WO2024225580A1 - Novel compound and organic light-emitting element comprising same - Google Patents

Abstract

The present invention relates to novel organic light-emitting material and an organic light-emitting element comprising same.

Description

Novel compound and organic light-emitting device comprising the same

Cross-citation with related application(s)

This application claims the benefit of priority to Korean Patent Application No. 10-2023-0055421, filed April 27, 2023 and Korean Patent Application No. 10-2024-0011002, filed January 24, 2024, the entire contents of which are incorporated herein by reference.

The present invention relates to a novel compound and an organic light-emitting device comprising the same.

In general, the organic luminescence phenomenon refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices utilizing the organic luminescence phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light-emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer is often composed of a multilayer structure composed of different materials in order 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, an electron injection layer, etc. In the structure of such an organic light-emitting device, when a voltage is applied between two electrodes, holes are injected into the organic layer from the anode and electrons are injected into the organic layer from the cathode, and when the injected holes and electrons meet, excitons are formed, and when these excitons fall back to the ground state, light is emitted.

There is a continuous demand for the development of new materials for organic substances used in organic light-emitting devices such as the above.

Prior art literature

Patent Documents

(Patent Document 1) Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel organic light-emitting material and an organic light-emitting device comprising the same.

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

[Chemical Formula 1]

In the above chemical formula 1,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L ₁ and L ₂ are each independently a single bond; a substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₃ is a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

X ₁ to X ₃ are each independently N or CR,

R is hydrogen; deuterium; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

D is deuterium,

a and c are each independently an integer from 0 to 3,

b and d are each independently an integer from 0 to 4,

At least one of a to d is greater than or equal to 1.

In addition, the present invention provides an organic light-emitting device including a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by the chemical formula 1.

The compound represented by the above-described chemical formula 1 can be used as a material of an organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light-emitting device. In particular, the compound represented by the above-described chemical formula 1 can be used as a hole injection, hole transport, electron blocking, luminescence, hole blocking, electron transport, and/or electron injection material.

Figure 1 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), a light-emitting layer (3), and a cathode (4).

Figure 2 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a first hole transport layer (6), a second hole transport layer (7), an electron blocking layer (8), a light-emitting layer (3), a hole blocking layer (9), an electron injection and transport layer (10), and a cathode (4).

Hereinafter, the present invention will be described in more detail to help understand the present invention.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connecting to another substituent.

The term "substituted or unsubstituted" as used herein means a group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylamine group; an arylphosphine group; or a heteroaryl group containing at least one of N, O, and S atoms, or a substituted or unsubstituted group in which two or more of the above-mentioned substituents are linked. For example, the "substituent linked with two or more substituents" can be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent in which two phenyl groups are connected. For example, the term "substituted or unsubstituted" can be understood to mean "unsubstituted or substituted with one or more, for example, 1 to 5, substituents selected from the group consisting of deuterium, halogen, C _1-10 alkyl, C _1-10 alkoxy, C _6-20 aryl, and C _2-20 heteroaryl including one or more heteroatoms of N, O and S." In addition, the term "substituted with one or more substituents" in the present specification can be understood to mean, for example, "substituted with 1 to 5 substituents", or "substituted with 1 or 2 substituents."

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it can be a substituent having the following structure, but is not limited thereto.

In the present specification, the ester group may have the oxygen of the ester group substituted with a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may have a substituent of the following structural formula, but is not limited thereto.

In this specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it can be a substituent having the following structure, but is not limited thereto.

In this specification, the silyl group specifically includes, but is 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, a phenylsilyl group, etc.

In this specification, the boron group specifically includes, but is not limited to, a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, etc.

In this specification, examples of halogen groups include 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 number of carbon atoms in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, These include, but are not limited to, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

In the present specification, the alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples include, but are not limited to, 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, and styrenyl.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, examples thereof include, but are 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 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 the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, or the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.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,

It can be, but is not limited to, the following.

In the present specification, a heteroaryl group is a heteroaryl group containing at least one of O, N, Si, and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the number of carbon atoms of the heteroaryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the heteroaryl group is 6 to 20. Examples of heteroaryl groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group, Examples include, but are not limited to, phenothiazinyl and dibenzofuranyl groups.

