from 0 to 3, R c And R is d Each independently selected from hydrogen; c (C) 6 -C 60 An aryl group; fluorenyl groups; c comprising at least one heteroatom of O, N, S, si and P 2 -C 60 A heterocyclic group; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; c (C) 1 -C 50 An alkyl group; c (C) 2 -C 20 An alkenyl group; c (C) 2 -C 20 An alkynyl group; c (C) 1 -C 30 An alkoxy group; c (C) 6 -C 30 An aryloxy group; and-L' -N (R) a )(R b )，
8) Wherein the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group, and aryloxy group may be substituted with one or more substituents selected from deuterium; halogen; a silane group; a siloxane group; a boron group; a germanium group; a cyano group; a nitro group; c (C) 1 -C 20 Alkylthio groups; c (C) 1 -C 20 An alkoxy group; c (C) 1 -C 20 An alkyl group; c (C) 2 -C 20 An alkenyl group; c (C) 2 -C 20 An alkynyl group; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group; fluorenyl groups; c (C) 2 -C 20 A heterocyclic group; c (C) 3 -C 20 Cycloalkyl groups; c (C) 7 -C 20 Arylalkyl group and C 8 -C 20 An arylalkenyl group, wherein the substituents may combine with each other to form a saturated or unsaturated ring, wherein the term "ring" means C 3 -C 60 Aliphatic rings or C 6 -C 60 Aromatic ring or C 2 -C 60 Heterocyclic groups or formed by combinations thereofCondensed rings.
Furthermore, the present invention provides an organic electric element, wherein A and B in formula 1 each independently include a compound represented by any one of the following formulas a-1 to a-7
In the formulae a-1 to a-7,
Z 1 to Z 48 Each independently is CR c Or N, or a combination of two,
is bonded to L 1 To L 3 Z of (2) 1 To Z 48 Is carbon (C),
R c and R is R a Is defined as the same as the definition of (a),
* Indicating the position to be condensed.
The present invention provides an organic electrical element comprising a compound wherein L in formula 1 or formula 2 1 To L 5 Represented by any one of the following formulas b-1 to b-13.
In the formulae b-1 to b-13,
y is N-L 5 -Ar 7 O, S or CR d R e ，
L 5 And L is equal to 3 Is defined as the same as the definition of (a),
Ar 7 with Ar 5 Is defined as the same as the definition of (a),
R d and R is e And R is R a Is defined as the same as the definition of (a),
a. c, d and e are each independently integers from 0 to 4, b is an integer from 0 to 6,
f and g are each independently an integer of 0 to 3, h is an integer of 0 to 2, i is an integer of 0 or 1,
R 1 、R 2 and R is 3 Each independently is hydrogen; deuterium; tritium; halogen; a cyano group; a nitro group; c (C) 6 -C 60 An aryl group; fluorenyl groups; c comprising at least one heteroatom in O, N, S, si or P 2 -C 60 A heterocyclic group; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; c (C) 1 -C 50 An alkyl group; c (C) 2 -C 20 An alkenyl group; c (C) 2 -C 20 An alkynyl group; c (C) 1 -C 30 An alkoxy group; c (C) 6 -C 30 An aryloxy group; and-L a -N(R f )(R g ) The method comprises the steps of carrying out a first treatment on the surface of the Or in the case where a, b, c, d, e, f and g are 2 or more and h is 2 or more, each of the plurality is the same or different from each other, and the plurality R 1 Or a plurality of R 2 Or a plurality of R 3 Or adjacent R 1 And R is 2 Or adjacent R 2 And R is 3 May be combined with each other to form an aromatic ring or a heteroaromatic ring,
wherein L is a Selected from single bonds; c (C) 6 -C 60 An arylene group; fluorenylene groups; c containing at least one heteroatom of O, N, S, si and P 2 -C 60 A heterocyclic group; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; and C 3 -C 60 Aliphatic hydrocarbon groups;
R f and R is g Each independently selected from C 6 -C 60 An aryl group; fluorenyl groups; c containing at least one heteroatom of O, N, S, si and P 2 -C 60 A heterocyclic group; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of the aromatic ring,
Z 49 、Z 50 and Z 51 Each independently is CR h Or N, or a combination of two,
Z 4 、Z 50 and Z 51 At least one of which is N,
R h selected from the group consisting ofHydrogen; deuterium; tritium; halogen; a cyano group; a nitro group; c (C) 6 -C 60 An aryl group; fluorenyl groups; c comprising at least one heteroatom in O, N, S, si or P 2 -C 60 A heterocyclic group; c (C) 3 -C 60 Aliphatic ring and C 6 -C 60 Condensed ring groups of aromatic rings; c (C) 1 -C 50 An alkyl group; c (C) 2 -C 20 An alkenyl group; c (C) 2 -C 20 An alkynyl group; c (C) 1 -C 30 An alkoxy group; c (C) 6 -C 30 An aryloxy group; and adjacent R 1 And R is h May be combined with each other to form an aromatic ring or a heteroaromatic ring.
The present invention provides a compound, wherein the first host compound represented by formula 1 includes a compound represented by any one of the following formulas 3 to 5.
3
4. The method is to
5. The method is to
In the formulae 3 to 5,
X 1 、A、B、L 1 、L 2 、Ar 2 、Ar 3 and Ar is a group 4 As in the case of the above-defined,
c and D are as defined for A,
w is N-L 7 -Ar 8 O, S or CR i R j ，
L 6 And L 7 And L is equal to 4 Is defined as the same as the definition of (a),
Ar 8 with Ar 5 Is defined as the same as the definition of (a),
R i and R is j And R is R a Is defined as the same as the definition of (a),
two Ar 8 Each of which is the same or different, two W are each the same or different, two C are each the same or different, and two D are each the same or different.
The present invention provides a compound, wherein the first host compound represented by formula 1 includes a compound represented by formula 6.
6. The method is to
In the case of the method of 6,
X 1 、Ar 2 、Ar 3 and Ar is a group 4 As in the case of the above-defined,
Z 1 、Z 2 、Z 3 and Z 4 Each independently is CR c Or N, or a combination of two,
z bound to N 1 To Z 4 Is carbon (C),
R c and R is R a Is defined as the same as the definition of (a),
w is N-L 7 -Ar 8 O, S or CR i R j ，
L 7 And L is equal to 4 Is defined as the same as the definition of (a),
Ar 8 with Ar 5 Is defined as the same as the definition of (a),
R i and R is j And R is R a Is the same as defined in the following.
