WO2024136070A1

WO2024136070A1 - Organic light-emitting device

Info

Publication number: WO2024136070A1
Application number: PCT/KR2023/016445
Authority: WO
Inventors: 최지영; 금수정; 전지예; 조우진; 차용범; 하재승; 황성현; 이우철
Original assignee: 주식회사 엘지화학
Priority date: 2022-12-21
Filing date: 2023-10-23
Publication date: 2024-06-27
Also published as: CN118542097A; KR20240099012A

Abstract

The present specification provides an organic light-emitting device comprising two or more types of a compound represented by chemical formula 1-1.

Description

organic light emitting device

This application claims the benefit of Korean Patent Application No. 10-2022-0180844 filed with the Korea Intellectual Property Office on December 21, 2022, the entire contents of which are incorporated herein by reference.

This specification relates to organic light emitting devices.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices that utilize the organic light-emitting phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

The development of new materials for organic light-emitting devices as described above continues to be required.

This specification seeks to provide an organic light emitting device.

An exemplary embodiment of the present specification includes an anode; cathode; An organic light-emitting device is provided, including a first organic material layer provided between the anode and the cathode, wherein the first organic material layer includes two or more compounds represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1,

X1 and X1' are the same or different from each other and are each independently O or S,

L1 is a direct bond or a substituted or unsubstituted arylene group,

Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 and R2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R3 is hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n1 is an integer from 0 to 8, and when n1 is 2 or more, 2 or more R1 are the same or different from each other,

n2 is an integer from 0 to 4, and when n2 is 2 or more, 2 or more R2 are the same or different from each other,

n3 is an integer from 0 to 6, and when n3 is 2 or more, 2 or more R3s are the same or different from each other.

The organic light emitting device described in this specification includes two or more compounds represented by Formula 1-1 in the first organic layer, thereby providing low driving voltage, high efficiency, and/or long lifespan.

1 shows a substrate (1), anode (2), hole injection layer (3), hole transport layer (4), electron blocking layer (5), light emitting layer (6), hole blocking layer (7), and electron transport layer (8). , shows an example of an organic light emitting device in which the electron injection layer 9 and the cathode 10 are sequentially stacked.

[Explanation of symbols]

1: substrate

2: Anode

3: Hole injection layer

4: Hole transport layer

5: Electronic blocking layer

6: Light-emitting layer

7: Hole blocking layer

8: Electron transport layer

9: Electron injection layer

10: cathode

Hereinafter, this specification will be described in more detail.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

In this specification, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In this specification, the deuterium substitution rate of the compound is determined by using TLC-MS (Thin-Layer Chromatography/Mass Spectrometry) to determine the maximum distribution of molecular weights at the end of the reaction. A method of calculating the substitution rate based on the value or a quantitative analysis method using NMR can be determined by adding DMF as an internal standard and calculating the D-substitution rate from the integral amount of the total peak using the integration rate on 1H NMR. You can.

In this specification, “energy level” means energy level. Therefore, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, a low or deep energy level means that the absolute value increases in the minus direction from the vacuum level.

In this specification, HOMO (highest occupied molecular orbital) refers to the molecular orbital (highest occupied molecular orbital) in the region with the highest energy in the region where electrons can participate in bonding, and LUMO (lowest unoccupied molecular orbital) refers to the molecular orbital function (lowest unoccupied molecular orbital) in which an electron is located in the lowest energy region of the antibonding region, and the HOMO energy level refers to the distance from the vacuum level to HOMO. Additionally, the LUMO energy level refers to the distance from the vacuum level to the LUMO.

In this specification, bandgap refers to the energy level difference between HOMO and LUMO, that is, the HOMO-LUMO gap (Gap).

In this specification, the HOMO energy level can be measured using an atmospheric photoelectron spectrometer (AC3 manufactured by RIKEN KEIKI Co., Ltd.), and the LUMO energy level can be calculated from the wavelength value measured through photoluminescence (PL). You can.

Examples of substituents in this specification are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent. The position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and if two or more substituents are substituted. , two or more substituents may be the same or different from each other.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group (-CN); nitro group; hydroxyl group; Alkyl group; Cycloalkyl group; Alkoxy group; Phosphine oxide group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; alkenyl group; silyl group; boron group; amine group; Aryl group; Alternatively, it means that it is substituted with one or two or more substituents selected from the group consisting of heterocyclic groups, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituents. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group; silyl group; Alkoxy group; Aryloxy group; Alkyl group; Aryl group; and a heterocyclic group, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; Alkyl group; Aryl group; and a heterocyclic group, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituent.

Examples of the above substituents are described below, but are not limited thereto.

In this specification, examples of halogen groups include fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

In the present specification, the silyl group may be represented by the formula -SiYaYbYc, where Ya, Yb, and Yc are each hydrogen; Substituted or unsubstituted alkyl group; Or, it may be a substituted or unsubstituted aryl group. The silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. No.

In the present specification, the boron group may be represented by the chemical formula -BYdYe, where Yd and Ye are each hydrogen; Substituted or unsubstituted alkyl group; Or, it may be a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, and phenyl boron group.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the carbon number of the alkyl group is 1 to 30. According to another embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, etc., but are not limited to these.

In the present specification, the description of the alkyl group described above can be applied, except that the arylalkyl group is substituted with an aryl group.

In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, t-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, It may be isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, etc., but is not limited thereto. .