In this specification, the aryl group among the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the examples of the aryl group described above. In this specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the alkyl group described above. In this specification, the heteroaryl among the heteroarylamine may be applied to the description of the heteroaryl group described above. In this specification, the alkenyl group among the aralkenyl group is the same as the examples of the alkenyl group described above. In this specification, the description of the aryl group described above may be applied to the arylene except that it is a divalent group. In this specification, the description of the heteroaryl group described above may be applied to the heteroarylene except that it is a divalent group. In this specification, the description of the aryl group or the cycloalkyl group described above may be applied to the hydrocarbon ring except that it is not a monovalent group and is formed by combining two substituents. In this specification, the description of the heteroaryl group described above may be applied, except that the heteroaryl is not monovalent and is formed by combining two substituents.

Preferably, Ar ₁ and Ar ₂ can each independently be a substituted or unsubstituted C _6-20 aryl; or a C _2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S.

More preferably, Ar ₁ and Ar ₂ can each independently be phenyl, biphenylyl, or dibenzofuranyl, wherein the phenyl, biphenylyl, or dibenzofuranyl can be unsubstituted or substituted with at least one deuterium.

Most preferably, Ar ₁ and Ar ₂ can each independently be phenyl, phenyl substituted with 5 deuterium atoms, biphenylyl, or dibenzofuranyl.

Preferably, at least one of Ar ₁ and Ar ₂ can be a substituted or unsubstituted C _6-20 aryl.

Preferably, at least one of Ar ₁ and Ar ₂ may be C _6-20 aryl which is unsubstituted or substituted with deuterium.

More preferably, at least one of Ar ₁ and Ar ₂ may be phenyl or phenyl substituted with 5 deuterium atoms.

Preferably, L ₁ and L ₂ can each independently be a single bond; a substituted or unsubstituted C _6-20 arylene; or a C _2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S.

More preferably, L ₁ and L ₂ may each independently be a single bond; substituted or unsubstituted C _6-20 arylene.

More preferably, L ₁ and L ₂ can each independently be a single bond, or phenylene which is unsubstituted or substituted with at least one deuterium.

Most preferably, L ₁ and L ₂ can each independently be a single bond or phenylene.

Preferably, at least one of L ₁ and L ₂ can be a single bond.

Preferably, Ar ₃ may be a substituted or unsubstituted C _6-20 aryl; or a C _2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S.

More preferably, Ar ₃ can be a substituted or unsubstituted C _6-20 aryl.

More preferably, Ar ₃ can be a C _6-20 aryl which is unsubstituted or substituted with deuterium.

More preferably, Ar ₃ may be phenyl or biphenylyl, wherein said phenyl or biphenylyl may be unsubstituted or substituted with at least one deuterium.

Most preferably, Ar ₃ can be phenyl, phenyl substituted with 5 deuterium atoms, biphenylyl, or biphenylyl substituted with 9 deuterium atoms.

Preferably, at least one of X ₁ to X ₃ may be N and the rest may be CR.

More preferably, at least two of X ₁ to X ₃ may be N and the rest may be CR.

Most preferably, X ₁ to X ₃ can each be N.

Preferably, a and c may each be 3, and b and d may each be 4.

Representative examples of compounds represented by the chemical formula 1 are as follows:

.

.

The compound represented by the above chemical formula 1 can be manufactured, for example, by a manufacturing method such as the following reaction scheme 1, and the remaining compounds can also be manufactured similarly.

[Reaction Formula 1]

In the above reaction scheme 1, Ar ₁ to Ar ₃ , L ₁ , L ₂ , X ₁ to X ₃ , R, D and a to d are as defined in the above chemical formula 1, Z is halogen, and preferably Z is chloro or bromo.

The above reaction scheme 1 is a Suzuki coupling reaction, which is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The above manufacturing method can be more specifically described in the manufacturing example described below.

In addition, the present invention provides an organic light-emitting device comprising a compound represented by the chemical formula 1. As an example, the present invention provides an organic light-emitting device comprising a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one layer of the organic layers comprises a compound represented by the chemical formula 1.

The organic layer of the organic light-emitting device of the present invention may be formed as a single-layer structure, but may be formed as a multilayer structure in which two or more organic layers are laminated. For example, the organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. as the organic layers. However, the structure of the organic light-emitting device is not limited thereto and may include a smaller number of organic layers.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer may include a compound represented by the chemical formula 1.

