CN110546143A - Novel heterocyclic compound and organic light emitting device comprising the same - Google Patents
Novel heterocyclic compound and organic light emitting device comprising the same Download PDFInfo
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- CN110546143A CN110546143A CN201880025969.0A CN201880025969A CN110546143A CN 110546143 A CN110546143 A CN 110546143A CN 201880025969 A CN201880025969 A CN 201880025969A CN 110546143 A CN110546143 A CN 110546143A
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Abstract
The invention provides a novel compound and an organic light-emitting element using the same.
Description
Technical Field
Cross reference to related applications
The present application claims priority based on korean patent application No. 10-2017-0087246, 10.7.2017 and korean patent application No. 10-2018-0078986, 6.7.7.2018, the entire contents of which are incorporated herein by reference.
The present invention relates to a novel heterocyclic compound and an organic light-emitting element including the same.
Background
In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting element using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
An organic light-emitting element generally has a structure including an anode and a cathode, and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting element, if a voltage is applied between both electrodes, holes are injected from the anode into the organic layer, electrons are injected from the cathode into the organic layer, excitons (exiton) are formed when the injected holes and electrons meet, and light is emitted when the excitons are transitioned again to the ground state.
Development of new materials for organic materials used in the organic light-emitting devices described above is continuously demanded.
Documents of the prior art
Patent document
(patent document 1) Korean patent laid-open No. 10-2000-0051826
disclosure of Invention
Problems to be solved
The present invention relates to a novel heterocyclic compound and an organic light-emitting element including the same.
means for solving the problems
The present invention provides a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1 described above,
X is O or S, and X is O or S,
Two adjacent ones of R1 to R3 are each bonded to the group of chemical formula 2 to form a condensed ring, and the remainder are hydrogen,
one of R4 and R5 is bonded to chemical formula 3, and the rest is hydrogen,
[ chemical formula 2]
[ chemical formula 3]
In the chemical formula 3 above, the first and second,
L is a bond; a substituted or unsubstituted C6-60 arylene group; or a substituted or unsubstituted C2-60 heteroarylene group containing one or more heteroatoms selected from O, N, Si and S,
each Z is independently N or CH, wherein at least one of Z is N,
ar1 and Ar2 are each independently substituted or unsubstituted C6-60 aryl; or a substituted or unsubstituted C2-60 heteroaryl group containing one or more heteroatoms selected from O, N, Si and S.
In addition, the present invention provides an organic light emitting element including: the organic light emitting device includes a first electrode, a second electrode provided to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include a compound represented by the chemical formula 1.
effects of the invention
the compound represented by the above chemical formula 1 may be used as a material of an organic layer of an organic light emitting element in which improvement of efficiency, improvement of low driving voltage and/or improvement of life characteristics can be achieved. In particular, the compound represented by the above chemical formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.
Drawings
Fig. 1 shows an example of an organic light-emitting element including a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light-emitting element composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4.
Detailed Description
Hereinafter, the present invention will be described in more detail to assist understanding thereof.
In the present specification, the term "single bond" means a bond to another substituent, and the term "single bond" means that no other atom is present in the moiety represented by L.
In the present specification, the term "substituted or unsubstituted" means substituted with a substituent selected from deuterium; a halogen group; a cyano group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio (Alkyl thio); arylthio (Aryl thio); alkylsulfonyl (Alkyl sulfonyl); arylsulfonyl (Aryl sulfonyl); a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroaryl amino group; an arylamine group; an aryl phosphine group; or one or more substituents of N, O and one or more heterocyclic groups containing S atoms, or substituted or unsubstituted by a substituent in which 2 or more substituents among the above-exemplified substituents are bonded. For example, "a substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which 2 phenyl groups are linked.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the compound may have the following structure, but is not limited thereto.
in the ester group, in the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the compound may be a compound of the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the compound may have the following structure, but is not limited thereto.