Substituents containing alkyl groups, alkoxy groups, and other alkyl group moieties described in this specification include both straight-chain or branched forms.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, etc., but are not limited to these.

In the present specification, the alkynyl group is a substituent containing a triple bond between carbon atoms, and may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, it includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but is not limited thereto.

In the present specification, the amine group is -NH ₂ , and the amine group may be substituted with the above-described alkyl group, aryl group, heterocyclic group, alkenyl group, cycloalkyl group, and combinations thereof. The number of carbon atoms of the substituted amine group is not particularly limited, but is preferably 1 to 30. According to one embodiment, the carbon number of the amine group is 1 to 20. According to one embodiment, the carbon number of the amine group is 1 to 10. Specific examples of substituted amine groups include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, 9,9-dimethylfluorenylphenylamine group, pyridylphenylamine group, and diphenylamine. group, phenylpyridylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, dibenzofuranylphenylamine group, 9-methylanthracenylamine group, diphenylamine group, phenylnaphthylamine group, Ditolylamine group, phenyltolylamine group, diphenylamine group, etc., but are not limited to these.

In the present specification, the aryl group is not particularly limited, but preferably has 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 monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or a quarterphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure.

When the fluorenyl group is substituted,

Spirofluorenyl group, etc.,

(9,9-dimethylfluorenyl group), and

It may be a substituted fluorenyl group such as (9,9-diphenylfluorenyl group). However, it is not limited to this.

In the present specification, the description regarding the aryl group described above may be applied to the aryl group in the aryloxy group.

In the present specification, the heterocyclic group is a cyclic group containing one or more of N, O, P, S, Si, and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the heterocyclic group has 2 to 30 carbon atoms. According to one embodiment, the heterocyclic group has 2 to 20 carbon atoms. Examples of heterocyclic groups include pyridine group, pyrrole group, pyrimidine group, quinoline group, pyridazinyl group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group, and carboxymethyl group. Examples include sol group, benzocarbazole group, naphthobenzofuran group, benzonaphthothiophene group, indenocarbazole group, and triazinyl group, but are not limited to these.

In the present specification, the description regarding the heterocyclic group described above can be applied, except that the heteroaryl group is aromatic.

In the present specification, the description of the aryl group may be applied, except that the arylene group is divalent.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic, or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group.

In this specification, an aliphatic hydrocarbon ring refers to a non-aromatic ring consisting only of carbon and hydrogen atoms. Examples of aliphatic hydrocarbon rings include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, and cyclooctene. It is not limited to this.

In this specification, an aromatic hydrocarbon ring refers to an aromatic ring consisting only of carbon and hydrogen atoms. Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, triphenylene, phenalene, pyrene, tetracene, chrysene, pentacene, fluorene, indene, acenaphthylene, Benzofluorene, spirofluorene, etc., but are not limited thereto. In the present specification, an aromatic hydrocarbon ring can be interpreted to have the same meaning as an aryl group.

As used herein, an aliphatic heterocycle refers to an aliphatic ring containing one or more heteroatoms. Examples of aliphatic heterocycles include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, and azocaine. , thiocane, etc., but is not limited thereto.

As used herein, an aromatic heterocycle refers to an aromatic ring containing one or more heteroatoms. Examples of aromatic heterocycles include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, parazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, and thiazole. Diazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, tetrazine, isoquinoline, quinoline, quinone, quinazoline, quinoxaline, naphthyridine, acridine , phenanthridine, diazanaphthalene, driazindene, indole, indolizine, benzothiazole, benzoxazole, benzoimidazole, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, carbazole, benzoyl Examples include, but are not limited to, carbazole, dibenzocarbazole, phenazine, imidazopyridine, phenoxazine, indolocarbazole, and indenocarbazole.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below.

The organic light emitting device of the present invention is characterized in that it includes a first organic material layer containing two or more compounds represented by Chemical Formula 1-1.

Hereinafter, Chemical Formula 1-1 will be described in detail.

[Formula 1-1]

In Formula 1-1,

L1 is a direct bond or a substituted or unsubstituted arylene group,

According to an exemplary embodiment of the present specification, X1 is O or S.

According to an exemplary embodiment of the present specification, X1' is O or S.

In an exemplary embodiment of the present specification, Formula 1-1 is represented by any one of the following Formulas 1-1-1 to 1-1-3.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

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

The definitions of X1,

In an exemplary embodiment of the present specification, the first organic layer includes two or more compounds represented by any one of the formulas 1-1-1 to 1-1-3.

In one embodiment of the present specification, the first organic layer is a compound represented by the following formula 1-1-1; and compounds represented by the following formula 1-1-2.

[Formula 1-1-1]

[Formula 1-1-2]

In the above formulas 1-1-1 and 1-1-2,

The definitions of X1,

Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group.

In one embodiment of the present specification, the first organic layer includes two types of compounds represented by the following formula 1-1-1.

[Formula 1-1-1]

In the above formula 1-1-1,

The definitions of X1, X1', R1, R2, R3, n1, n2, n3 and L1 are the same as in Formula 1-1,

In one embodiment of the present specification, the first organic layer includes two types of compounds represented by the following formula 1-1-2.

[Formula 1-1-2]

In the above formula 1-1-2,

According to an exemplary embodiment of the present specification, L1 is a direct bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

According to another embodiment, L1 is a direct bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

According to another embodiment, L1 is a direct bond.