In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially laminated on a substrate. In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having a structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially laminated on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is exemplified in FIGS. 1 and 2.

FIG. 1 illustrates an example of an organic light-emitting device comprising 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 device comprising a substrate (1), an anode (2), a hole injection layer (5), a first hole transport layer (6), a second hole transport layer (7), an electron blocking layer (8), a light-emitting layer (3), a hole blocking layer (9), an electron injection and transport layer (10), and a cathode (4). In this structure, the compound represented by the chemical formula 1 may be included in the light-emitting layer.

The organic light-emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes a compound represented by the chemical formula 1. In addition, when the organic light-emitting device includes a plurality of organic layers, the organic layers can be formed of the same material or different materials.

For example, the organic light-emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. At this time, a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a conductive metal oxide or an alloy thereof on the substrate to form an anode, and then an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer is formed thereon, and then a material that can be used as a cathode is deposited thereon, thereby manufacturing the device. In addition to this method, the organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on the substrate.

In addition, the compound represented by the above chemical formula 1 can be formed into an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited thereto.

In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing an organic layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited to this.

For 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.

As the above anode material, a material having a high work function is generally preferred so that hole injection into the organic layer can be smooth. Specific examples of the above anode material include, but are not limited to, 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); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

The cathode material is preferably a material having a low work function to facilitate electron injection into the organic layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF/Al or LiO ₂ /Al.

The above hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound that has the ability to transport holes, has an excellent hole injection effect at the anode, an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents movement of excitons generated in the light-emitting layer to the electron injection layer or the electron injection material, and further has excellent thin film forming ability. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include, but are not limited to, metal porphyrin, oligothiophene, arylamine series organic compounds, hexanitrilehexaazatriphenylene series organic compounds, quinacridone series organic compounds, perylene series organic compounds, anthraquinone, and conductive polymers of polyaniline and polythiophene series.

The above hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. A material having high mobility for holes is suitable as a hole transport material that can transport holes from the anode or the hole injection layer and transfer them to the light-emitting layer. Specific examples include, but are not limited to, arylamine-based organic substances, conductive polymers, and block copolymers having both conjugated and non-conjugated portions. Meanwhile, when two or more materials are used as the hole transport layer, they can be classified into a first hole transport layer, a second hole transport layer, etc., depending on the order of lamination during manufacturing.

The above electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and from passing to the hole transport layer. It is also called an electron blocking layer or electron suppression layer. A material having a lower electron affinity than the electron transport layer is preferable for the electron blocking layer.

The above-mentioned light-emitting material is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer respectively and combining them, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples thereof include, but are not limited to, 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; benzoxazole, benzthiazole, and benzimidazole compounds; poly(p-phenylenevinylene) (PPV) polymers; spiro compounds; polyfluorene, rubrene, etc.

The above-mentioned light-emitting layer may include a host material and a dopant material. The host material may include a condensed aromatic ring derivative or a heterocyclic compound. Specifically, the condensed aromatic ring derivative may include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and the heterocyclic compound may include, but is not limited to, carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, etc. Preferably, the compound represented by the above-mentioned chemical formula 1 may be used as the host material.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periflanthene, etc. having an arylamino group, and styrylamine compounds are compounds in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, and one or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but are not limited thereto. In addition, metal complexes include iridium complexes, platinum complexes, etc., but are not limited thereto.

The above hole-blocking layer is a layer placed between the electron transport layer and the light-emitting layer to prevent holes injected from the anode from being recombined in the light-emitting layer and from passing to the electron transport layer. It is also called a hole-suppression layer. A material with high ionization energy is preferable for the hole-blocking layer.

The above electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. As the electron transport material, a material that can well receive electrons from the cathode and transfer them to the light-emitting layer is suitable. A material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline; a complex including Alq ₃ ; an organic radical compound; and a hydroxyflavone-metal complex. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by an aluminum layer or a silver layer. Specific examples include cesium, barium, calcium, ytterbium and samarium, and in each case followed by an aluminum layer or a silver layer.

The above electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect for an electron injection effect from a cathode, an excellent electron injection effect for a light-emitting layer or a light-emitting material, prevents movement of excitons generated in the light-emitting layer to a hole injection layer, and further, a compound having excellent thin-film forming ability is preferable. Specific examples thereof include, but are not limited to, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

As the above metal complex compounds, 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-naphtholato)aluminum, Bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc., but are not limited thereto.