In the present specification, specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.
in the present specification, the boron group includes specifically a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group and the like, but is not limited thereto.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methylbutyl group, a 1-ethylbutyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3, 3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, a n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, a n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propyl, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
in the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the above alkenyl group is 2 to 6. Specific examples thereof include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylethen-1-yl, 2-diphenylethen-1-yl, 2-phenyl-2- (naphthalen-1-yl) ethen-1-yl, 2-bis (biphenyl-1-yl) ethen-1-yl, stilbenyl, styryl and the like.
In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the number of carbon atoms of the above cycloalkyl group is 3 to 6. Specifically, there may be mentioned, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylene group, a fluorenyl group, or the like, but is not limited thereto.
In the present specification, the fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, the number is not limited. But is not limited thereto.
in the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl (phenanthroline), thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, and dibenzofuranyl.
In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group is the same as the above-mentioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamino group is the same as the above-mentioned examples of the alkyl group. In the present specification, the heteroaryl group in the heteroarylamine can be applied to the above description about the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned examples of the alkenyl group. In the present specification, the arylene group is a 2-valent group, and the above description of the aryl group can be applied thereto. In the present specification, a heteroarylene group is a 2-valent group, and in addition to this, the above description about a heterocyclic group can be applied. In the present specification, the hydrocarbon ring is not a 1-valent group but is formed by combining 2 substituents, and in addition to this, the above description about the aryl group or the cycloalkyl group can be applied. In the present specification, the heterocyclic group is not a 1-valent group but a combination of 2 substituents, and the above description of the heterocyclic group can be applied.
In another aspect, the present invention provides a compound represented by the above chemical formula 1.
In the above chemical formula 1, X is O or S.
In chemical formula 1, two adjacent R1 to R3 are each bonded to x of chemical formula 2 to form a fused ring, and the remainder are hydrogen. Adjacent two functional groups among R1 to R3 of the above chemical formula 1 refer to functional groups each substituted on 2 carbon atoms forming a chemical bond with each other in the above chemical formula 1, and for example, (R1 and R2), (R2 and R3) may correspond thereto.
Specifically, for example, R1 and R2 may be combined with · of chemical formula 2 to form a condensed ring in chemical formula 1, or R2 and R3 may be combined with · of chemical formula 2 to form a condensed ring in chemical formula 1.
In chemical formula 1, when two adjacent R1 to R3 are bonded to each other to form a condensed ring in chemical formula 2, the remaining functional groups that do not form a bond with chemical formula 2 may be hydrogen.
That is, the above-mentioned compound may be represented by the following chemical formula 1-1 or 1-2:
[ chemical formula 1-1]
[ chemical formulas 1-2]
in the above chemical formulas 1-1 and 1-2,
X, R4 and R5 are as defined in chemical formula 1 above.
On the other hand, adjacent two of R1 to R3 of chemical formula 1 are each bonded to chemical formula 2 to form a fused ring, and one of R4 and R5 of chemical formula 1 may be bonded to chemical formula 3.
In this case, after one of R4 and R5 is bonded to chemical formula 3 to form a fused ring, the remaining functional groups that do not form a bond to chemical formula 3 may be hydrogen.
As described above, adjacent two of R1 to R3 of chemical formula 1 are each bonded to x of chemical formula 2 to form a fused ring, and one of R4 and R5 of chemical formula 1 is bonded to x of chemical formula 3, whereby an organic light emitting element using the compound of chemical formula 1 can have high efficiency, low driving voltage, high luminance, and long life.
On the other hand, in the above chemical formula 3,
L may be a bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthyl group, and more specifically, for example, L1 may be a bond or a phenylene group. As an example of the above-mentioned phenylene group, any one selected from the following groups can be cited:
In the above chemical formula 3, each Z is independently N or CH, wherein at least one of Z may be N.
in addition, in the above chemical formula 3, Ar1 and Ar2 each independently may be a substituted or unsubstituted C6-60 aryl group; or a substituted or unsubstituted C2-60 heteroaryl group containing one or more heteroatoms selected from O, N, Si and S. More specifically, for example, each of Ar1 and Ar2 described above may be independently a phenyl group, a biphenyl group, a terphenyl group, a dimethylfluorenyl group, a naphthyl group, a pyridyl group, a dibenzofuranyl group, or a dibenzothienyl group.
