CN112204042A

CN112204042A - Novel compound and organic light-emitting element using same

Info

Publication number: CN112204042A
Application number: CN201980034898.5A
Authority: CN
Inventors: 河宰承; 金性昭; 千民承
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2018-08-22
Filing date: 2019-07-22
Publication date: 2021-01-08
Anticipated expiration: 2039-07-22
Also published as: KR20200022248A; WO2020040434A1; CN112204042B; KR102281249B1

Abstract

The invention provides a novel compound and an organic light-emitting element using the same.

Description

Novel compound and organic light-emitting element using same

Technical Field

To the related applicationAre cited in

The present application claims priority based on korean patent application No. 10-2018-0098139, 8/22/2018, the entire contents of which are incorporated herein by reference.

The present invention relates to a novel compound and an organic light emitting device 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. In the structure of such an organic light emitting element, if a voltage is applied between the electrodes, holes are injected from the anode into the organic layer, electrons are injected from the cathode into the organic layer, and when the injected holes and electrons meet, excitons (exiton) are formed, which emit light when they transition to the ground state again.

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

Means for solving the problems

The present invention provides a compound represented by the following chemical formula 1:

[ chemical formula 1]

In the above-described chemical formula 1,

L₁and L₂Each independently a single bond, phenylene, biphenylene, or naphthylene,

Ar₁to Ar₃Each independently is substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

a is any one of groups represented by the following chemical formulae 2-1 to 2-3,

in the above chemical formulas 2-1 to 2-3,

Z₁to Z₇Each independently is hydrogen; deuterium; halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C_1-60An alkyl group; substituted or unsubstituted C_1-60A haloalkyl group; substituted or unsubstituted C_1-60An alkoxy group; substituted or unsubstituted C_1-60Haloalkoxy, substituted or unsubstituted C_3-60A cycloalkyl group; substituted or unsubstituted C_2-60An alkenyl group; substituted or unsubstituted C_6-60An aryl group; substituted or unsubstituted C_6-60An aryloxy group; or substituted or unsubstituted C comprising one or more selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

n1 and n2 are each independently an integer from 0 to 4,

n3 is an integer from 0 to 3,

when n1 to n3 are each 2 or more, the structures in parentheses of 2 or more are the same as or different from each other,

represents L of the chemical formula 1₂Bit of connectionThe device is placed in a water tank,

R₁to R₄Each independently hydrogen, or substituted or unsubstituted C_1-60An alkyl group.

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 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 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, lower driving voltage, and/or improvement of life characteristics can be achieved.

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 illustrates 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 context of the present specification,

represents a bond with other substituent, and a single bond means a bond represented by L₁And L₂The portion represented is absent other atoms.

In the present specification, the term "substituted or unsubstituted" means substituted with a substituent selected from deuterium; a halogen group; a cyano group; a nitro 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 thioaxy); arylthio (aryl thioaxy); alkylsulfonyl (alkyl sulfonyl xy); 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 1 or more substituents of 1 or more heteroaryl groups containing N, O and S atoms, or substituted or unsubstituted by 2 or more substituents of the above-exemplified substituents. 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 present specification, in the ester group, 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 specifically includes 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, as examples of the halogen group, there are fluorine, chlorine, bromine or 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-, 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, and styryl.

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 number of carbon atoms of the cycloalkyl group is 3 to 30. 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 aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a perylene group,

And a fluorenyl group, 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. In the case where the above-mentioned fluorenyl group is substituted, it may be

And the like. But is not limited thereto.

In the present specification, the heteroaryl group is a heteroaryl group containing 1 or more of O, N, Si and S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 2 to 60. Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, thienyl,

Azolyl group,

Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinyl

Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl (phenanthroline), isoquinoyl

Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the aryl group described above. 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 alkyl group. In the present specification, the heteroaryl group in the heteroarylamine can be applied to the above description about the heteroaryl group. In the present specification, the alkenyl group in the aralkenyl group is the same as exemplified above for the alkenyl group. In the present specification, the arylene group is a 2-valent group, and in addition thereto, the above description about the aryl group can be applied. In the present specification, a heteroarylene group is a 2-valent group, and in addition to this, the above description about a heteroaryl 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 ring is not a 1-valent group but is formed by combining 2 substituents, and in addition to this, the above description on the heteroaryl group can be applied.