Meanwhile, in the present invention, the "electron injection and transport layer" is a layer that performs the roles of both the electron injection layer and the electron transport layer, and materials performing the roles of each layer may be used alone or in combination, but are not limited thereto.

The organic light-emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided emission device, and in particular, may be a bottom emission device requiring relatively high luminous efficiency.

In addition, the compound represented by the above chemical formula 1 can be included in an organic solar cell or an organic transistor in addition to an organic light-emitting device.

Hereinafter, the present invention will be described in more detail to help understand the present invention. However, the following examples are only intended to illustrate the present invention, and the content of the present invention is not limited to the following examples.

[Manufacturing example]

Manufacturing Example 1: Manufacturing of compound GH1

(Manufacturing Example 1-1: Preparation of compound GH1-a)

In a nitrogen atmosphere, 4-bromo-9-phenyl-9H-carbazole (30 g, 93.1 mmol) and 4-chloro-9H-carbazole (18.8 g, 93.1 mmol) were added to 450 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (26.8 g, 279.3 mmol) was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium (1.4 g, 2.8 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature and the produced solid was filtered. The solid was dissolved in 825 ml of chloroform, washed twice with water, separated into the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to give a white solid compound GH1-a (31.3 g, 76 %, MS: [M+H] ⁺ = 444).

(Manufacturing Example 1-2: Preparation of compound GH1-b)

Compound GH1-a (25 g, 56.4 mmol) and aluminium chloride (AlCl ₃ ) (6.8 g, 28.2 mmol) were added to C ₆ D- (800 ml) and stirred for 3 hours. After the reaction was completed, D ₂ O (100 ml) was added and stirred for 30 minutes, then trimethylamine (10 ml) was added dropwise. The reaction solution was transferred to a separatory funnel and extracted with water and toluene. After drying over anhydrous magnesium sulfate, the organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to prepare compound GH1-b (22.9 g, 88 %, [M + H] ⁺ = 463).

(Manufacturing Example 1-3: Preparation of compound GH1-c)

In a nitrogen atmosphere, compound GH1-b (50 g, 108.2 mmol) and bis(pinacolato)diboron (27.7 g, 119 mmol) were added to 1000 ml of Diox, stirred and refluxed. Then, potassium acetate (31.2 g, 324.6 mmol) was added, and after sufficient stirring, palladium dibenzylideneacetonepalladium (1.9 g, 3.2 mmol) and tricyclohexylphosphine (1.8 g, 6.5 mmol) were added. After 3 hours of reaction, the mixture was cooled to room temperature and the produced solid was filtered. The solid was dissolved in 1797 ml of chloroform, washed twice with water, separated the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to give a gray solid compound GH1-c (50.3 g, 84 %, MS: [M+H] ⁺ = 554).

(Manufacturing Example 1-4: Preparation of compound GH1)

In a nitrogen atmosphere, compound GH1-c (30 g, 54.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (14.5 g, 54.2 mmol) were added to 900 ml of tetrahydrofuran, stirred and refluxed. Then, potassium carbonate (22.5 g, 162.6 mmol) dissolved in 22 ml of water was added, and after sufficient stirring, tetrakistriphenyl-phosphinopalladium (1.9 g, 1.6 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature and the produced solid was filtered. The solid was added to 1785 ml of chloroform, dissolved, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to give a white solid compound GH1 (22.9 g, 64%, MS: [M+H] ⁺ = 659).

Manufacturing Example 2: Manufacturing of compound GH2

Compound GH2 ([M+H] + = 669) was prepared in the same manner as in Preparation Example 1-4, except that 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine was used instead of 2-chloro- ^4,6 -diphenyl-1,3,5-triazine.

Manufacturing Example 3: Manufacturing of compound GH3

(Manufacturing Example 3-1: Preparation of compound GH3-a)

Compound GH3-a ([M+H] ⁺ = 443) was prepared in the same manner as in Preparation Example 1-1, except that 2-chloro-9H-carbazole was used instead of 4-chloro-9H-carbazole.

(Manufacturing Example 3-2: Preparation of compound GH3-b)

Compound GH3-b ([M+H] ⁺ = 463) was prepared in the same manner as in Manufacturing Example 1-2, except that compound GH3-a was used instead of compound GH1-a.