In one embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to another embodiment, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to another embodiment, Ar1 is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with deuterium, or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with deuterium.

According to another exemplary embodiment, Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group.

In another exemplary embodiment, Ar1 is a phenyl group unsubstituted or substituted with deuterium; Biphenyl group substituted or unsubstituted with deuterium; Or it is a naphthyl group substituted or unsubstituted with deuterium.

According to an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to another exemplary embodiment, R1 and R2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to another embodiment, R1 and R2 are the same as or different from each other, and are each independently hydrogen or deuterium.

According to an exemplary embodiment of the present specification, R3 is the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to another exemplary embodiment, R3 is the same as or different from each other, and each independently represents hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to another embodiment, R3 is the same as or different from each other, and each independently represents hydrogen or deuterium.

According to an exemplary embodiment of the present specification, n1 is an integer from 0 to 8, and when n1 is 2 or more, 2 or more R1 are the same or different from each other.

According to an exemplary embodiment of the present specification, n2 is an integer from 0 to 4, and when n2 is 2 or more, 2 or more R2 are the same or different from each other.

According to an exemplary embodiment of the present specification, n3 is an integer from 0 to 6, and when n3 is 2 or more, 2 or more R3 are the same or different from each other.

According to an exemplary embodiment of the present specification, when Ar1 of Formula 1-1 is a phenyl group substituted or unsubstituted with deuterium, injection and movement of holes can be improved, and Ar1 is substituted with deuterium, a naphthyl group, or a deuterium group. In the case of a substituted or unsubstituted biphenyl group, injection and movement of electrons can be improved. Therefore, one compound in which Ar1 of Formula 1-1 is a phenyl group substituted or unsubstituted with deuterium and a naphthyl group in which Ar1 of Formula 1-1 is substituted or unsubstituted with deuterium, or a ratio in which Ar1 of Formula 1-1 is substituted or unsubstituted with deuterium An organic light-emitting device using a combination of one type of phenyl compound can improve both injection and movement of holes and electrons. In addition, it has the feature of not only lowering the driving voltage of the organic light-emitting device, but also improving efficiency and lifespan characteristics by optimizing charge balance.

According to an exemplary embodiment of the present specification, the deuterium substitution rate of Chemical Formula 1-1 is 40% to 100%.

According to an exemplary embodiment of the present specification, a combination of two compounds in which Ar1 of Formula 1-1 is an aryl group substituted with deuterium and R1 to R3 are all deuterium can be applied. These organic light emitting devices can lower the driving voltage, improve efficiency, and significantly improve lifespan characteristics.

In one embodiment of the present specification, Formula 1-1 is represented by any one of the following compounds.

The core structure of the compound represented by Chemical Formula 1-1 according to an exemplary embodiment of the present specification may be manufactured as in the method of the synthesis example described later. Substituents may be combined by methods known in the art, and the type, position, or number of substituents may be changed according to techniques known in the art.

In the present specification, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure of the compound represented by Formula 1-1. In addition, in the present specification, the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents into the core structure of the above structure.

Hereinafter, the organic light emitting device will be described.

In this specification, when a part “includes” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

The organic light emitting device according to the present specification includes an anode; cathode; It includes a first organic material layer provided between the anode and the cathode, and the first organic material layer is characterized in that it includes two or more types of compounds represented by the following Chemical Formula 1-1.

The organic light emitting device of the present invention can be manufactured by conventional organic light emitting device manufacturing methods and materials, except that the first organic material layer is formed using two or more compounds represented by the above-mentioned Chemical Formula 1-1. .

When manufacturing an organic light-emitting device including the first organic material layer, the organic material layer may be formed by a solution coating method as well as a vacuum deposition method. Here, the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention is an organic material layer that includes one layer among a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole transport and injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection layer. It may have a structure that includes the above. However, the structure of the organic light emitting device of the present specification is not limited to this and may include fewer or more organic material layers.

In the organic light emitting device according to an exemplary embodiment of the present specification, the first organic material layer may be a hole transport layer, a hole injection layer, a hole transport and injection layer, or an electron blocking layer.

In the organic light emitting device according to an exemplary embodiment of the present specification, the first organic material layer may be a light emitting layer and may further include a dopant material. At this time, two or more compounds of the above-mentioned formula 1-1 are the hosts of the light-emitting layer.

Examples of the dopant material include phosphorescent materials such as (4,6-F ₂ ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), PFO-based polymer, and PPV. Fluorescent materials such as polymers, anthracene-based compounds, pyrene-based compounds, boron-based compounds, etc. may be used, but are not limited thereto. At this time, the dopant in the light emitting layer is included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the host.

In the organic light emitting device according to an exemplary embodiment of the present specification, the first organic material layer may be an electron transport layer, an electron injection layer, an electron transport and injection layer, or a hole blocking layer.

The organic light emitting device of the present specification is further provided with one or more organic material layers between the anode and the cathode, and the organic material layer includes a hole transport layer, a hole injection layer, a hole transport and injection layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer. , it may further include one or more layers of an electron transport and injection layer and a hole blocking layer.

In the organic light-emitting device according to an exemplary embodiment of the present specification, the first organic material layer includes two types of compounds of Formula 1-1 described above, and the mass ratio of the two types of compounds of Formula 1-1 is 90:10 to 10. :Could be 90.

The structure of the organic light emitting device of this specification may have the same structure as shown in FIG. 1, but is not limited thereto.