In the present invention, as another example, the first host compound represented by formula 1 includes a compound represented by formula 7 or formula 8 or formula 9.
7. The method of the invention
8. The method is used for preparing the product
9. The invention is applicable to
In the formulae 7 to 9,
X 1 、Ar 2 、Ar 3 and Ar is a group 4 ，Z 1 、Z 2 、Z 3 、Z 4 And W is the same as defined above.
In another aspect, the second host compound represented by formula 2 includes a compound represented by any one of formulas 10 to 13.
In the formulae 10 to 13,
X 2 、L 3 、L 4 、L 5 、Ar 5 、Ar 6 、R c 、R d x, y are the same as defined above.
Further, the second host compound represented by formula 2 includes a compound represented by formula 14.
14, of the order of magnitude
In the formula (14) of the present invention,
1)X 2 、L 3 、L 4 、L 5 、Ar 5 、R c 、R d x, y are the same as defined above,
2)X 3 and X is 2 Is defined as the same as the definition of (a),
3)R e and R is f And R is R d And R is c Is defined as the same as the definition of (a),
4) n is as defined for y, and m is as defined for x.
The second host compound represented by formula 2 includes compounds represented by formulas 15 to 18.
In the formulae 15 to 18,
X 2 、L 3 、L 4 、L 5 、Ar 5 、R c 、R d 、x、y、X 3 、R e 、R f m, n are as defined above.
Further, the compound represented by formula 2 includes a compound represented by formula 19.
19, of the order of magnitude
In the process of 19, the process is carried out,
a is the following formula A-1 or formula A-2,
X 11 and X 12 Each independently is O or S,
a ', b', c 'and d' are each independently 0 or 1,
Ar 11 、Ar 12 、Ar 13 and Ar is a group 14 Each independently is C 6 -C 18 An aryl group.
The compound represented by formula 19 includes a compound represented by the following formula 20 or formula 21.
In the formulae 20 and 21,
X 11 、X 12 a ', b', cd' is the same as defined above.
As another example, the compound represented by formula 2 includes a compound represented by formula 22.
These compounds may be mixed with a second host such as biscarbazoles, tertiary amines, and polycyclic heterocyclic compounds for use in the emissive layer.
< 22>
In the formula (22) of the present invention,
a is the following formula A-1 or formula A-2,
Ar 11 is C 6 -C 18 An aryl group is used as a substituent,
X 11 、X 12 and X 13 Each independently is O or S,
m 'and n' are each independently 0 or 1,
a 'and c' are each independently integers of any one of 0 to 5,
d' is an integer of any one of 0 to 4,
R 21 is C 6 -C 18 An aryl group is used as a substituent,
Ar 13 and Ar is a group 14 Each independently is C 6 -C 18 An aryl group.
Further, the compound represented by formula 22 may be represented by the following formula 23 or formula 24.
In the formulae 23 and 24,
X 11 、X 12 、X 13 、a'、c'、d'、m'、n'、Ar 13 、Ar 14 、R 21 the same as defined above.
The compound included in formula 2 may be mixed with a second host such as a biscarbazole, a tertiary amine, and a polycyclic heterocyclic compound for an emissive layer, and more particularly, the compound included in formula 19 or formula 22 may be used.
As another example, the first host compound represented by formula 1 includes compounds 1-1 to 1-175.
As another example, the second host compound represented by formula 2 includes the following compounds. Namely, compound 1'-1 to compound 1' -84, compound 2-1 to compound 2-60, compound 3-1 to compound 3-36, compound P-1 to compound P-120, compound 4-1 to compound 4-12, compound 5-1 to compound 5-20, compound 6-1 to compound 6-16 and compound 7-1 to compound 7-24.
Referring to fig. 1, an organic electric element (100) according to the present invention includes a first electrode (120) formed on a substrate (110), a second electrode (180), and an organic material layer including a compound represented by formula 1 between the first electrode (120) and the second electrode (180). Here, the first electrode (120) may be an anode (positive electrode), and the second electrode (180) may be a cathode (negative electrode). In the case of an inverted organic electrical element, the first electrode may be a cathode and the second electrode may be an anode.
The organic material layer may include a hole injection layer (130), a hole transport layer (140), an emission layer (150), an emission auxiliary layer (151), an electron transport layer (160), and an electron injection layer (170) sequentially formed on the first electrode (120). Here, the remaining layers other than the emission layer (150) may not be formed. The organic material layer may further include a hole blocking layer, an electron blocking layer, an emission assisting layer (151), an electron transporting assisting layer, a buffer layer (141), and the like, and the electron transporting layer (160) and the like may function as a hole blocking layer.
Although not shown, the organic electric element according to the present invention may further include a protective layer formed on at least one side of the first electrode and the second electrode, the side being opposite to the organic material layer.
Otherwise, even if the same core is used, the band gap, electrical characteristics, interface characteristics, and the like may vary depending on which substituent is bonded at which position, and therefore, selection of the core and the sub-substituent combination related thereto is also very important, and particularly, when an optimal combination of the energy level and T1 value of each organic material layer and unique properties (mobility, interface characteristics, and the like) of the material are achieved, both long life and high efficiency can be achieved.
The organic electroluminescent device according to the embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) method. For example, after forming an anode by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate and forming an organic material layer including a hole injection layer (130), a hole transport layer (140), an emission layer (150), an electron transport layer (160), and an electron injection layer (170) thereon, an organic electroluminescent device according to an embodiment of the present invention may be manufactured by depositing a material that can be used as a cathode thereon.
In addition, an emission auxiliary layer (151) may be formed between the hole transport layer (140) and the emission layer (150), and an electron transport auxiliary layer may be formed between the emission layer (150) and the electron transport layer (160).
Accordingly, the present invention includes at least one hole transport layer between the first electrode and the emission layer, wherein the hole transport layer includes a hole transport layer, an emission auxiliary layer, or both, and wherein the hole transport layer includes a compound represented by formula 1.