In addition, the above compound may be any one selected from the following compounds:
In another aspect, the present invention provides an organic light emitting element comprising the compound represented by the above chemical formula 1. As an example, the present invention provides an organic light emitting element including: the organic light emitting device includes a first electrode, a second electrode provided to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include a compound represented by the chemical formula 1.
The organic layer of the organic light-emitting device of the present invention may have a single-layer structure, or may have a multilayer structure in which two or more organic layers are stacked. For example, the organic light-emitting element of the present invention may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like as an organic layer. However, the structure of the organic light-emitting element is not limited to this, and a smaller number of organic layers may be included.
In addition, the organic layer may include a hole injection layer, a hole transport layer, or a layer simultaneously performing hole injection and transport, and the hole injection layer, the hole transport layer, or the layer simultaneously performing hole injection and transport includes the compound represented by the chemical formula 1.
in addition, the organic layer may include a light emitting layer, and the light emitting layer may include the compound represented by chemical formula 1.
In addition, the electron transport layer, the electron injection layer, or the layer simultaneously transporting and injecting electrons may be included, and the electron transport layer, the electron injection layer, or the layer simultaneously transporting and injecting electrons may include the compound represented by the above chemical formula 1.
In addition, the organic layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by the chemical formula 1.
The organic light-emitting element may further include, in addition to the organic layer, an Electron Blocking Layer (EBL) between the Hole transport layer and the light-emitting layer and/or a Hole Blocking Layer (HBL) between the light-emitting layer and the Electron transport layer. In this structure, the compound represented by the above chemical formula 1 may be contained in 1 or more layers of the above electron blocking layer and the above hole blocking layer. The electron blocking layer and the hole blocking layer may be organic layers adjacent to the light emitting layer.
In this case, the compound represented by the above chemical formula 1 may be included in the above light emitting layer, the above electron transport layer, or the above hole blocking layer.
The organic layer of the organic light-emitting device of the present invention may be formed of a single layer structure, or may be formed of a multilayer structure in which two or more organic layers are stacked. For example, the organic light-emitting element of the present invention may have a structure further including, as an organic layer, a hole injection layer and a hole transport layer between the first electrode and the light-emitting layer, and an electron transport layer and an electron injection layer between the light-emitting layer and the second electrode, in addition to the light-emitting layer. However, the structure of the organic light emitting element is not limited thereto, and fewer or more organic layers may be included.
In addition, the organic light emitting element according to the present invention may be an organic light emitting element having a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting element according to the present invention may be an inverted (inverted) type organic light emitting element in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, a structure example of an organic light emitting element according to an embodiment of the present invention is shown in fig. 1 and 2.
Fig. 1 shows an example of an organic light-emitting element including a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be included in the above light emitting layer.
Fig. 2 shows an example of an organic light-emitting element including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.
The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that one or more of the organic layers include the compound represented by the above chemical formula 1. In addition, when the organic light emitting element includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic light emitting element according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. This can be produced as follows: the organic el display device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical Vapor Deposition) method such as a sputtering method or an electron beam evaporation method (e-beam evaporation) method to form an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition to this method, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting element.
in addition, the compound represented by the above chemical formula 1 may be formed into an organic layer by not only a vacuum evaporation method but also a solution coating method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
In addition to these methods, an organic light-emitting element can be manufactured by depositing a cathode material, an organic material layer, and an anode material on a substrate in this order (WO 2003/012890). However, the production method is not limited thereto.
In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); a combination of a metal such as ZnO, Al or SNO2, Sb, etc., and an oxide; and conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDOT), polypyrrole, polyaniline, and the like, but the present invention is not limited thereto.
The cathode material is preferably a material having a small work function in order to easily inject electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; and a multilayer structure such as LiF/Al or LiO2/Al, but not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the following compounds are preferable as the hole injection substance: has an ability to transport holes, has a hole injection effect from the anode, has an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material, and has excellent thin film-forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting substance is between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and is preferably a material having a high mobility to holes. Specific examples thereof include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.