1 shows a substrate (1), anode (2), hole injection layer (3), hole transport layer (4), electron blocking layer (5), light emitting layer (6), hole blocking layer (7), and electron transport layer (8). , the structure of an organic light emitting device in which the electron injection layer 9 and the cathode 10 are sequentially stacked is illustrated. In this structure, the first organic layer of the present specification may be the light-emitting layer (6).

According to an exemplary embodiment of the present specification, the organic light emitting device may have a tandem structure in which two or more independent devices are connected in series. In one embodiment, the tandem structure may be in a form in which each organic light-emitting device is bonded to a charge generation layer. Tandem-structured devices can be driven at lower currents than unit devices based on the same brightness, which has the advantage of greatly improving the device's lifespan characteristics.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light-emitting device of the present invention can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that the first organic layer is formed using two types of compounds represented by the above-mentioned Chemical Formula 1-1.

According to an exemplary embodiment of the present specification, the first organic layer containing two types of compounds represented by Chemical Formula 1-1 may be formed by vacuum deposition or solution application.

According to an exemplary embodiment of the present specification, the first organic layer is co-deposited using each deposition source; Alternatively, it may be formed through premixed deposition using a single deposition source. The co-deposition is to form a first organic material layer using a deposition source containing one type of compound of Chemical Formula 1-1 and a deposition source containing an additional compound of Chemical Formula 1-1, and the premix deposition is One compound of Chemical Formula 1-1 and one additional compound of Chemical Formula 1-1 are mixed and placed in one deposition source to form a first organic layer. When forming an organic material layer containing the same compound, premix deposition allows smoother interactions between compounds compared to co-deposition, thereby improving processability and improving the characteristics of the manufactured device.

When manufacturing the organic light emitting device of the present specification, the organic material layer may be formed by a solution coating method as well as a vacuum deposition method. Here, the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

For example, the organic light emitting device according to the present specification uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to deposit a metal, a conductive metal oxide, or an alloy thereof on a substrate. An anode is formed by depositing an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. can be manufactured. In addition to this method, an organic light-emitting device can also be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic layer may further include one or more of a hole transport layer, a hole injection layer, an electron blocking layer, an electron transport and injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and a hole transport and injection layer.

The anode of the present invention is an electrode that injects holes, and the anode material is generally preferably a material with a large work function to ensure smooth hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combination of metal and oxide such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

The cathode of the present invention is an electrode that injects electrons, and the cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

The hole injection layer of the present invention is a layer that serves to facilitate the injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can easily inject holes from the anode at a low voltage. The HOMO (HOMO) of the hole injection material is It is preferable that the highest occupied molecular orbital is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include the above-mentioned compounds or metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrilehexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. (perylene)-based organic materials, anthraquinone, and polyaniline- and polythiophene-based conductive polymers, etc., but are not limited to these.

The hole transport layer of the present invention can play a role in facilitating the transport of holes. The hole transport material is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include, but are not limited to, the above-described compounds or arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.

An additional hole buffer layer may be provided between the hole injection layer and the hole transport layer, and may include the above-described compound or a hole injection or transport material known in the art.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The above-described compounds or materials known in the art may be used in the electron blocking layer.

The light-emitting layer may emit red, green, or blue light and may be made of a phosphorescent material or a fluorescent material. The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

Host materials for the light emitting layer include condensed aromatic ring derivatives or heterocyclic ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

When the light-emitting layer emits red light, the light-emitting dopants include PIQIr(acac)(bis(1-phenylsoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), and PQIr(tris(1-phenylquinoline)iridium). ), phosphorescent materials such as PtOEP (octaethylporphyrin platinum), or fluorescent materials such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but are not limited to these. If the light-emitting layer emits green light, the light-emitting dopant may be a phosphor such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium), Alq ₃ (tris(8-hydroxyquinolino)aluminum), an anthracene compound, or pi. Fluorescent substances such as ren-based compounds and boron-based compounds may be used, but are not limited thereto. If the light-emitting layer emits blue light, the light-emitting dopant may be a phosphorescent material such as (4,6-F2ppy)2Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), or PFO. Fluorescent materials such as polymers, PPV-based polymers, anthracene-based compounds, pyrene-based compounds, boron-based compounds, etc. may be used, but are not limited to these.

A hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used.

The electron transport layer may play a role in facilitating the transport of electrons. The electron transport material is a material that can easily receive electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complex containing Alq3; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these.

The electron injection layer may serve to facilitate the injection of electrons. The electron injection material has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light emitting layer or a light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also has an excellent electron injection effect from the cathode to the light emitting layer or light emitting material. , Compounds with excellent thin film forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metals. These include, but are not limited to, complex compounds and nitrogen-containing five-membered ring derivatives.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and can generally be formed under the same conditions as the hole injection layer. Specifically, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc. are included, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

Hereinafter, in order to explain the present specification in detail, examples will be given in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described in detail below. The embodiments of this application are provided to more completely explain the present specification to those with average knowledge in the art.