Furthermore, the compounds represented by formulas 1 and 2 are mixed at a ratio of any one of 1:9 to 9:1 to be included in the emission layer, preferably mixed at a ratio of 1:9 to 5:5, more preferably mixed at a ratio of 2:8 or 3:7 to be included in the emission layer.
The present invention may further include a light efficiency enhancing layer formed on at least one of a side of the first electrode opposite to the organic material layer or a side of the second electrode opposite to the organic material layer.
Further, the organic material layer is formed by one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, or a roll-to-roll process, and since the organic material layer according to the present invention may be formed by various methods, the scope of the present invention is not limited by the method of forming the organic material layer.
The organic electric element according to the embodiment of the present invention may be of a front emission type, a rear emission type, or a double-side emission type depending on the material used.
WOLED (white organic light emitting device) is easy to achieve high resolution and excellent workability, while having an advantage that it can be manufactured using existing LCD color filter technology. Various structures of white organic light emitting devices mainly used as backlight devices have been proposed and patented. In general, R (red), G (green), B (blue) light emitting members are arranged in a side-by-side manner, and R, G, B light emitting layers are stacked one on top of the other, and blue (B) electroluminescence is performed by an organic light emitting layer, and a photoluminescent Color Conversion Material (CCM) method using an inorganic phosphor using light therefrom and the present invention can be applied to such WOLEDs.
The invention also provides an electronic device comprising a display device with an organic electrical element; and a control unit for driving the display device.
According to another aspect, the invention provides an electronic device wherein the organic electrical element is at least one of an OLED, an organic solar cell, an organic photoconductor, an organic transistor and an element for mono-or white illumination. At this time, the electronic device may be a wired/wireless communication terminal that is currently used or will be used in the future, and encompasses all kinds of electronic devices including mobile communication terminals, such as cellular phones, personal Digital Assistants (PDAs), electronic dictionaries, point-to-multipoint (PMPs), remote controllers, navigation units, game consoles, various kinds of televisions, and various kinds of computers.
Hereinafter, synthesis examples of the compounds represented by formulas 1 and 2 according to the present invention and preparation examples of the organic electric element of the present invention will be described in detail by way of examples, but are not limited to the following examples of the present invention.
Synthesis example 1
The final product 1 represented by formula 1 according to the present invention may be synthesized through a reaction between Sub 1 and Sub 2 as shown in the following reaction scheme 1, but is not limited thereto. X is X 1 、A、B、L 1 、L 2 、Ar 1 Or Ar 4 Can be the same as defined in formula 1, and Hal 1 Is Br or Cl.
< reaction scheme 1>
Synthesis example of Sub 1
Sub 1 of reaction scheme 1 is synthesized by the following reaction pathway of reaction scheme 2, but is not limited thereto.
< reaction scheme 2>
Synthesis example of sub 1-1
Starting material Sub 2-1 (15.22 g,89.94 mmol) was added to a round bottom flask and dissolved in toluene (750 mL) and Sub 1-1-c (CAS registry number: 669773-34-6) (46.14 g,134.91 mmol), pd was added 2 (dba) 3 (2.47g，2.70mmol)、P(t-Bu) 3 (1.46 g,7.19 mmol), naOt-Bu (25.93 g,269.81 mmol) and stirred at 80 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 23.61g of a product. (yield: 61%)
Synthesis example of sub 1-3
Sub 1-3-e (CAS registry number: 201138-91-2) (31.08 g,95.35 mmol), pd were added to the starting material Sub 2-12 (13.94 g,63.57 mmol) 2 (dba) 3 (1.75g，1.91mmol)、P(t-Bu) 3 (1.03 g,5.09 mmol), naOt-Bu (18.33 g,190.71 mmol), toluene (530 ml), the same procedure as described for the synthesis of Sub 1-1 was conducted to obtain 19.78g of a product. (yield: 67%).
Synthesis example of sub 1-5
(1) Synthesis of Sub 1-5-a
The starting material (2-bromo-6-iodophenyl) (ethyl) sulfane (9.94 g,28.98 mmol) was added to a round bottom flask and dissolved in THF (100 mL), and (4-chlorophenyl) boric acid (4.53 g,28.98 mmol), pd (PPh) 3 ) 4 (1.00 g,0.87 mmol), naOH (2.32 g,57.96 mmol), water (50 ml) and stirring at 80 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 8.55g of a product. (yield: 90%)
(2) Synthesis of Sub 1-5-b
To Sub 1-5-a (8.55 g,26.09 mmol) obtained in the above synthesis was added acetic acid (90 ml), 35% hydrogen peroxide (H 2 O 2 ) (2.66 g,78.28 mmol) and stirred at room temperature. When the reaction was completed, after neutralization with aqueous NaOH, extraction was performed with EA and washing with water. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography to obtain 8.70g of a product. (yield: 97%)
(3) Synthesis of Sub 1-5-c
To Sub 1-5-b (8.70 g,25.32 mmol) obtained in the above synthesis was added sulfuric acid (H 2 SO 4 ) (50 ml) and stirred at room temperature. When the reaction was completed, after neutralization with aqueous NaOH, extraction was performed with MC and washing with water. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography to obtain 7.16g of a product. (yield: 95%)
(4) Synthesis of Sub 1-5
The obtained Sub 1-5-c (7.16 g,24.06 mmol) was added to a round bottom flask and dissolved in toluene (240 mL), sub 2-11 (5.28 g,24.06 mmol), pd was added 2 (dba) 3 (0.66g，0.72mmol)、P(t-Bu) 3 (0.49 g,2.41 mmol), naOt-Bu (4.62 g,48.12 mmol) and stirred at 80 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 8.08g of a product. (yield: 77%)
Synthesis example of sub 1-17
(1) Synthesis of Sub 1-17-a
To a starting material (4-bromo-2-iodophenyl) (ethyl) sulfane (10.65 g,31.05 mmol) was added (4-chloro- [1,1' -biphenyl) ]-2-yl) boronic acid (7.22 g,31.05 mmol), pd (PPh) 3 ) 4 (1.08 g,0.93 mmol), naOH (2.48 g,62.10 mmol), THF (100 ml), water (50 ml), and the same procedure as described in the synthesis of Sub 1-5-a was carried out to obtain 9.90g of a product. (yield: 79%).