The light-emitting substance is a substance that can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combine them to emit light in the visible light region, and a substance having a high quantum efficiency with respect to fluorescence or phosphorescence is preferable. As specific examples, there are 8-hydroxyquinoline aluminum complex (Alq 3); a carbazole-based compound; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline metal compounds; benzoxazole, benzothiazole and benzimidazole compounds; poly (p-phenylene vinylene) (PPV) polymers; spiro (spiroo) compounds; polyfluorene, rubrene, and the like, but are not limited thereto.
The light-emitting layer may contain a host material and a dopant material as described above. The host material may include an aromatic fused ring derivative, a heterocyclic ring-containing compound, or the like, in addition to the compound represented by chemical formula 1. Specifically, the aromatic fused ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocyclic ring-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound (), a pyrimidine derivative, and the like, but is not limited thereto.
As the dopant material, there are an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, and the like. Specifically, the aromatic amine derivative is an aromatic fused ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, diindenopyrene, etc., having an arylamine group, and the styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine group, and is substituted or unsubstituted with one or two or more substituents selected from an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrimethylamine, and styryltretramine. The metal complex includes, but is not limited to, iridium complexes and platinum complexes.
The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting substance is a substance that can inject electrons from the cathode well and transfer the electrons to the light emitting layer, and a substance having a high electron mobility is preferable. Specific examples thereof include, but are not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic radical compounds, and hydroxyflavone-metal complexes. The electron transport layer may be used with any desired cathode material as used in the art. Examples of suitable cathode substances are, in particular, the customary substances having a low work function and accompanied by an aluminum or silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum or silver layer.
the electron injection layer is a layer for injecting electrons from the electrode, and is preferably a compound of: has an ability to transport electrons, an electron injection effect from a cathode, an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and is excellent in thin-film formability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complexes, nitrogen-containing five-membered ring derivatives, and the like, but the present invention is not limited thereto.
Examples of the metal complex include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), and gallium tris (8-quinolinolato), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) gallium chloride, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.
The organic light emitting element according to the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used.
In addition, the compound represented by the above chemical formula 1 may be included in an organic solar cell or an organic transistor, in addition to the organic light emitting element.
The production of the compound represented by the above chemical formula 1 and the organic light emitting element comprising the same is specifically described in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
[ Synthesis examples ]
< Synthesis example 1> (Synthesis of intermediate 1)
1-1) Synthesis of intermediate 1-1
In a three-necked flask, 4,5,5-tetramethyl-2- (triphenylen-2-yl) -1,3,2-dioxaborolan (4,4,5, 5-tetramethyll-2- (triphenylen-2-yl) -1,3, 2-dioxaborolan) (40.0g, 112.9mmol), 2-bromo-3-chlorophenol (2-bromo-3-chlorophenol) (24.6g, 118.6mmol) were dissolved in 1000ml of THF, and K2CO3(62.4g, 451.6mmol) was dissolved in 500ml of H2O and added. To this, tetrakis (triphenylphosphine) palladium (Pd (PPh3)4) (1.3g, 1.1mmol) was added, and the mixture was stirred under argon reflux conditions for 8 hours, after the reaction was completed and cooled to room temperature, the reaction mixture was transferred to a separatory funnel, extracted with CH2Cl2, the extract was dried over MgSO4, filtered and concentrated, and then the sample was purified by silica gel column chromatography to obtain 31.3g of intermediate 1-1. (yield 78%, MS [ M + H ] + ═ 354)