In another aspect, the present invention provides an anthracene derivative compound represented by the above chemical formula 1. Such a compound has both a silyl group and a benzimidazolyl group, and thus high efficiency, low driving voltage, long life, and the like of an organic light-emitting element using a compound having only a silyl group or a benzimidazolyl group can be achieved.

In the above chemical formula 1, L₁And L₂May each independently be any one selected from a single bond and the following groups:

in addition, Ar₁To Ar₃Each independently is phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothienyl, or carbazolyl,

wherein Ar is₁To Ar₃Is unsubstituted; or may be substituted with 1 or 2 substituents each independently selected from methyl, phenyl, dibenzofuranyl and dibenzothiophenyl.

Specifically, Ar₁To Ar₃May each independently be any one selected from the following groups:

in the above-mentioned group, the group,

x is O, S, C (methyl)₂Or N (phenyl).

In addition, in the above chemical formulas 2-1 to 2-3,

Z₁to Z₇Can be independently hydrogen or C_1-4Alkyl radical, C_6-10Aryl, or C containing 1 or 2N atoms_2-10A heteroaryl group.

Specifically, Z₁To Z₇May each independently be hydrogen, methyl, ethyl, isopropyl, phenyl, naphthyl, pyridyl, or quinolinyl.

For example, Z₁To Z₄Each independently hydrogen, methyl, ethyl, isopropyl, phenyl, naphthyl, pyridyl, or quinolyl,

Z₅to Z₇May each independently be hydrogen, methyl, ethyl, or phenyl.

In addition, R₁To R₄Are all hydrogen, or

R₁And R₂Each independently is C_1-4Alkyl radical, R₃And R₄Is hydrogen, or

R₁And R₂Is hydrogen, R₃And R₄May each independently be C_1-4An alkyl group.

At this time, R₁And R₂May be identical to each other, R₃And R₄May be identical to each other.

For example, R₁To R₄Are all hydrogen, or

R₁And R₂Is methyl, ethyl, or tert-butyl, R₃And R₄Is hydrogen, or

R₁And R₂Is hydrogen, R₃And R₄And may be methyl, ethyl, or tert-butyl.

In addition, the above compound may be represented by any one of the following chemical formulas 1-1 to 1-3:

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

In the above chemical formulas 1-1 to 1-3,

for L₁、L₂、Ar₁To Ar₃、R₁To R₄And Z₁To Z₆The description thereof is the same as that in the above chemical formula 1,

for Z₅' and Z₆The description of' refers to Z individually₅And Z₆And (4) description.

For example, the above compound may be any one selected from the following compounds:

on the other hand, as an example, the compound represented by the above chemical formula 1 may be produced by a production method as shown in the following reaction formula 1.

[ reaction formula 1]

In the above reaction formula 1, X is halogen, preferably bromine or chlorine, and the definitions of the remaining substituents are the same as those described above. The above reaction is a reaction of producing the compound represented by chemical formula 1 by suzuki coupling reaction of compound F2 and compound G or H, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group for the suzuki coupling reaction can be modified according to a technique known in the art. Such a manufacturing method can be further embodied in the manufacturing examples described later.

As an example, the compound F2 of the above reaction formula 1 can be produced by the method shown in the following reaction formula 2. Specifically, in L₁When not a single bond, compound F2 can be produced by the reaction procedure shown in (1), at L₁In the case of a single bond, compound F2 can be produced by the reaction step shown in (2).

[ reaction formula 2]

In the above reaction formula 2, each X is independently a halogen, preferably bromine or chlorine, and the definitions of the remaining substituents are the same as those described above. Each of the above steps 1-1 and 1' -1 is preferably carried out in the presence of a strong base as the nucleophilic substitution reaction. The above step 1-2 is a step of introducing a boronic acid substituent to the above compound a by boronation (borylation), and the above steps 1-3 and 1' -2 are steps of producing an intermediate compound F1 by combining the compound SM4 with the intermediate compound each by suzuki coupling reaction. In addition, the above-mentioned steps 1 to 4 are steps of introducing a bromine group into the compound F1 and then preparing a compound F2 by boronization.