(2) Synthesis of Sub 1-17-b
Sub 1-17-a (9.90 g,24.52 mmol), acetic acid (80 ml), 35% hydrogen peroxide (H) 2 O 2 ) (2.50 g,73.56 mmol) Synthesis method for Sub 1-5-b. Thus, 9.78g (yield: 95%) of a product was obtained.
(3) Synthesis of Sub 1-17-c
Sub 1-17-b (9.78 g,23.30 mmol) obtained in the above synthesis was used for the synthesis method of Sub 1-5-c. Thus, 7.84g (yield: 90%) of a product was obtained.
(4) Synthesis of Sub 1-17
To Sub 1-17-c (7.84 g,20.98 mmol) obtained in the above synthesis was added Sub2-78 (7.02 g,20.98 mmol), pd 2 (dba) 3 (0.58g，0.63mmol)、P(t-Bu) 3 (0.42 g,2.10 mmol), naOt-Bu (4.03 g,41.96 mmol) and toluene (210 ml), and the same procedure as described in the synthesis of Sub1-5 was performed to obtain 10.79g of a product. (yield: 82%).
Synthesis example of sub 1-82
To starting material Sub 2-1 (16.48 g,97.38 mmol), sub 1-82-c (CAS registry number 83834-10-0) (49.96 g,146.07 mmol), pd were added 2 (dba) 3 (2.68g，2.92mmol)、P(t-Bu) 3 (1.58 g,7.79 mmol), naOt-Bu (28.08 g,292.15 mmol), toluene (810 ml), and the same procedure as described in the synthesis of Sub 1-1 was performed to obtain 26.40g of a product. (yield: 63%).
Synthesis example of sub 1-102
(1) Synthesis of Sub 1-102-d
To a starting material of 4-bromo-2-iodophenol (39.85 g,133.32 mmol) was added (2-chlorophenyl) boronic acid (20.85 g,133.32 mmol), pd (PPh) 3 ) 4 (4.62 g,4.00 mmol), naOH (10.67 g,266.64 mmol), THF (440 ml), water (220 ml), and the same procedure as described in the synthesis of Sub1-5-a was carried out to obtain 28.73g of a product. (yield: 76%).
(2) Synthesis of Sub 1-102-e
To Sub 1-102-d (28.73 g,101.32 mmol) obtained in the above synthesis was added Pd (OAc) 2 (2.27 g,10.13 mmol), 3-nitropyridine (1.26 g,10.13 mmol), bzOOtBu (t-butyl peroxybenzoate) (39.36 g,202.65 mmol), C 6 F 6 (hexafluorobenzene) (150 ml), DMI (N, N' -dimethylimidazolidone) (100 ml) and refluxed at 90℃for 3 hours. When the reaction was complete, the temperature of the reaction product was cooled to room temperature, extracted with EA, and washed with water. The organic layer was dried over MgSO 4 The organic material was dried and concentrated, and the resulting organic material was separated using a silica gel column to obtain 13.69g (48%) of a product.
(3) Synthesis of Sub 1-102
To Sub 1-102-e (13.69 g,48.63 mmol) obtained in the above synthesis was added Sub 2-29 (13.39 g,48.63 mmol), pd 2 (dba) 3 (1.34g，1.46mmol)、P(t-Bu) 3 (0.98 g,4.86 mmol), naOt-Bu (9.35 g,97.25 mmol), toluene (490 ml), and the same steps as described in the synthesis of Sub 1-5 were performed to obtain 19.67g of a product. (yield: 85%).
Synthesis example of sub 1-104
Sub 1-104-c (CAS registry number: 31574-87-5) (27.73 g,81.07 mmol), pd were added to starting material Sub 2-1 (9.15 g,54.04 mmol) 2 (dba) 3 (1.48g，1.62mmol)、P(t-Bu) 3 (0.87 g,4.32 mmol), naOt-Bu (15.58 g,162.13 mmol), toluene (450 ml), andthe same procedure as described in the synthesis of Sub 1-1 was followed to obtain 15.12g of the product. (yield: 65%).
Synthesis example of sub 1-112
(1) Synthesis of Sub 1-112-a
To the starting material (3-bromo-2-iodophenyl) (and) sulfane (12.73 g,37.11 mmol) was added (2-chlorophenyl) boric acid (5.80 g,37.11 mmol), pd (PPh) 3 ) 4 (1.29 g,1.11 mmol), naOH (2.97 g,74.22 mmol), THF (120 ml), water (60 ml), and the same steps as described in the synthesis of Sub 1-5-a were carried out to obtain 9.48g of a product. (yield: 78%).
(2) Synthesis of Sub 1-112-b
Sub 1-112-a (9.48 g,28.93 mmol), acetic acid (95 ml), 35% hydrogen peroxide (H) obtained in the above synthesis were added 2 O 2 ) (2.95 g,86.80 mmol), and the same procedure as described in the synthesis method of Sub1-5-b was carried out to obtain 9.74g of a product. (yield: 98%).
(3) Synthesis of Sub 1-112-c
Sub 1-112-b (9.74 g,28.34 mmol) obtained in the above synthesis, sulfuric acid (H) 2 SO 4 ) (60 ml), and the same procedure as described in the synthesis method of Sub 1-5-c was carried out to obtain 7.76g of a product. (yield: 92%).
(4) Synthesis of Sub 1-112
To Sub 1-112-c (7.76 g,26.08 mmol) obtained in the above synthesis was added Sub 2-1 (4.41 g,26.08 mmol), pd 2 (dba) 3 (0.72g，0.78mmol)、P(t-Bu) 3 (0.53 g,2.61 mmol), naOt-Bu (5.01 g,52.15 mmol), toluene (260 ml), and the same steps as described in the synthesis of Sub1-5 were carried out to obtain 5.84g of a product. (yield)：58％)。
The compounds belonging to Sub1 may be, but are not limited to, the following compounds, and table 1 shows FD-MS (field desorption-mass spectrometry) values of some of the compounds belonging to Sub 1.
TABLE 1
II.Sub
2 synthesis
Sub 2 of reaction scheme 3 may be synthesized by the following reaction pathway of reaction scheme 3 (starting in korean patent registration No. 10-1251451 of the applicant (registration at 5 of 4 th 2013)), but is not limited thereto.