(Manufacturing Example 3-3: Preparation of compound GH3-c)

Compound GH3-c ([M+H] ⁺ = 554) was prepared in the same manner as in Preparation Example 1-3, except that compound GH3-b was used instead of compound GH1-b.

(Manufacturing Example 3-4: Preparation of compound GH3)

Compound GH3 ([M+H] + = 669) was prepared in the same manner as in Preparation Example 1-4, except that compound GH3-c was used instead of compound GH1-c and 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl- ^1,3,5 -triazine.

Manufacturing Example 4: Manufacturing of compound GH4

(Manufacturing Example 4-1: Preparation of compound GH4-a)

Compound GH4-a ([M+H] + = 443) was prepared in the same manner as in Preparation Example 1-1, except that 2-bromo ^- 9-phenyl-9H-carbazole was used instead of 4-bromo-9-phenyl-9H-carbazole and 2-chloro-9H-carbazole was used instead of 4-chloro-9H-carbazole.

(Manufacturing Example 4-2: Preparation of compound GH4-b)

Compound GH4-b ([M+H] ⁺ = 463) was prepared in the same manner as in Manufacturing Example 1-2, except that compound GH4-a was used instead of compound GH1-a.

(Manufacturing Example 4-3: Preparation of compound GH4-c)

Compound GH4-c ([M+H] ⁺ = 554) was prepared in the same manner as in Preparation Example 1-3, except that compound GH4-b was used instead of compound GH1-b.

(Manufacturing Example 4-4: Preparation of compound GH4)

Compound GH4 ([M+H] + = 735) was prepared in the same manner as in Preparation Example 1-4, except that compound GH4-c was used instead of compound GH1-c ^and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine.

Manufacturing Example 5: Manufacturing of compound GH5

(Manufacturing Example 5-1: Preparation of compound GH5-a)

Compound GH5-a ([M+H] + = 443) was prepared using the same method as in Preparation Example 1-1, except that 3-bromo ^- 9-phenyl-9H-carbazole was used instead of 4-bromo-9-phenyl-9H-carbazole and 1-chloro-9H-carbazole was used instead of 4-chloro-9H-carbazole.

(Manufacturing Example 5-2: Preparation of compound GH5-b)

Compound GH5-b ([M+H] ⁺ = 463) was prepared in the same manner as in Preparation Example 1-2, except that compound GH5-a was used instead of compound GH1-a.

(Manufacturing Example 5-3: Preparation of compound GH5-c)

Compound GH5-c ([M+H] ⁺ = 554) was prepared in the same manner as in Preparation Example 1-3, except that compound GH5-b was used instead of compound GH1-b.

(Manufacturing Example 5-4: Preparation of compound GH5)

Compound GH5 ([M+H] + = 669) was prepared in the same manner as in Preparation Example 1-4, except that compound GH5-c was used instead of compound GH1-c and 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl- ^1,3,5 -triazine.

Manufacturing Example 6: Manufacturing of compound GH6

(Manufacturing Example 6-1: Preparation of compound GH6-a)

Compound GH6-a ([M+H] + = 443) was prepared in the same manner as in Preparation Example 1-1, except that 1-bromo-9-phenyl-9H-carbazole was used instead of 4-bromo ^- 9-phenyl-9H-carbazole and 3-chloro-9H-carbazole was used instead of 4-chloro-9H-carbazole.

(Manufacturing Example 6-2: Preparation of compound GH6-b)

Compound GH6-b ([M+H] ⁺ = 463) was prepared in the same manner as in Preparation Example 1-2, except that compound GH6-a was used instead of compound GH1-a.

(Manufacturing Example 6-3: Preparation of compound GH6-c)

Compound GH6-c ([M+H] ⁺ = 554) was prepared in the same manner as in Preparation Example 1-3, except that compound GH6-b was used instead of compound GH1-b.

(Manufacturing Example 6-4: Preparation of compound GH6)

Compound GH6 ([M+H] + = 669) was prepared in the same manner as in Preparation Example 1-4, except that compound GH6-c was used instead of compound GH1-c and 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl- ^1,3,5 -triazine.