In addition, as an example, the compound G of the above reaction formula 1 may be produced through a reaction step shown in (1) of the following reaction formula 3, and the compound H of the above reaction formula 1 may be produced through a reaction step shown in (2) of the following reaction formula 3.

[ reaction formula 3]

In the above reaction formula 3, each X is independently a halogen, and the definitions of the remaining substituents are the same as those described above. Each of the above (1) and (2) is a step of producing the compounds G and H by a cyclization removal reaction after producing an amide by a reaction of a nitro compound with a carbonyl halide.

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 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 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 2 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 thereto, and a smaller number of organic layers may be included.

In addition, the organic layer may include a light emitting layer including the compound represented by the chemical formula 1.

In addition, the organic layer may include a light emitting layer, an electron transport layer including the compound represented by the chemical formula 1, and an electron injection layer.

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 2 or more organic layers are stacked. For example, the organic light-emitting element of the present invention may have a structure 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 a smaller or greater number of 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, 1 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, 1 or more organic layers, and an anode are sequentially stacked on a substrate. For example, fig. 1 and 2 show an example of the structure of an organic light-emitting element according to an embodiment of the present invention.

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 illustrates 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. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in 1 or more layers among the above hole injection layer, hole transport layer, light emitting layer, and electron transport layer.

The organic light emitting element according to the present invention may be manufactured using materials and methods known in the art, except that 1 or more of the above 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 material or different materials.

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. In this case, the following production can be performed: 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 may 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); ZnO-Al or SnO₂A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, 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; LiF/Al or LiO₂And a multilayer structure material such as 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: a compound having an ability to transport holes, having an effect of injecting holes from an anode, having an excellent hole injection effect for a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to an electron injection layer or an electron injection material, and having an excellent thin film-forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting species is between the work function of the anode species 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 substance is a substance 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 substance 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 is preferably a substance having high quantum efficiency with respect to fluorescence or phosphorescence. As a specific example, there is an 8-hydroxyquinoline aluminum complex (Alq)₃) (ii) a A carbazole-based compound; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (b) is

Azole, benzothiazole and benzimidazole-based 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 further contain an aromatic fused ring derivative, a heterocyclic ring-containing compound, or the like. 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 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 arylamino group, and includes pyrene, anthracene, or the like having an arylamino group,

Diindenopyrene, and the like, and styrylamine compounds are compounds substituted with at least 1 arylvinyl group in substituted or unsubstituted arylamines, and are substituted or unsubstituted with 1 or 2 or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. 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 favorably receive electrons from the cathode and transfer the electrons to the light emitting layer, and is preferably a substance having a high mobility to electrons. As the electron transporting substance, a compound represented by the above chemical formula 1 may be used. Alternatively, the compound represented by the above chemical formula 1 may be used together with a commonly used electron transporting substance. Specific examples of the electron transporting substance generally used include metal complexes, Al complexes of 8-hydroxyquinoline, and compounds containing Alq₃Organic radical compounds, hydroxyl brass-metal complexes, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in the art. In particular, it is possible to use,examples of suitable cathode substances are the usual 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: a compound having an ability to transport electrons, having an effect of injecting electrons from a cathode, having an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and having an excellent thin-film-forming ability. Specifically, there are fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,

Azole,

Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are 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 device comprising the same is specifically described in the following examples. However, the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

Synthesis example 1: preparation of intermediate Compounds F2-1 to F2-14

Step 1-1: preparation of intermediate compounds A1 to A8

To produce the intermediate compounds a1 to A8, respectively, starting material 1(1 equivalent) of table 1 below was dissolved in THF (excess), the temperature was lowered to-78 degrees, and then 2.5M n-BuLi (0.95 equivalent) was added dropwise to obtain reaction product 1. In another flask, starting material 2(1 equivalent) of table 1 below was dissolved in THF (excess), the temperature was reduced to-78 degrees, 2.5M n-BuLi (1 equivalent) was added dropwise and stirred for 3 hours, and then starting material 3(1 equivalent) of table 1 below was added to produce reactant 2. To the reaction product 2 thus formed, the reaction product 1 previously formed was added dropwise, slowly heated to room temperature, and stirred for 10 hours. After completion of the reaction, water was added to conduct layer separation to remove the solvent, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane 1:15) to obtain products a1 to A8 shown in table 1 below, and the respective yields and MS data are shown below.