1-2) Synthesis of intermediate 1
after dissolving intermediate 1-1(30.0g, 84.5mmol) in 350ml of Toluene (Toluene) in a three-necked flask, palladium (II) acetate (palladium (II) acetate, P d (OAc)2) (0.9g, 4.2mmol), 1,3-bis (2,6-diisopropylphenyl) -1, 3-dihydro-2H-imidazol-2-ylidene (1,3-bis (2,6-diisopropylphenyl) -1, 3-dihydro-2H-imidozol-2-ylene, IPr) (3.3g, 8.5mmol), sodium 2,4, 6-trimethylbenzoate (sodium 2,4, 6-trimethylbenzoate, MesCOONa) (7.9g, 42.3mmol), K2CO3(23.4g, 1.5 mmol), and stirring under argon atmosphere for 169 hours under reflux for 24 ml. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the reaction mixture was transferred to a separatory funnel and extracted with CH2Cl 2. The extract was dried over MgSO4, filtered and concentrated, and then the sample was purified by silica gel column chromatography to obtain 16.7g of intermediate 1. (yield 56%, MS [ M + H ] + ═ 352)
< Synthesis example 2> (Synthesis of intermediate 2)
2-1) Synthesis of intermediate 2-1
in a three-necked flask, 4-triphenylen-2-ol (4triphenylen-2-ol) (30.0g, 122.8mmol), 2-bromo-1-chloro-3-fluorobenzene (2-bromo-1-chloro-3-fluorobenzene) (27.0g, 128.9mmol) and K2CO3(25.5g, 184.2mmol) were dissolved in 500ml of DMAc and stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added to the reaction mixture, and the reaction mixture was transferred to a separatory funnel and extracted with ethyl acetate (ethyl acetate). The extract was purified by silica gel column chromatography to obtain 39.9g of intermediate 2-1. (yield 75%, MS [ M + H ] + ═ 433)
2-2) Synthesis of intermediate 2
In a three-necked flask, intermediate 2-1(30.0g, 102.5mmol), palladium (II) acetate (palladium (II) acetate, Pd (OAc)2) (1.2g, 5.1mmol), tricyclohexylphosphine (2.9g, 10.2mmol), K2CO3(42.5g, 307.5mmol), 425ml of DMAc were added and stirred under reflux conditions of argon atmosphere for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the reaction mixture was transferred to a separatory funnel and extracted with CH2Cl 2. The extract was dried over MgSO4, filtered and concentrated, and then the sample was purified by silica gel column chromatography to obtain 15.2g of intermediate 2. (yield 42%, MS [ M + H ] + ═ 352)
< Synthesis example 3> (Synthesis of Compound 1)
Intermediate 1(10.0g, 28.3mmol) and intermediate a (12.2g, 34.0mmol) obtained in < synthesis example 1> above were dissolved in 285ml of THF in a three-necked flask, and K2CO3(15.7g, 113.4mmol) was dissolved in 142ml of H2O and then added. Tetrakis (triphenylphosphine) palladium (palladium-tetrakis (triphenylphoshine), Pd (PPh3)4) (0.3g, 0.3mmol) was added thereto, and stirred under argon atmosphere reflux for 8 hours. After cooling to room temperature at the end of the reaction, the reaction solution was transferred to a separatory funnel and extracted with CH2Cl 2. The extract was dried over MgSO4, filtered and concentrated, and then the sample was purified by silica gel column chromatography and then purified by sublimation to obtain 5.3g of Compound 1. (yield 34%, MS [ M + H ] + ═ 549)
< Synthesis example 4> (Synthesis of Compound 2)
Compound 2 was synthesized in the same manner as in the synthesis of compound 1 except that intermediate a was used instead of intermediate B in < synthesis example 3 >. (MS [ M + H ] + ═ 639)
< Synthesis example 5> (Synthesis of Compound 3)
Compound 3 was synthesized in the same manner as in the synthesis of compound 1 except that intermediate a was used instead of intermediate C in < synthesis example 3 >. (MS [ M + H ] + ═ 625)
< Synthesis example 6> (Synthesis of Compound 4)
Compound 4 was synthesized in the same manner as in the synthesis of compound 1 except that intermediate a was used instead of intermediate D in < synthesis example 3 >. (MS [ M + H ] + ═ 625)
< Synthesis example 7> (Synthesis of Compound 5)
compound 5 was synthesized in the same manner as in the synthesis of compound 1 except that in < synthesis example 3> described above, intermediate 1 was used instead of intermediate 2 obtained in < synthesis example 2 >. (MS [ M + H ] + ═ 549)
< Synthesis example 8> (Synthesis of Compound 6)