<합성예><Synthesis example>

합성예 1-1. BH1-1의 합성Synthesis Example 1-1. Synthesis of BH1-1

<1-1-a> 화합물 BH 1-1-a의 합성<1-1-a> Synthesis of compound BH 1-1-a

9-Bromoanthracene-1,2,3,4,5,6,7,8,10-d9 (50 g, 188 mmol) and phenylboronic acid (25.2 g, 20.6 mmol) were reacted with 1,4-dioxane ( After dissolving in 500ml), Pd(PPh ₃ ) ₄ (10.9g, 9.4 mmol) and K ₂ CO ₃ (52.2g, 376mmol) were dissolved in 150ml of distilled water and stirred under reflux for 24 hours. The reaction solution was cooled, the water layer was removed, and 1,4-dioxane was removed by distillation under reduced pressure. After dissolving in chloroform, it was placed in a separatory funnel, washed three times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. Afterwards, chloroform was removed under reduced pressure and recrystallized with ethyl acetate (EA) to obtain compound BH 1-1-a (45 g, yield 91%).

<1-1-b> 화합물 BH 1-1-b의 합성<1-1-b> Synthesis of compound BH 1-1-b

The compound BH 1-1-a (45 g, 171 mmol) was dispersed in 450 ml of chloroform, and n-bromosuccinimide (30.4 g, 171 mmol) solution dissolved in 50 ml of dimethylformamide was slowly added dropwise. After reaction at room temperature for 2 hours, 100 ml of 20% aqueous solution of Na ₂ S ₂ O ₃ was added dropwise, the organic layer was separated using a separatory funnel, and washed three times with distilled water. Afterwards, residual moisture was removed with anhydrous magnesium sulfate, chloroform was removed by distillation under reduced pressure, and recrystallized from ethyl acetate (EA) to obtain compound BH 1-1-b (50 g, yield 86%).

<1-1-c> 화합물 BH 1-1의 합성<1-1-c> Synthesis of compound BH 1-1

Compound BH 1-1-b (50 g, 147 mmol) and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[1,2-b :4,3-b'] Bisbenzofuran (62g, 161mmol) was dissolved in 1,4-dioxane (500ml), then Pd(PPh ₃ ) ₄ (8.46g, 7.3 mmol) and K ₂ CO ₃ (40.5 g, 293 mmol) was dissolved in 150 ml of distilled water and refluxed for 24 hours. The reaction solution was cooled, the resulting solid was filtered, dissolved in chloroform, placed in a separatory funnel, and washed three times with distilled water. Afterwards, the organic layer was dried with anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and the mixture was recrystallized with ethyl acetate (EA) to obtain compound BH 1-1 (52 g, yield 68%). [M+H ⁺ ]=519.2

합성예 1-2. BH 1-2의 합성Synthesis Example 1-2. Synthesis of BH 1-2

<1-2-a> 화합물 BH 1-2-a의 합성<1-2-a> Synthesis of compound BH 1-2-a

Compound BH 1-2-a was obtained in the same manner as in Synthesis Example 1-1-a, except that naphthalen-1-yl boronic acid was used instead of phenylboronic acid.

<1-2-b> 화합물 BH 1-2-b의 합성<1-2-b> Synthesis of compound BH 1-2-b

BH 1-2-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-2-a was used instead of compound BH 1-1-a.

<1-2-c> 화합물 BH 1-2의 합성<1-2-c> Synthesis of compound BH 1-2

BH 1-2 was obtained by the same synthesis in Synthesis Example 1-1-c, except that compound BH 1-2-b was used instead of compound BH 1-1-b. [M+H ⁺ ]=569.2

합성예 1-3. 화합물 BH 1-3의 합성Synthesis Example 1-3. Synthesis of Compound BH 1-3

<1-3-a> 화합물 BH 1-3-a의 합성<1-3-a> Synthesis of compound BH 1-3-a

In Synthesis Example 1-1-a, 9-bromoanthracene was used instead of 9-bromoanthracene-1,2,3,4,5,6,7,8,10-d9, and [1,1' was used instead of phenylboronic acid. Compound BH 1-3-a was obtained by the same synthesis except that -biphenyl]-4-ylboronic acid was used.

<1-3-b> 화합물 BH 1-3-b의 합성<1-3-b> Synthesis of compound BH 1-3-b

BH 1-3-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-3-a was used instead of compound BH 1-1-a.

<1-3-c> 화합물 BH 1-3의 합성<1-3-c> Synthesis of compound BH 1-3

BH 1-3 was obtained by the same synthesis in Synthesis Example 1-1-c, except that compound BH 1-3-b was used instead of compound BH 1-1-b. [M+H ⁺ ]=587.2

합성예 1-4. 화합물 BH 1-4의 합성Synthesis Example 1-4. Synthesis of Compound BH 1-4

<1-4-a> 화합물 BH 1-4-a의 합성<1-4-a> Synthesis of compound BH 1-4-a

Compound was synthesized in the same manner as in Synthesis Example 1-1-a, except that 9-bromoanthracene was used instead of 9-bromoanthracene-1,2,3,4,5,6,7,8,10-d9. BH 1-4-a was obtained.

<1-4-b> 화합물 BH 1-4-b의 합성<1-4-b> Synthesis of compound BH 1-4-b

BH 1-4-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-4-a was used instead of compound BH 1-1-a.