[ TABLE 1]

Step 1-2: production of intermediate compounds B1-B8

To produce the intermediate compounds B1 to B8, respectively, one (1 equivalent) of the intermediate compounds a1 to a8 produced in the above step 1-1 was dissolved in THF (excess), the temperature was reduced to-78 degrees, then 2.5M n-BuLi (1.5 equivalents) was added dropwise, triisopropyl borate (1.3 equivalents) was added after 30 minutes, and stirring was carried out for 1 hour after rising to RT. 1N HCl (excess) was added, and after stirring for 30 minutes, layer separation was performed to remove the solvent, and then after purification with ethyl acetate, the obtained solid was added to acetic acid (excess), and then 1ml sulfuric acid was added dropwise, stirred and refluxed. The temperature was reduced to normal temperature, neutralized with water, and the filtered solid was recrystallized from ethyl acetate and hexane to obtain the following products B1 to B8 of table 2, the respective yields and MS data of which are shown below.

[ TABLE 2]

Step 1-3: preparation of intermediate Compounds F1-1 to F1-11

To produce intermediate compounds F1-1 to F1-11, respectively, starting material 1(1 equivalent) of table 3 below and starting material 2 of table 3 below were added to THF (excess), 2M aqueous potassium carbonate solution (30 vol% with respect to THF) was added, tetrakis (triphenylphosphine) palladium (2 mol%) was added, and the mixture was stirred under heating for 10 hours. And (4) cooling the temperature to normal temperature, removing the potassium carbonate aqueous solution after the reaction is finished, and carrying out layer separation. The solvent was removed, vacuum distillation was performed, and recrystallization was performed using THF and ethyl acetate, thereby obtaining F1-1 to F1-11 of the following Table 3, the respective yields and MS data are shown below.

[ TABLE 3]

Step 1' -1: production of intermediate Compound C1

To produce intermediate compound C1, starting material 1(1 equivalent) of table 4 below was dissolved in THF (excess), the temperature was reduced to-78 degrees, 2.5M n-BuLi (0.95 equivalent) was added dropwise, starting material 2(1 equivalent) of table 4 below was added dropwise, the mixture was slowly heated to room temperature, and the mixture was stirred for 10 hours. After completion of the reaction, water was added to conduct layer separation to remove the solvent, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane 1:15) to obtain product C1 shown in table 4 below, wherein the yield and MS data are as follows.

[ TABLE 4 ]

Step 1' -2: preparation of intermediate Compounds F1-12 to F1-14

To prepare intermediate compounds F1-12 to F1-14, starting material 2 of Table 5 below was dissolved in THF (excess), the temperature was lowered to-78 deg.C, 2.5M n-BuLi (1.5 equiv.) was added dropwise, starting material 1 of Table 5 below (1.05 equiv.) was added after 30 minutes, the mixture was allowed to warm to RT and stirred for 1 hour. 1N HCl (excess) was added, and after stirring for 30 minutes, the layers were separated to remove the solvent, followed by recrystallization from THF and ethyl acetate to obtain the following products F-12 to F1-14 of Table 5, the respective yields and MS data of which are shown below.