Compound 6 was synthesized in the same manner as in the synthesis of compound 1 except that in < synthesis example 3> described above, intermediate 1 was changed to intermediate 2 and intermediate a was changed to intermediate B and used. (MS [ M + H ] + ═ 639)
< Synthesis example 9> (Synthesis of Compound 7)
Compound 7 was synthesized in the same manner as in the synthesis of compound 1 except that in < synthesis example 3> described above, intermediate 1 was changed to intermediate 2 and intermediate a was changed to intermediate D. (MS [ M + H ] + ═ 625)
[ examples ]
< example 1>
The glass substrate coated with ITO (Indium Tin Oxide) in a thin film of the above thickness was put in distilled water in which a detergent was dissolved, and washed by ultrasonic waves. In this case, the detergent used was a product of fisher (Fischer Co.) and the distilled water used was distilled water obtained by twice filtration using a Filter (Filter) manufactured by Millipore Co. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the completion of the distilled water washing, the resultant was ultrasonically washed with a solvent of isopropyl alcohol, acetone, or methanol, dried, and then transported to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.
On the ITO transparent electrode thus prepared, thermal vacuum evaporation was performed at a thickness of 95 wt% of HT-a and 5 wt% of a P-type DOPANT (P-DOPANT), and then only HT-a was evaporated at the thickness to form a hole transport layer.
On the hole transport layer, the following HT-B was thermally vacuum-deposited to a thickness of the electron blocking layer.
Next, thermal vacuum deposition was performed at a thickness of 47 wt% for the following compound 1 as a first host material of the light-emitting layer, 47 wt% for the following GH as a second host material, and 6 wt% for the following GD as a dopant material.
N mutext, as a hole-blocking layer, thermal vacuum deposition was performed to a thickness of ET-a described below.
Next, as the electron transporting and injecting layer, ET-B and Liq described below were thermally vacuum-evaporated at a ratio of 2:1 and at a thickness, and then LiF and magnesium were vacuum-evaporated at a ratio of 1:1 and at a thickness.
On the electron injection layer, magnesium and silver were deposited at a ratio of 1:4 and a thickness of the layer was set to form a cathode, thereby producing an organic light-emitting device.
< examples 2 to 7 and comparative examples 1 to 4>
Organic light-emitting elements of examples 2 to 7 and comparative examples 1 to 4 were produced by the same method as in example 1, except that the first host material was changed as shown in table 1 below.
The organic light-emitting elements produced in examples 1 to 7 and comparative examples 1 to 4 were applied with current, and the voltage, efficiency, and lifetime (T95) were measured, and the results are shown in table 1 below. In this case, the voltage, the efficiency were measured by applying a current density of 10mA/cm2, and T95 means the time required for the initial luminance to decrease to 95% at a current density of 20mA/cm 2.
[ Table 1]
From the results shown in table 1, it was confirmed that when the compounds represented by chemical formula 1 (compounds 1 to 7 of examples 1 to 7) were applied to the light-emitting layer host of the organic electroluminescent element, the element having high light-emitting efficiency and long life could be obtained.
[ notation ] to show
1: substrate 2: anode
3: light-emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: light-emitting layer 8: an electron transport layer.
Claims (6)
1. a compound represented by the following chemical formula 1:
Chemical formula 1
In the chemical formula 1, the metal oxide is represented by,
X is O or S, and X is O or S,
Two adjacent ones of R1 to R3 are each bonded to the group of chemical formula 2 to form a condensed ring, and the remainder are hydrogen,
One of R4 and R5 is bonded to chemical formula 3, and the rest is hydrogen,
Chemical formula 2
Chemical formula 3
In the chemical formula 3, the first and second organic solvents,
L is a bond; a substituted or unsubstituted C6-60 arylene group; or a substituted or unsubstituted C2-60 heteroarylene group containing one or more heteroatoms selected from O, N, Si and S,
Each Z is independently N or CH, wherein at least one of Z is N,
Ar1 and Ar2 are each independently substituted or unsubstituted C6-60 aryl; or a substituted or unsubstituted C2-60 heteroaryl group containing one or more heteroatoms selected from O, N, Si and S.