<1-4-c> 화합물 BH 1-4의 합성<1-4-c> Synthesis of compound BH 1-4

In Synthesis Example 1-1-c, compound BH 1-4-b was replaced with compound BH 1-1-b, and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)benzo[1,2-b:4,3-b']bisbenzofuran instead of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- 1) BH 1-4 was obtained by the same synthesis except that benzo[1,2-b:4,3-b']bisbenzofuran was used. [M+H ⁺ ]=511.2

합성예 1-5. 화합물 BH 1-5의 합성Synthesis Example 1-5. Synthesis of compounds BH 1-5

In Synthesis Example 1-1-c, compound BH 1-2-b was replaced with compound BH 1-1-b, and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)benzo[1,2-b:4,3-b']bisbenzofuran instead of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- 1) BH 1-5 was obtained by the same synthesis except that benzo[1,2-b:4,3-b']bisbenzofuran was used. [M+H ⁺ ]=569.2

합성예 1-6. 화합물 BH 1-6의 합성Synthesis Example 1-6. Synthesis of compound BH 1-6

<1-6-a> 화합물 BH 1-6-a의 합성<1-6-a> Synthesis of compound BH 1-6-a

In Synthesis Example 1-1-a, 9-bromoanthracene was used instead of 9-bromoanthracene-1,2,3,4,5,6,7,8,10-d9, and [1,1' was used instead of phenylboronic acid. Compound BH 1-6-a was obtained by the same synthesis except that -biphenyl]-2-ylboronic acid was used.

<1-6-b> 화합물 BH 1-6-b의 합성<1-6-b> Synthesis of compound BH 1-6-b

BH 1-6-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-6-a was used instead of compound BH 1-1-a.

<1-6-c> 화합물 BH 1-6의 합성<1-6-c> Synthesis of compound BH 1-6

BH 1-6 was obtained by the same synthesis in Synthesis Example 1-1-c, except that compound BH 1-6-b was used instead of compound BH 1-1-b. [M+H ⁺ ]=587.2

합성예 1-7. 화합물 BH 1-7의 합성Synthesis Example 1-7. Synthesis of compound BH 1-7

<1-7-a> 화합물 BH 1-7-a의 합성<1-7-a> Synthesis of compound BH 1-7-a

In Synthesis Example 1-1-a, 9-bromoanthracene was used instead of 9-bromoanthracene-1,2,3,4,5,6,7,8,10-d9, and naphthalene-2-ylbo was used instead of phenylboronic acid. Compound BH 1-7-a was obtained by the same synthesis except that ronic acid was used.

<1-7-b> 화합물 BH 1-7-b의 합성<1-7-b> Synthesis of compound BH 1-7-b

BH 1-7-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-7-a was used instead of compound BH 1-1-a.

<1-7-c> 화합물 BH 1-7-c의 합성<1-7-c> Synthesis of compound BH 1-7-c

BH 1-7-c was obtained by the same synthesis in Synthesis Example 1-1-c, except that compound BH 1-7-b was used instead of compound BH 1-1-b.

<1-7-d> 화합물 BH 1-7의 합성<1-7-d> Synthesis of compound BH 1-7

50g of compound BH 1-7-c, 10g of 5wt.% Pt/C, 300ml of toluene, and 700ml of D ₂ O were placed in a high pressure reactor and then charged with hydrogen. After raising the temperature to 180°C, the reaction was carried out for 24 hours. After completion of the reaction, the catalyst was filtered through a Celite pad and then extracted. 38g of BH 1-7 was obtained through tetrahydrofuran/ethyl acetate (THF/EA) recrystallization. (yield 73%). [M+H ⁺ ]=585.3

합성예 1-8. 화합물 BH 1-8의 합성Synthesis Example 1-8. Synthesis of compound BH 1-8

<1-8-a> 화합물 BH 1-8-a의 합성<1-8-a> Synthesis of compound BH 1-8-a

Compound BH 1-8-a was obtained in the same manner as in Synthesis Example 1-1-a, except that naphthalen-2-yl boronic acid was used instead of phenylboronic acid.

<1-8-b> 화합물 BH 1-8-b의 합성<1-8-b> Synthesis of compound BH 1-8-b

BH 1-8-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-8-a was used instead of compound BH 1-1-a.

<1-8-c> 화합물 BH 1-8의 합성<1-8-c> Synthesis of compound BH 1-8

In Synthesis Example 1-1-c, compound BH 1-8-b was replaced with compound BH 1-1-b, and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)benzo[1,2-b:4,3-b']bisbenzofuran instead of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- 1) BH 1-8 was obtained by the same synthesis except that benzo[1,2-b:4,5-b']bisbenzofuran was used. [M+H ⁺ ]=567.2

합성예 1-9. 화합물 BH 1-9의 합성Synthesis Example 1-9. Synthesis of compound BH 1-9

<1-9-a> 화합물 BH 1-9-a의 합성<1-9-a> Synthesis of compound BH 1-9-a

In Synthesis Example 1-1-a, 9-bromoanthracene was used instead of 9-bromoanthracene-1,2,3,4,5,6,7,8,10-d9, and dibenzo[b, c]Compound BH 1-9-a was obtained by the same synthesis except that furan-2-ylboronic acid was used.

<1-9-b> 화합물 BH 1-9-b의 합성<1-9-b> Synthesis of compound BH 1-9-b

BH 1-9-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-9-a was used instead of compound BH 1-1-a.