[ TABLE 5 ]

Step 1-4: preparation of intermediate Compounds F2-1 to F2-14

To produce the intermediate compounds F2-1 to F2-14, respectively, one (1 equivalent) of F1-1 to F1-14 produced in the above steps 1-3 and 1' -2 was dissolved in chloroform, and N-bromosuccinimide (NBS, 1.01 equivalent) was dissolved in chloroform and added dropwise. After completion of the reaction, 1N HCl (excess) was added, and after extraction, the solid obtained by distillation under reduced pressure was dried in a vacuum oven for 24 hours to obtain a white solid. After dissolving the above solid in THF (excess), the temperature was lowered to-78 deg.C, then 2.5M n-BuLi (1.5 equiv.) was added dropwise, triisopropyl borate (1.3 equiv.) was added after 30 minutes, the mixture was allowed to warm to RT and stirred for 1 hour. 1N HCl (excess) was added, and after stirring for 30 minutes, layer separation was performed to remove the solvent, followed by purification with ethyl acetate, and the obtained solid was added to acetic acid (excess), and then 1ml sulfuric acid was added dropwise, stirred and refluxed. The temperature was lowered to room temperature, neutralized with water, and the filtered solid was recrystallized from chloroform and ethyl acetate to give products F2-1 to F2-14 shown in Table 6 below, in the respective yields and MS data shown below.

[ TABLE 6 ]

Synthesis example 2: production of intermediate compounds G1 to G8 and H1 to H7

Step 2-1: preparation of intermediate Compounds D1-1 to D1-5

To produce the intermediate compounds D1-1 to D1-5, respectively, starting material 1(1 equivalent), starting material 2(1.5 equivalents) and 8.8g (2.5 equivalents) of sodium acetate of table 7 below were heated and stirred at 160 ℃ for 9 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, diluted with ethyl acetate and filtered. The filtrate was concentrated and purified by silica gel column chromatography (hexane) to obtain the products D1-1 to D1-5 shown in table 7 below, in the respective yields and MS data shown below.

[ TABLE 7 ]

Step 2-2 and 2-3: preparation of intermediate compounds G1-G8

To produce the intermediate compounds G1 to G8, respectively, 9.9G (33.8mmol) of starting material 1(1 eq) of table 8 below was dissolved in 75ml of THF and a solution of sodium bisulfite (5.5 eq)/water (25% v/v%) was added dropwise under nitrogen at room temperature with stirring. An excess of methanol was further added and stirred for 3 hours. Then, ethyl acetate (5 eq) was added and sodium bicarbonate (excess) was added. Further, starting material 2(1 equivalent) of table 8 below was prepared as a solution of ethyl acetate (25% v/v%) and added dropwise, and stirred at room temperature for 5 hours. The solution was extracted with ethyl acetate, washed with water, a 10% potassium carbonate aqueous solution and saturated brine in this order, dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under reduced pressure to obtain a solid (intermediate D2 in table 8 below), which was added with p-toluenesulfonic acid monohydrate (0.3 eq) in a xylene solvent, heated under reflux for 5 hours and subjected to azeotropic dehydration. After the reaction, the reaction mixture was cooled, the solvent was distilled off under reduced pressure, and the solid was washed with ethanol to obtain products G1 to G8 shown in table 8 below, wherein the yield and MS data are as follows.

[ TABLE 8 ]

Step 3-1: preparation of intermediate Compounds E1-1 to E1-6

The same procedure as in step 2-1 was used except that the starting

materials

1 and 2 of the following table 9 were used instead of the starting

materials

1 and 2 of the above table 7 in order to produce the intermediate compounds E1-1 to E1-6, respectively, to obtain the products E1-1 to E1-6 of the following table 9, the respective yields and MS data of which are shown below.

[ TABLE 9 ]

Step 3-2 and 3-3: production of intermediate compounds H1-H6

The same methods as in steps 2-2 and 2-3 were used except that the starting

materials

1 and 2 of the following table 10 were used instead of the starting

materials

1 and 2 of the above table 8 in order to produce the intermediate compounds H1 to H5, respectively, to thereby obtain H1 to H6 of the following table 10, with the respective yields and MS data shown below.