2. The compound according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 1-1 or 1-2:
Chemical formula 1-1
Chemical formula 1-2
In the chemical formulas 1-1 and 1-2,
X, R4 and R5 are as defined in claim 1 above.
3. The compound of claim 1, wherein L is a bond or phenylene.
4. The compound of claim 1, wherein Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, dimethylfluorenyl, naphthyl, pyridinyl, dibenzofuranyl, or dibenzothiophenyl.
5. The compound of claim 1, wherein the compound is any one selected from the group consisting of:
6. An organic light-emitting element comprising: a first electrode, a second electrode provided so as to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers contain the compound according to any one of claims 1 to 5.
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| KR102442580B1 (en) * | 2020-04-09 | 2022-09-13 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
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| KR20240043527A (en) * | 2022-09-27 | 2024-04-03 | 삼성에스디아이 주식회사 | Composition for optoelectronic device and organic optoelectronic device and display device |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013001997A1 (en) * | 2011-06-28 | 2013-01-03 | Canon Kabushiki Kaisha | Triphenyleno-benzofuran compound and organic light emitting element including the same |
| WO2013009079A1 (en) * | 2011-07-11 | 2013-01-17 | 주식회사 두산 | Triphenylene-based compound and organic electroluminescent diode using same |
| US20150001489A1 (en) * | 2013-07-01 | 2015-01-01 | Samsung Display Co., Ltd. | Organic light emitting diode device |
| US9172046B1 (en) * | 2014-06-09 | 2015-10-27 | Samsung Display Co., Ltd. | Organic light-emitting device |
| CN105377822A (en) * | 2013-07-10 | 2016-03-02 | 三星Sdi株式会社 | Organic composition, and organic optoelectronic element and display device |
| CN106459018A (en) * | 2014-05-05 | 2017-02-22 | 默克专利有限公司 | Materials for organic light emitting devices |
| KR20180040296A (en) * | 2016-10-12 | 2018-04-20 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic device and organic optoelectronic device and display device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100430549B1 (en) | 1999-01-27 | 2004-05-10 | 주식회사 엘지화학 | New organomattalic complex molecule for the fabrication of organic light emitting diodes |
-
2018
- 2018-07-06 KR KR1020180078986A patent/KR102020029B1/en active IP Right Grant
- 2018-07-09 CN CN201880025969.0A patent/CN110546143B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013001997A1 (en) * | 2011-06-28 | 2013-01-03 | Canon Kabushiki Kaisha | Triphenyleno-benzofuran compound and organic light emitting element including the same |
| WO2013009079A1 (en) * | 2011-07-11 | 2013-01-17 | 주식회사 두산 | Triphenylene-based compound and organic electroluminescent diode using same |
| US20150001489A1 (en) * | 2013-07-01 | 2015-01-01 | Samsung Display Co., Ltd. | Organic light emitting diode device |
| CN105377822A (en) * | 2013-07-10 | 2016-03-02 | 三星Sdi株式会社 | Organic composition, and organic optoelectronic element and display device |
| CN106459018A (en) * | 2014-05-05 | 2017-02-22 | 默克专利有限公司 | Materials for organic light emitting devices |
| US9172046B1 (en) * | 2014-06-09 | 2015-10-27 | Samsung Display Co., Ltd. | Organic light-emitting device |
| KR20180040296A (en) * | 2016-10-12 | 2018-04-20 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic device and organic optoelectronic device and display device |
| CN109890937A (en) * | 2016-10-12 | 2019-06-14 | 三星Sdi株式会社 | For the compound of Organic photoelectronic components, Organic photoelectronic components and display device |
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