Z 1 Is Ar 1 Or Ar 3 ，Z 2 Is Ar 2 Or Ar 4 。
< reaction scheme 3>
The compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and table 2 shows FD-MS (field desorption-mass spectrometry) values of some compounds belonging to Sub 2.
TABLE 2
III Synthesis of the end product
After dissolution of Sub 1 (1 eq.) in toluene in a round bottom flask, sub 2 (1 eq.) Pd 2 (dba) 3 (0.03 eq), (t-Bu) 3 P (1.00 eq.) and NaOt-Bu (2 eq.) were stirred at 100deg.C. When the reaction is complete, the resulting compound is reacted with CH 2 Cl 2 And water extraction and the organic layer was subjected to MgSO 4 Dried and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain the final product 1.
The compounds 1-30, 1-32, 1-35, 1-37, 1-67, 1-80, 1-86, 1-94, 1-111, 1-119, and 1-133 of the present invention were produced by the synthetic methods disclosed in korean patent registration No. 10-1668448 (registered 10-17 in 2016) and korean patent registration No. 10-1789998 (registered 19 in 10-10 in 2017) of the present applicant.
1.1-1 Synthesis example
The obtained Sub 1-1 (5.97 g,13.87 mmol) was added to a round bottom flask and dissolved in toluene (140 mL), sub 2-17 (3.74 g,13.87 mmol), pd was added 2 (dba) 3 (0.38g，0.42mmol)、P(t-Bu) 3 (0.28 g,1.39 mmol), naOt-Bu (2.67 g,27.74 mmol) and stirred at 100deg.C. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 6.09g of a product. (yield: 71%)
2.1-2 Synthesis examples
To Sub 1-1 (5.29 g,12.29 mmol) obtained in the above synthesis was added Sub2-37 (4.32 g,12.29 mmol), pd 2 (dba) 3 (0.34g，0.37mmol)、P(t-Bu) 3 (0.25 g,1.23 mmol), naOt-Bu (2.36 g,24.58 mmol), toluene (125 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.81g of a product. (yield: 79%).
3.1-4 Synthesis examples
To Sub 1-3 (6.13 g,13.20 mmol) obtained in the above synthesis was added Sub2-41 (4.08 g,13.20 mmol), pd 2 (dba) 3 (0.36g，0.40mmol)、P(t-Bu) 3 (0.27 g,1.32 mmol), naOt-Bu (2.54 g,26.40 mmol), toluene (130 ml), and the synthesis procedure described for 1-1 was followedThe same procedure was followed to obtain 7.32g of the product. (yield: 80%).
4.1-10 Synthesis examples
To Sub 1-5 (5.56 g,12.75 mmol) obtained in the above synthesis was added Sub2-43 (4.28 g,12.75 mmol), pd 2 (dba) 3 (0.35g，0.38mmol)、P(t-Bu) 3 (0.26 g,1.28 mmol), naOt-Bu (2.45 g,25.51 mmol), toluene (130 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 8.06g of a product. (yield: 86%).
5.1-24 Synthesis examples
To Sub 1-17 (6.18 g,9.85 mmol) obtained in the above synthesis was added Sub2-1 (1.67 g,9.85 mmol), pd 2 (dba) 3 (0.27g，0.30mmol)、P(t-Bu) 3 (0.20 g,0.99 mmol), naOt-Bu (1.89 g,19.71 mmol), toluene (100 ml), and the same procedure as described in the synthesis method of 1-1 was performed to obtain 5.62g of a product. (yield: 75%).
6.1-122 Synthesis examples
To Sub 1-82 (5.05 g,11.73 mmol) obtained in the above synthesis was added Sub2-49 (4.12 g,11.73 mmol), pd 2 (dba) 3 (0.32g，0.35mmol)、P(t-Bu) 3 (0.24 g,1.17 mmol), naOt-Bu (2.26 g,23.47 mmol), toluene (120 ml), and the same procedure as described in the synthesis of 1-1 was performed to obtain 7.65g of a product. (yield: 93%).
7.1-125 Synthesis examples
To Sub 1-82 (5.20 g,12.08 mmol) obtained in the above synthesis was added Sub2-40 (3.13 g,12.08 mmol), pd 2 (dba) 3 (0.33g，0.36mmol)、P(t-Bu) 3 (0.24 g,1.21 mmol), naOt-Bu (2.32 g,24.17 mmol), toluene (120 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.69g of a product. (yield: 91%).
8.1-141 Synthesis examples
To Sub 1-102 (6.26 g,13.15 mmol) obtained in the above synthesis was added Sub2-1 (2.23 g,13.15 mmol), pd 2 (dba) 3 (0.36g，0.39mmol)、P(t-Bu) 3 (0.27 g,1.32 mmol), naOt-Bu (2.53 g,26.30 mmol), toluene (130 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.57g of a product. (yield: 82%).
9.1-146 Synthesis examples
To Sub 1-104 (6.12 g,14.22 mmol) obtained in the above synthesis was added Sub2-83 (5.84 g,14.22 mmol), pd 2 (dba) 3 (0.39g，0.43mmol)、P(t-Bu) 3 (0.29 g,1.42 mmol), naOt-Bu (2.73 g,28.43 mmol), toluene (140 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 8.00g of a product. (yield: 74%).
10.1-158 Synthesis examples
To Sub 1-112 (5.75 g,14.90 mmol) obtained in the above synthesis was addedSub2-29 (4.10 g,14.90 mmol), pd 2 (dba) 3 (0.41g，0.45mmol)、P(t-Bu) 3 (0.30 g,1.49 mmol), naOt-Bu (2.86 g,29.80 mmol), toluene (150 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.24g of a product. (yield: 67%).
Meanwhile, FD-MS values of the inventive compounds 1-1 to 1-175 prepared according to the above-described synthesis examples are shown in table 3 below.
TABLE 3
Synthesis example 2
The compound (final product) represented by formula 2 according to the present invention may be prepared by reacting Sub 3 and Sub 4 as shown in the following reaction scheme 4, but is not limited thereto.