<1-9-c> 화합물 BH 1-9의 합성<1-9-c> Synthesis of compound BH 1-9

In Synthesis Example 1-1-c, compound BH 1-9-b was replaced with compound BH 1-1-b, and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) benzo[1,2-b:4,3-b']bisbenzofuran instead of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- 1) BH 1-9 was obtained by the same synthesis except that benzo[2,1-b:3,4-b']bisbenzofuran was used. [M+H ⁺ ]=601.2

합성예 1-10. 화합물 BH 1-10의 합성Synthesis Example 1-10. Synthesis of compound BH 1-10

In Synthesis Example 1-1-c, compound BH 1-7-b was replaced with compound BH 1-1-b, and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) benzo[1,2-b:4,3-b']bisbenzofuran instead of 9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- 1) BH 1-10 was obtained by the same synthesis except that benzo[2,1-b:3,4-b']bisbenzofuran was used. [M+H ⁺ ]=561.2

합성예 1-11. 화합물 BH 1-11의 합성Synthesis Example 1-11. Synthesis of compound BH 1-11

<1-11-a> 화합물 BH 1-11-a의 합성<1-11-a> Synthesis of compound BH 1-11-a

Compound BH 1-11-a was obtained in the same manner as in Synthesis Example 1-1-a, except that [1,1'-biphenyl]-2-ylboronic acid was used instead of phenylboronic acid.

<1-11-b> 화합물 BH 1-11-b의 합성<1-11-b> Synthesis of compound BH 1-11-b

BH 1-11-b was obtained by the same synthesis in Synthesis Example 1-1-b, except that compound BH 1-11-a was used instead of compound BH 1-1-a.

<1-11-c> 화합물 BH 1-11의 합성<1-11-c> Synthesis of compound BH 1-11

BH 1-11 was obtained by the same synthesis in Synthesis Example 1-1-c, except that compound BH 1-11-b was used instead of compound BH 1-1-b. [M+H ⁺ ]=595.2

합성예 1-12. 화합물 BH 1-12의 합성Synthesis Example 1-12. Synthesis of compound BH 1-12

In Synthesis Example 1-1-c, compound BH 1-2-b was replaced with compound BH 1-1-b, and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)benzo[1,2-b:4,3-b']bisbenzofuran instead of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- 1) BH 1-12 was obtained by the same synthesis except that benzo[1,2-b:3,4-b']bisbenzofuran was used. [M+H ⁺ ]=569.2

합성예 1-13. 화합물 BH 1-13의 합성Synthesis Example 1-13. Synthesis of compound BH 1-13

Compound BH 1-13 was obtained by the same synthesis in Synthesis Example 1-7-d, except that compound BH 1-1 was used instead of compound BH 1-7-c. [M+H ⁺ ]=533.3

합성예 1-14. 화합물 BH 1-14의 합성Synthesis Example 1-14. Synthesis of compound BH 1-14

Compound BH 1-14 was obtained by the same synthesis in Synthesis Example 1-7-d, except that compound BH 1-2 was used instead of compound BH 1-7-c. [M+H ⁺ ]=585.3

합성예 1-15. 화합물 BH 1-15의 합성Synthesis Example 1-15. Synthesis of compound BH 1-15

Compound BH 1-15 was obtained by the same synthesis in Synthesis Example 1-7-d, except that compound BH 1-3 was used instead of compound BH 1-7-c. [M+H ⁺ ]=613.4

합성예 1-16. 화합물 BH 1-16의 합성Synthesis Example 1-16. Synthesis of compound BH 1-16

Compound BH 1-16 was obtained by the same synthesis in Synthesis Example 1-7-d, except that compound BH 1-4 was used instead of compound BH 1-7-c. [M+H ⁺ ]=533.3

<실험예><Experimental example>

<실험예 1><Experimental Example 1>

The evaporation temperatures of BH 1-1 to BH 1-16 prepared in the above synthesis examples were measured and listed in Table 1 below. Evaporation temperature was measured by TGA (thermal gravity analysis). The temperature at which a 1% weight loss of the sample occurs is called T _d -1%, and starting from that temperature, it is deposited at a lower temperature of 60°C to 80°C. The pressure at this time is in the range of 10 ^-4 torr to 10 ^-6 torr. The evaporation temperature may have fluidity within a range understandable by those skilled in the art and may include a fluctuation range of ±10°C.

[Table 1]

<실험예 2><Experimental Example 2>

실시예 1.Example 1.

A substrate on which ITO (indium tin oxide)/Ag/ITO was deposited at 70Å/1000Å/70Å as an anode was cut into 50mm x 50mm x 0.5mm, placed in distilled water with a dispersant dissolved in it, and washed ultrasonically. Detergent was used from Fischer Co., and distilled water was from Millipore Co. Secondary filtered distilled water was used as a product filter. After washing the ITO for 30 minutes, it was ultrasonic washed twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed in the following solvent order: isopropyl alcohol, acetone, and methanol, and then dried.

HAT-CN was thermally vacuum deposited to a thickness of 50 Å on the anode to form a hole injection layer, and HTL1, a hole transport material, was vacuum deposited to a thickness of 1150 Å on the anode to form a hole transport layer. Then, an electron blocking layer was formed using HTL2 (150Å). Next, BD-1 (2% by mass of the total weight of the emitting layer) as a dopant and compounds BH 1-1 and BH 1-2 (weight ratio 50:50) as hosts were deposited by co-deposition to form a 20 nm thick emitting layer. formed. Then, 50Å of ETL2 was deposited to form a hole blocking layer, and the compound ETL1 and lithium quinolate (Liq) were mixed in a ratio of 7:3 to form an electron transport layer with a thickness of 250Å. Sequentially, magnesium and lithium fluoride (LiF) with a thickness of 50 Å were formed as an electron injection layer.