[ TABLE 10 ]

Production of intermediate Compound H7

10.0g (41mmol) of 4-iodobenzoic acid were suspended in 100ml of 1, 2-dichloroethane, and 3 drops of N, N-dimethylformamide were added. 7.3g (61mmol) of thionyl chloride was further added, and heated under reflux for 2 hours. Subsequently, the solvent was removed by evaporation, the residue was dissolved in 100ml of N-methylpyrrolidone, and 5.0g (41mmol) of N-ethyl-1, 2-phenylenediamine was added under cooling on ice, and the mixture was stirred at room temperature for 5 hours. After the reaction was completed, water was added to the reaction mixture, and the precipitated solid was filtered, and then ethyl acetate and water were added to the obtained solid to extract an organic layer (insoluble matter was separated by filtration). The organic layer was washed with 5% aqueous potassium carbonate solution, water and brine, and dried over sodium sulfate. The solvent was removed by evaporation to obtain 11g of a mixture of crude 4-iodo-N- (2-ethylamino-phenyl) benzamide and crude N- (2-aminophenyl) -4-iodo-N-ethylbenzamide.

11g (31mmol) of the obtained mixture and 1.75g (9mmol) of p-toluenesulfonic acid monohydrate were dispersed in 100ml of xylene and heated under reflux for 7 hours. After the reaction was completed, the mixture was cooled, and 5% aqueous potassium carbonate solution and toluene were added to extract an organic layer. The organic layer was washed with 5% aqueous potassium carbonate solution, water and brine, and dried over sodium sulfate. The solvent was removed by evaporation, and the obtained brown oil was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate 3/1), thereby obtaining H7(2.7g, yield: 20%).

MS[M+H]⁺＝349.19

Production example 1: production of Compound 1

F2-1(1 equivalent) produced in synthesis example 1 and G1(1.02 equivalent) produced in synthesis example 2 were added to THF (excess), and then 2M potassium carbonate aqueous solution (30 vol% to THF) was added, and tetrakis (triphenylphosphine) palladium (2 mol%) was added, followed by stirring with heating for 10 hours. The temperature was lowered to room temperature, and after the reaction was completed, the aqueous potassium carbonate solution was removed to conduct layer separation. After removal of the solvent, vacuum distillation was performed, and recrystallization was performed with THF and ethyl acetate to produce the title compound.

Production example 2: production of Compound 2

The title compound was produced by the same method as in production example 1, except that compound G4 was used instead of compound G1.

Production example 3: production of Compound 3

The title compound was produced by using the same method as in production example 1, except that the compound F2-2 was used instead of the compound F2-1 and the compound G2 was used instead of the compound G1.

Production example 4: production of Compound 4

The title compound was produced by using the same method as in production example 1, except that the compound F2-3 was used instead of the compound F2-1 and the compound G5 was used instead of the compound G1.

Production example 5: production of Compound 5

The title compound was produced by using the same method as in production example 1, except that the compound F2-12 was used instead of the compound F2-1 and the compound G7 was used instead of the compound G1.

Production example 6: production of Compound 6

The title compound was produced by using the same method as in production example 1, except that the compound F2-13 was used instead of the compound F2-1 and the compound G6 was used instead of the compound G1.

Production example 7: production of Compound 7

The title compound was produced by using the same method as in production example 1, except that the compound F2-4 was used instead of the compound F2-1 and the compound G2 was used instead of the compound G1.

Production example 8: production of Compound 8

The title compound was produced by using the same method as in production example 1, except that compound F2-5 was used instead of compound F2-1 and compound G3 was used instead of compound G1.

Production example 9: production of Compound 9

The title compound was produced by using the same method as in production example 1, except that compound F2-6 was used instead of compound F2-1 and compound G5 was used instead of compound G1.

Production example 10: production of Compound 10

The title compound was produced by using the same method as in production example 1, except that the compound F2-7 was used instead of the compound F2-1 and the compound G4 was used instead of the compound G1.

Production example 11: production of Compound 11

The title compound was produced by using the same method as in production example 1, except that the compound F2-8 was used instead of the compound F2-1 and the compound G2 was used instead of the compound G1.

Production example 12: production of Compound 12

The title compound was produced by using the same method as in production example 1, except that the compound F2-9 was used instead of the compound F2-1 and the compound G8 was used instead of the compound G1.