< reaction scheme 4>
Synthesis example of 1' -1
In the case of Sub 1 (1) (34.7 g,80 mmol) and Sub2 (1) (30.9 g,80 mmol), K 2 CO 3 (19.3g，140mmol)、Pd(PPh 3 ) 4 (2.8 g,2.4 mmol) was placed in a round-bottomed flask, and THF and water were added to dissolve it, Then refluxed at 80℃for 12 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, and CH was used 2 Cl 2 Extracted and washed with water. The organic layer was dried over MgSO 4 The mixture was dried and concentrated, and the resulting organic material was separated using a silica gel column to obtain the desired product (37.4 g, 71%).
1' -6 Synthesis example
The synthesis method using 1' -1 was used with Sub 1 (6) (44.6 g,80 mmol) and Sub 2 (2) (30.9 g,80 mmol) to obtain the product (43.2 g, 69%).
1' -12 Synthesis example
The synthesis method using 1' -1 was used with Sub 1 (12) (42.7 g,80 mmol) and Sub 2 (33) (34.9 g,80 mmol) to obtain the product (42.7 g, 66%).
Synthesis example of 1' -33
The synthesis method using 1' -1 was used with Sub 1 (27) (40.8 g,80 mmol) and Sub 2 (9) (43.1 g,80 mmol) to obtain the product (51.0 g, 72%).
Synthesis example of 1' -44
The synthesis method using 1' -1 was used with Sub 1 (27) (40.8 g,80 mmol) and Sub 2 (10) (37.0 g,80 mmol) to obtain the product (45.4 g, 70%).
Synthesis example of 1' -53
The synthesis method using 1' -1 was used with Sub 1 (34) (44.0 g,80 mmol) and Sub 2 (29) (29.6 g,80 mmol) to obtain the product (41.2 g, 68%).
1' -64 Synthesis example
The synthesis method using 1' -1 was used with Sub 1 (37) (48.2 g,80 mmol) and Sub 2 (34) (34.9 g,80 mmol) to obtain the product (45.6 g, 71%).
1' -75 synthesis example
The synthesis method using 1' -1 was used with Sub 1 (25) (34.7 g,80 mmol) and Sub 2 (35) (41.8 g,80 mmol) to obtain the product (46.4 g, 73%).
Synthesis example of 2-1
The synthesis method using 1' -1 was used with Sub 1 (1) (34.7 g,80 mmol) and Sub 2 (27) (37.0 g,80 mmol) to obtain the product (42.3 g, 72%).
Synthesis examples of 2 to 22
The synthesis method using 1' -1 was used with Sub 1 (38) (50.7 g,80 mmol) and Sub 2 (24) (37.0 g,80 mmol) to obtain the product (51.6 g, 69%).
Synthesis examples 2 to 33
The synthesis method using 1' -1 was used with Sub 1 (27) (40.8 g,80 mmol) and Sub 2 (36) (49.2 g,80 mmol) to obtain the product (53.9 g, 70%).
Synthesis examples of 2 to 40
The synthesis method using 1' -1 was used with Sub 1 (25) (34.7 g,80 mmol) and Sub 2 (37) (43.1 g,80 mmol) to obtain the product (44.7 g, 69%).
Synthesis examples of 2-51
The synthesis method using 1' -1 was used with Sub 1 (33) (36.0 g,80 mmol) and Sub 2 (38) (35.7 g,80 mmol) to obtain the product (41.1 g, 70%).
Synthesis examples of 2 to 55
The synthesis method using 1' -1 was used with Sub 1 (39) (42.1 g,80 mmol) and Sub 2 (23) (37.0 g,80 mmol) to obtain the product (44.9 g, 68%).
Synthesis examples of 2 to 58
The synthesis method using 1' -1 was used with Sub 1 (25) (34.7 g,80 mmol) and Sub 2 (39) (47.9 g,80 mmol) to obtain the product (45.9 g, 66%).
Synthesis examples 3 to 10
The synthesis method using 1' -1 was used with Sub 1 (37) (28.6 g,80 mmol) and Sub 2 (10) (37.0 g,80 mmol) to obtain the product (38.9 g, 74%).
Synthesis example of P-41
Core 2 (5 g,14 mmol), sub 1 (4.6 g,15.2 mmol), pd (PPh) 3 ) 4 (0.5g，0.4mmol)、K 2 CO 3 (5.7 g,41.3 mmol), THF and water were added to the round-bottomed flask and stirred at 90 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 4.6g of P-41. (yield: 57%)
Synthesis example of P-91
Core 1 (5 g,14 mmol), sub 9 (5.8 g,15.4 mmol), pd (PPh) 3 ) 4 (0.5g，0.4mmol)、K 2 CO 3 (5.8 g,41.9 mmol), THF and water were added to the round-bottomed flask and stirred at 90 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 4.7g of P-91. (yield)：51％)
Synthesis example of P-106
Core 1 (5 g,14 mmol), sub 16 (5.8 g,15.4 mmol), pd (PPh) 3 ) 4 (0.5g，0.4mmol)、K 2 CO 3 (5.8 g,41.9 mmol), THF and water were added to the round-bottomed flask and stirred at 90 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 5.8g of P-106. (yield: 63%)
Synthesis example of P-146
Core 1 (5 g,14 mmol), sub 2 (5.8 g,15.4 mmol), pd (PPh) 3 ) 4 (0.5g，0.4mmol)、K 2 CO 3 (5.8 g,41.9 mmol), THF and water were added to the round-bottomed flask and stirred at 90 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 4.7g of P-146. (yield: 51%)
Synthesis example of P-4
Core 1 (5 g,14 mmol), sub 6 (5.9 g,15.4 mmol), pd (PPh) 3 ) 4 (0.5g，0.4mmol)、K 2 CO 3 (5.8 g,41.9 mmol), THF and water were added to the round-bottomed flask and stirred at 90 ℃. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 6.1g of P-4. (yield: 66%)
Synthesis example of 4-1
The obtained Sub 1-1 '(50 g,98.04 mmol) was added to a round bottom flask and dissolved with toluene (359 mL) and Sub 2-1' (52.51 g,117.65 mmol), pd (PPh) 3 ) 4 (4.53g，3.92mmol)、K 2 CO 3 (40.65 g,294.12 mmol) and water (180 mL) and stirred at reflux. After completion of the reaction, CH is used 2 Cl 2 And water extraction of the reaction mixture. The organic layer was dried over MgSO 4 Dried and concentrated. Thereafter, the concentrate was passed through a silica gel column and recrystallized to obtain 64.61g of a product. (yield: 83%)
Synthesis example of 5-3
The obtained Sub 1-1 "(60 g,133.35 mmol) was added to a round bottom flask and dissolved with toluene (489 mL) and Sub 2-3" (58.28 g,160.01 mmol), pd (PPh) was added 3 ) 4 (6.16g，5.33mmol)、K 2 CO 3 (55.29 g,400.04 mmol) and water (244 mL) and stirred at reflux. After the reaction was completed, the resulting mixture was extracted with ether and water. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 73.40g of a product. (yield: 75%)
Synthesis examples of 7 to 8
2-chloro-4-phenyl-6- (7-phenyldibenzo [ b, d)]Furan-2-yl) -1,3, 5-triazine (58 g,133.35 mmol) was added to a round bottom flask and dissolved with THF (489 mL) and [1,1':3', 1': 3", 1'" -tetrabiphenyl was added]-3-Ylboronic acid (56 g,160.01 mmol), pd (PPh) 3 ) 4 (6.16g，5.33mmol)、K 2 CO 3 (55.29 g,400.04 mmol) and water (244 mL) and stirred at reflux. After the reaction was completed, the resulting mixture was extracted with ether and water. The organic layer was dried over MgSO 4 Dried and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 71.33g of a product. (yield: 76%)
TABLE 4