After forming the cathode with 200Å of magnesium and silver (1:4), 600Å of CP1 was deposited to complete the device. In the above process, the deposition rate of organic matter was maintained at 1Å/sec.

실시예 2 내지 27.Examples 2 to 27.

The same method as Example 1 except that the compounds specified in Table 2 below were used as materials for the light-emitting layer in Example 1, and the method of forming the light-emitting layer (co-deposition or premixing) and mixing ratio (mass ratio) were different. The device was manufactured. In Example 1, a light-emitting layer was formed (co-deposited) using two types of compounds of Chemical Formula 1-1 through different deposition sources. In the examples and comparative examples using the premix deposition method in Table 2 below, before forming the light-emitting layer The materials (host) were mixed in advance, and the light-emitting layer was formed through one deposition source.

비교예 1 내지 13.Comparative Examples 1 to 13.

A device was manufactured in the same manner as in Example 1, except that the material for the light emitting layer in Example 1 was different from the compound specified in Table 2 below.

The driving voltage, efficiency, and time to reach 97% of initial luminance (T97) were measured for the devices manufactured in Examples 1 to 23 and Comparative Examples 1 to 13 at a current density of 20 mA/cm ² , and the results are shown in Table 2 below. shown in

[Table 2]

It can be confirmed from the above experimental results that Examples 1 to 27 of the present application are superior to Comparative Examples 1 and 2 using a type of compound of Chemical Formula 1-1 and Comparative Example 3 using a type of conventional compound in terms of driving voltage, efficiency, and lifespan. there is.

In addition, Examples 1 to 27 of the present application are superior in driving voltage, efficiency and characteristics to Comparative Examples 4 to 10 and 13 using one compound of Formula 1-1 and one compound not corresponding to Formula 1-1. This can be confirmed from the experimental results.

In addition, it can be confirmed from the above experimental results that Examples 1 to 27 of the present application are superior to Comparative Examples 11 and 12 using two types of compounds that do not correspond to Chemical Formula 1-1 in driving voltage, efficiency, and characteristics.

In particular, one compound in which Ar1 of Formula 1-1 is a phenyl group substituted or unsubstituted with deuterium and a naphthyl group in which Ar1 of Formula 1-1 is substituted or unsubstituted with deuterium, or a ratio in which Ar1 of Formula 1-1 is substituted or unsubstituted with deuterium It can be confirmed that an organic light emitting device using a combination of one type of phenyl compound improves both injection and movement of holes and electrons, lowers the driving voltage of the organic light emitting device, and improves efficiency and lifespan characteristics by optimizing charge balance. there is.

Claims

anode;

cathode;

Comprising a first organic material layer provided between the anode and the cathode,

An organic light-emitting device wherein the first organic material layer includes two or more compounds represented by the following Chemical Formula 1-1:

[Formula 1-1]

In Formula 1-1,

X1 and X1' are the same or different from each other and are each independently O or S,

L1 is a direct bond or a substituted or unsubstituted arylene group,

Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 and R2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R3 is hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n1 is an integer from 0 to 8, and when n1 is 2 or more, 2 or more R1 are the same or different from each other,

n2 is an integer from 0 to 4, and when n2 is 2 or more, 2 or more R2 are the same or different from each other,

n3 is an integer from 0 to 6, and when n3 is 2 or more, 2 or more R3s are the same or different from each other.
In claim 1,

Formula 1-1 is an organic light emitting device represented by any one of the following formulas 1-1-1 to 1-1-3:

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

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

The definitions of X1,
In claim 1,

The organic light emitting device wherein Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
In claim 1,

The first organic layer is a compound represented by the following formula 1-1-1; And an organic light-emitting device comprising a compound represented by the following formula 1-1-2:

[Formula 1-1-1]

[Formula 1-1-2]

In the above formulas 1-1-1 and 1-1-2,

The definitions of X1,

Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group.
In claim 1,

The first organic material layer is an organic light-emitting device comprising two types of compounds represented by the following formula 1-1-1:

[Formula 1-1-1]

In the above formula 1-1-1,

The definitions of X1, X1', R1, R2, R3, n1, n2, n3 and L1 are the same as in Formula 1-1,

Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group.
In claim 1,

The first organic material layer is an organic light-emitting device comprising two types of compounds represented by the following formula 1-1-2:

[Formula 1-1-2]

In the above formula 1-1-2,

The definitions of X1, X1', R1, R2, R3, n1, n2, n3 and L1 are the same as in Formula 1-1,

Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group.
In claim 1,

Formula 1-1 is an organic light emitting device represented by any one of the following compounds:
In claim 1,

An organic light emitting device wherein the first organic material layer is a hole transport layer, a hole injection layer, a hole transport and injection layer, or an electron blocking layer.
In claim 1,

An organic light-emitting device wherein the first organic material layer is a light-emitting layer.
In claim 9,

An organic light emitting device wherein the light emitting layer further includes a dopant.
In claim 1,

An organic light emitting device wherein the first organic material layer is an electron transport layer, an electron injection layer, an electron transport and injection layer, or a hole blocking layer.
In claim 1,

One or more organic layers are additionally provided between the anode and the cathode, and the organic layer includes a hole transport layer, a hole injection layer, a hole transport and injection layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and an electron transport and injection layer. An organic light-emitting device that further includes one or more layers of a layer and a hole blocking layer.