Production example 13: production of Compound 13

The title compound was produced by using the same method as in production example 1, except that compound F2-4 was used instead of compound F2-1 and compound H2 was used instead of compound G1.

Production example 14: production of Compound 14

The title compound was produced by the same method as in production example 1, except that compound H4 was used instead of compound G1.

Production example 15: production of Compound 15

The title compound was produced by using the same method as in production example 1, except that the compound F2-14 was used instead of the compound F2-1 and the compound H3 was used instead of the compound G1.

Production example 16: production of Compound 16

The title compound was produced by using the same method as in production example 1, except that the compound F2-14 was used instead of the compound F2-1 and the compound H5 was used instead of the compound G1.

Production example 17: production of Compound 17

The title compound was produced by using the same method as in production example 1, except that compound F2-10 was used instead of compound F2-1 and compound H6 was used instead of compound G1.

Production example 18: preparation of Compound 18

The title compound was produced by using the same method as in production example 1, except that the compound F2-11 was used instead of the compound F2-1 and the compound H7 was used instead of the compound G1.

The yields and MS data of the compounds 1 to 18 produced in the above production examples 1 to 18 are shown in the following table 11.

[ TABLE 11 ]

Example 1

As anode, will be 70/1000

The ITO/Ag/ITO-evaporated substrate was cut into a size of 50 mm. times.50 mm. times.0.5 mm, and placed in distilled water in which a dispersant was dissolved, and washed by ultrasonic waves. The detergent used was a product of Fisher Co, and the distilled water was filtered 2 times 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, ultrasonic washing was performed in the order of solvents of isopropyl alcohol, acetone, and methanol, and then dried.

On the anode thus prepared, the following compound HI-1 was added

Is formed by thermal vacuum evaporation, and on the hole injection layer, HT1 as a hole transport substance is formed in a thickness of

Vacuum evaporation is performed to form a hole transport layer. Next, the following compound HT2 was used

To form a hole-accommodating layer, followed by the addition of host BH1 and dopant BD1(2 wt.%) to form a hole-accommodating layer

The thickness of (2) is vacuum-evaporated to form a light-emitting layer. Then, compound 1 produced in production example 1 and Liq were mixed at 5:5 to form a thickness

The electron transport layer of (1). In turn, will

Magnesium and lithium fluoride (LiF) in a thickness as an electron injection layer and then as a cathode to form a film

Forming magnesium and silver (1:4) and then

CP1 is evaporated, thereby completing the element. In the above process, the evaporation speed of the organic material is maintained

In seconds.

Examples 2 to 27 and comparative examples 1 to 7

Organic light-emitting elements were produced in the same manner as in example 1, except that the compounds shown in table 12 below were used as the electron transport layer material and the host material, and in examples 25 to 27, an electron control layer was further provided between the electron transport layer and the light-emitting layer.

The compounds used in examples 1 to 27 and comparative examples 1 to 7 described above are shown below.

Experimental example 1

When a current was applied to the organic light emitting elements manufactured in examples 1 to 27 and comparative examples 1 to 7 described above, the voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in table 12 below. T95 refers to the time required for the luminance to decrease from the initial luminance to 95%.

[ TABLE 12 ]

Example 28

As an anode, will

The ITO-coated substrate was cut into a size of 50 mm. times.50 mm. times.0.5 mm, and placed in distilled water in which a dispersant was dissolved, and washed by ultrasonic waves. The detergent used was a product of Fisher Co, and the distilled water was filtered 2 times 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, ultrasonic washing was performed in the order of solvents of isopropyl alcohol, acetone, and methanol, and then dried.

On the anode thus prepared, HI-1 was added

Is formed by thermal vacuum evaporation, and on the hole injection layer, HT3 as a hole transport substance is formed in a thickness of

Vacuum evaporation is performed to form a hole transport layer. Then, using HT4

To form a first hole-adjusting layer, followed by the addition of host BH1 and dopant BD1(2 wt.%) to form a second hole-adjusting layer

The thickness of (2) is vacuum-evaporated to form a light-emitting layer. Then, compound 1 produced in production example 1 was used to form a thickness

The electron transport layer of (1). In turn, after ET6

The thickness of the film was co-evaporated with lithium (2 wt%) to form an electron injection layer, and then aluminum was added as a cathode

The evaporation was performed to complete the device. In the above process, the evaporation speed of the organic material is maintained

In seconds.