Manufacture and evaluation of organic electrical components
Example 1) manufacture and evaluation of green organic light emitting diodes
First, the glass is formedOn the ITO layer (anode) on the glass substrate, N is added 1 - (naphthalen-2-yl) -N 4 ,N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 Phenyl benzene-1, 4-diamine (hereinafter abbreviated as 2-TNATA) was vacuum deposited to form a hole injection layer having a thickness of 60 nm. 4, 4-bis [ N- (1-naphthyl) -N-phenylamino ] an amino group]Biphenyl (hereinafter abbreviated as-NPD) was vacuum deposited to form a hole transporting layer having a thickness of 60 nm. Subsequently, a 6:4 mixture of the compounds of the invention represented by formulas 1 and 2 was used as a host, and Ir (ppy) was doped by 95:5 by weight 3 [ tris (2-phenylpyridine) -iridium]As a dopant, an emission layer having a thickness of 30nm was deposited on the hole transport layer. (1, 1' -biphenyl) -4-bonded) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10nm as a hole blocking layer, and tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq 3) was deposited to a thickness of 40nm as an electron transport layer. Thereafter, an alkali metal halide (LiF) was vacuum deposited to a thickness of 0.2nm as an electron injection layer, and Al was deposited to a thickness of 150nm to form a cathode, thereby manufacturing an OLED.
Forward bias dc voltage was applied to the OLEDs manufactured by examples and comparative examples, electroluminescent (EL) properties were measured using PR-650 of photosearch co, and lifetime measuring device manufactured by McScience inc was used at 5000cd/m 2 The reference brightness measurement T95 lifetime of (c). In the following table, the results of the device fabrication and evaluation are shown.
Comparative example 1
An organic electroluminescent device was manufactured in the same manner as in example 1, but using only comparative compound 1 as a main body.
Comparative example 2
An organic electroluminescent device was manufactured in the same manner as in example 1, but using only comparative compound 2 as a main body.
Comparative example 3
An organic electroluminescent device was manufactured in the same manner as in example 1, but using only comparative compound 3 as a main body.
Comparative examples 4 and 5
An organic electroluminescent device was manufactured in the same manner as in example 1, but using only the compound represented by formula 2 as a main body.
Comparative example 6
An organic electroluminescent device was manufactured in the same manner as in example 1, but comparative compound 1 and the compound represented by formula 2 were mixed and used as a host.
Comparative example 7
An organic electroluminescent device was manufactured in the same manner as in example 1, but comparative compound 2 and the compound represented by formula 2 were mixed and used as a host.
Comparative example 8
An organic electroluminescent device was manufactured in the same manner as in example 1, but comparative compound 3 and the compound represented by formula 2 were mixed and used as a host.
TABLE 5
As can be seen from the results of table 5, when the materials of the organic electroluminescent devices of the present invention represented by formulas 1 and 2 were mixed and used as phosphorescent hosts (examples 1 to 56), the driving voltage, efficiency and lifetime were significantly improved, as compared to the devices using a single compound (comparative examples 1 to 5) or the devices mixed with the comparative compounds (comparative examples 6 to 8). When the tertiary amine compound, the comparative compound 2 and the comparative compound 3 are used as phosphorescent hosts of a single material, driving, efficiency and lifetime all show poor results, and the comparative compound 1 is optimal in terms of lifetime. When the compound represented by formula 2 is used alone, there is a slight increase in driving voltage and efficiency as compared to the comparative compound, but when the comparative compound 1 to the comparative compound 3 are mixed with the compound represented by formula 2 and used as a phosphorescent host, all effects are improved as compared to that used as a single compound. When the comparative compound 1 having a strong hole transporting ability and the compound represented by formula 2 are mixed, it shows a remarkable effect in terms of lifetime, and when the tertiary amine compound, the comparative compound 2 and the comparative compound 3 are mixed, it shows a remarkable effect in terms of driving. From the results only, it can be seen that even a compound having poor properties of a single body can improve the effect when mixed with a compound having good charge balance.
Further, it was confirmed that examples 1 to 56 in which the compounds of formula 1 and formula 2 of the present invention were mixed and used as a host were significantly improved as compared with the cases of comparative examples 1 to 8.
Based on the above experimental results, the present inventors determined that in the case of the mixture of the compound of formula 1 and the compound of formula 2, each compound has new properties other than those of the compound, and measured PL lifetime using the compound of formula 1, the compound of formula 2, and the mixture of the present invention, respectively. As a result, it was confirmed that when the compounds of the present invention (formula 1 and formula 2) were mixed, a new PL wavelength was formed, unlike the single compound, and the reduction and disappearance time of the newly formed PL wavelength was about 60 to about 360 times less than that of each of the compounds of formula 1 and formula 2. It is believed that not only does the electrons and holes move through the energy level of each compound when mixed with the compounds of the present invention, but also the efficiency and lifetime are increased by electron, hole transport or energy transfer of a new region (exciplex) having a new energy level formed by the mixing. As a result, when the mixture of the present invention is used, the mixed film is an important example showing the processes of energy transfer and luminescence of the exciplex.
Further, the combination of the present invention is superior to comparative examples 6 to 8 in which the comparative compound is mixed and used as a phosphorescent host in that hole characteristics are improved by using the compound represented by formula 1 in which one more amine group is added to the comparative compound 2 and the comparative compound 3, and has a good electrochemical synergistic effect with the compound represented by formula 2 having a strong electron property. Therefore, charge balance between holes and electrons in the emission layer is increased so that light emission is well performed inside the emission layer instead of the hole transport layer interface, thereby reducing degradation at the HTL interface, maximizing the driving voltage, efficiency, and lifetime of the entire device.
Example 2) manufacture and evaluation of green organic light emitting diodes by mixing ratio
TABLE 6
As shown in table 6, devices were made and measured in the same manner as in example 1 by using mixtures of the compounds of the invention in different ratios (7:3, 5:5, 4:6, 3:7). As a result of the measurement by the ratio, it was similar to that of example 1 measured at 6:4 in the case of 7:3, but the results of the driving voltage, efficiency, and lifetime gradually decreased in the case of 5:5, 4:6, and 3:7 in which the ratio of the first body was decreased. This can be explained because the charge balance in the emission layer is maximized when the compound represented by formula 1 having strong hole properties is mixed in an appropriate equivalent such as 7:3 and 4:6.
Example 3) manufacture and evaluation of green organic light emitting diodes
First, N is deposited on an ITO layer (anode) formed on a glass substrate 1 - (naphthalen-2-yl) -N 4 ,N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 Phenyl benzene-1, 4-diamine (hereinafter abbreviated as 2-TNATA) was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Subsequently, 4-bis [ N- (1-naphthyl) -N-phenylamino ] an amino group is added]Biphenyl (hereinafter abbreviated as NPD) was vacuum deposited on the film to form a hole transport layer having a thickness of 60 nm. Subsequently, the compound of the present invention represented by formula 19 and formula 21 is used as a host, and by5:5 weight doped Ir (ppy) 3 [ tris (2-phenylpyridine) -iridium]As a dopant, an emission layer having a thickness of 30nm was deposited on the hole transport layer. (1, 1' -biphenyl) -4-bonded) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10nm as a hole blocking layer, and tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq 3) was deposited to a thickness of 40nm as an electron transport layer. Thereafter, an alkali metal halide (LiF) was vacuum deposited to a thickness of 0.2nm as an electron injection layer, and Al was deposited to a thickness of 150nm to form a cathode, thereby manufacturing an OLED.
Forward bias direct current voltage was applied to the OLEDs manufactured by examples and comparative examples, electroluminescence (EL) was measured using PR-650 of photosearch co. And lifetime measuring device manufactured using McScience inc. At 5000cd/m 2 The reference brightness measurement T95 lifetime of (c). In the following table, the results of the device fabrication and evaluation are shown.
Comparative example 9-comparative example 12
An organic electroluminescent device was manufactured in the same manner as in example 3, but comparative compounds 4 to 7 were used as unitary bodies, respectively.
TABLE 7
As described above, it can be seen that the organic electroluminescent device using the compound of the present invention as a phosphorescent host significantly improves all driving voltages, efficiency and lifetime as compared to the organic electroluminescent device using the comparative compound. The difference between the comparative compound 4 and the present invention is the presence or absence of a linking group of m-phenylene, and the comparative compound 5 is different from the comparative compound 6 in the presence or absence of a secondary substituent such as phenyl or biphenyl in dibenzofuran, and the comparative compound 7 is different in the number of substituents of dibenzofuran. Comprehensive judgment device data prove that the m-phenylene linking group has the effect of improving efficiency, and particularly the secondary substituent of dibenzofuran has the effect of obviously improving service life. This means that even with the same core, the energy levels of the compounds (HOMO level, LUMO level, T1 level) are significantly different due to the substitution of specific substituents, and this difference in physical properties of the compounds acts as a major factor (e.g., energy balance) in improving device performance during device deposition, indicating that these different device results can be obtained.
Although exemplary embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Accordingly, the embodiments disclosed in the present invention are intended to exemplify the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiments.
The scope of the present invention should be construed based on the appended claims, and should be construed as including all technical ideas within the scope equivalent to the claims.
Industrial applicability
According to the present invention, an organic device having excellent device characteristics of high luminance, high light emission, and long life can be manufactured, and thus has industrial applicability.
Claims (3)
1. A compound represented by formula 22
< 22>
In the formula (22) of the present invention,
a is the following formula A-1 or formula A-2,
Ar 11 is C 6 -C 18 An aryl group is used as a substituent,
X 11 、X 12 and X 13 Each independently is O or S,
m 'and n' are each independently 0 or 1,
a 'and c' are each independently integers from 0 to 5,
d' is an integer of any one of 0 to 4,
R 21 is C 6 -C 18 An aryl group is used as a substituent,
Ar 13 and Ar is a group 14 Each independently is C 6 -C 18 An aryl group.
2. The compound according to claim 1, wherein the compound represented by formula 22 is represented by the following formula 23 or formula 24,
In the formulae 23 and 24,
X 11 、X 12 、X 13 、a'、c'、d'、m'、n'、Ar 13 、Ar 14 、R 21 as defined in claim 1.
3. The compound according to claim 1, wherein the compound represented by formula 22 is any one of the following compounds:
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| KR1020190029346A KR20190114764A (en) | 2018-03-29 | 2019-03-14 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| CN201980018624.7A CN111836872B (en) | 2018-03-29 | 2019-03-18 | Compound for organic electric element, organic electric element using the same, and electronic device using the same |
| PCT/KR2019/003116 WO2019190101A1 (en) | 2018-03-29 | 2019-03-18 | Compound for organic electric element, organic electric element using same, and electronic device therefor |
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| CN113994496A (en) * | 2020-03-11 | 2022-01-28 | 株式会社Lg化学 | Organic light emitting device |
| KR20210138823A (en) * | 2020-05-11 | 2021-11-22 | 삼성디스플레이 주식회사 | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
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