Examples 29 to 54 and comparative examples 8 to 13

Organic light-emitting elements were produced in the same manner as in example 28, except that the compounds shown in table 13 below were used as the electron-transporting material and the host material, and that examples 52 to 54 further included an electron-controlling layer between the electron-transporting layer and the light-emitting layer.

Experimental example 2

When a current was applied to the organic light emitting elements manufactured in examples 28 to 54 and comparative examples 8 to 13 described above, the voltage, efficiency, color coordinates, and lifetime were measured, and the results thereof are shown in table 13 below. T95 refers to the time required for the luminance to decrease from the initial luminance to 95%.

[ TABLE 13 ]

As shown in tables 12 and 13, it was confirmed that the organic light emitting device using the compound of the present invention as an electron transport layer material exhibited superior characteristics in terms of driving voltage, efficiency, and stability by smoothly injecting electrons into a light emitting layer, adjusting smooth transport of carriers, and balancing of holes and electrons according to a chemical structure, as compared to the organic light emitting device using the compound of the comparative example as an electron transport layer material.

Description of the symbols

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

1. A compound represented by the following chemical formula 1:

chemical formula 1

In the chemical formula 1, the first and second organic solvents,

Ar₁to Ar₃Each independently is substituted or unsubstituted C_6-60An aryl group; or substituted or unsubstituted C comprising one or more selected from N, O and S_2-60(ii) a heteroaryl group, wherein,

in the chemical formulas 2-1 to 2-3,

n1 and n2 are each independently an integer from 0 to 4,

n3 is an integer from 0 to 3,

represents L of the chemical formula 1₂The position of the connection is such that,

2. The compound of claim 1, wherein L₁And L₂Each independently is selected from a single bond and any one of the following groups:

3. the compound of claim 1, wherein Ar₁To Ar₃Each independently is phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothienyl, or carbazolyl,

wherein Ar is₁To Ar₃Is unsubstituted; or substituted with 1 or 2 substituents each independently selected from methyl, phenyl, dibenzofuranyl, and dibenzothiophenyl.

4. The compound of claim 1, wherein Ar₁To Ar₃Each independently is any one selected from the following groups:

in the above-mentioned group, the group,

x is O, S, C (methyl)₂Or N (phenyl).

5. The compound according to claim 1, wherein, in the chemical formulas 2-1 to 2-3,

Z₁to Z₇Each independently is hydrogen, C_1-4Alkyl radical, C_6-10Aryl, or C containing 1 or 2N atoms_2-10A heteroaryl group.

6. The compound according to claim 1, wherein, in the chemical formulas 2-1 to 2-3,

Z₁to Z₄Each independently hydrogen, methyl, ethyl, isopropyl, phenyl, naphthyl, pyridyl, or quinolyl,

Z₅to Z₇Each independently hydrogen, methyl, ethyl, or phenyl.

7. The compound of claim 1, wherein R₁To R₄Are all hydrogen, or

R₁And R₂Is hydrogen, R₃And R₄Each independently is C_1-4An alkyl group.

8. The compound according to claim 1, wherein the compound is represented by any one of the following chemical formulas 1-1 to 1-3:

chemical formula 1-1

Chemical formula 1-2

Chemical formulas 1 to 3

In the chemical formulas 1-1 to 1-3,

L₁、L₂、Ar₁to Ar₃、R₁To R₄And Z₁To Z₆As defined in claim 1,

Z₅' and Z₆' respective reference to Z₅And Z₆And (4) description.

9. The compound of claim 1, wherein the compound is any one selected from the group consisting of:

10. an organic light-emitting element, comprising: a first electrode, a second electrode provided so as to face the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contain the compound according to any one of claims 1 to 9.