Manufacturing Example 7: Manufacturing of compound GH7

(Manufacturing Example 7-1: Preparation of compound GH7-a)

Compound GH7-a ([M+H] + = 520) was prepared in the same manner as in Preparation Example 1-1, except that 9-([1,1'-biphenyl] ^-3 -yl)-1-bromo-9H-carbazole was used instead of 4-bromo-9-phenyl-9H-carbazole.

(Manufacturing Example 7-2: Preparation of compound GH7-b)

Compound GH7-b ([M+H] ⁺ = 543) was prepared in the same manner as in Manufacturing Example 1-2, except that compound GH7-a was used instead of compound GH1-a.

(Manufacturing Example 7-3: Preparation of compound GH7-c)

Compound GH7-c ([M+H] ⁺ = 634) was prepared in the same manner as in Preparation Example 1-3, except that compound GH7-b was used instead of compound GH1-b.

(Manufacturing Example 7-4: Preparation of compound GH7)

Compound GH7 ([M+H] ⁺ = 740) was prepared in the same manner as in Preparation Example 1-4, except that compound GH7-c was used instead of compound GH1-c.

Manufacturing Example 8: Preparation of compound GH8

(Manufacturing Example 8-1: Preparation of compound GH8-a)

Compound GH8-a ([M+H] + = 458) was prepared in the same manner as in Preparation Example 1-1, except that 2-bromo-9-phenyl-9H-carbazole-1,3,4,5,6,7,8-d7 was used instead of 4-bromo-9-phenyl-9H-carbazole and 4-chloro-9H-carbazole-1,2,3,5,6,7,8-d7 was used instead of 4- ^chloro -9H-carbazole.

(Manufacturing Example 8-2: Preparation of compound GH8-b)

Compound GH8-b ([M+H] ⁺ = 549) was prepared in the same manner as in Preparation Example 1-3, except that compound GH8-a was used instead of compound GH1-b.

(Manufacturing Example 8-3: Preparation of compound GH8)

Compound GH8 ([M+H] + = 744) was prepared in the same manner as in Preparation Example 1-4, except that compound GH8- ^b was used instead of compound GH1-c and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine.

[Example]

Example 1

A glass substrate coated with a 100 nm thick ITO (indium tin oxide) film was placed in distilled water containing a detergent and cleaned using ultrasonic waves. The detergent used was a Fischer Co. product, and the distilled water used was distilled water that had been filtered twice through a Millipore Co. filter. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After the distilled water washing was complete, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, the substrate was transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum deposition machine.

The compound HI-A below was thermally vacuum deposited to a thickness of 60 nm on the ITO transparent electrode prepared in this manner to form a hole injection layer.

A first hole transport layer having a thickness of 5 nm was formed by vacuum depositing the compound HAT below on the hole injection layer, and a second hole transport layer having a thickness of 50 nm was formed by vacuum depositing the compound HT-A below on the first hole transport layer.

On the hole transport layer, the following compound HT-B was thermally vacuum deposited to a thickness of 45 nm to form an electron blocking layer. On the electron blocking layer, the previously prepared compound GH1 was mixed with the following compound GH-P at a weight ratio of 1:1, and then mixed with the following compound GD at a weight ratio of 90:10 and vacuum deposited to a thickness of 40 nm to form a light emitting layer. On the light emitting layer, the following compound ET-A was vacuum deposited to a thickness of 5 nm to form a hole blocking layer. On the hole blocking layer, the following compound ET-B and the following compound LiQ were vacuum deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 35 nm.

After lithium fluoride (LiF) was deposited with a thickness of 1 nm on the electron injection and transport layer, aluminum was then deposited with a thickness of 100 nm to form a cathode, thereby manufacturing an organic light-emitting device.

In the above process, the deposition rate of the organic material was maintained at 0.04 nm/sec to 0.09 nm/sec, the deposition rate of lithium fluoride was maintained at 0.03 nm/sec, and the deposition rate of aluminum was maintained at 0.2 nm/sec. The vacuum during deposition was maintained at 1*10 ^-7 torr to 5*10 ^-5 torr.

Examples 2 to 8 and Comparative Examples 1 to 5

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compounds described in Table 1 below were used instead of compound GH1 in Example 1. In Table 1 below, the structures of compounds GH9 to GH13 are as follows.

[Experimental example]

Current was applied to the organic light-emitting devices manufactured in Examples 1 to 8 and Comparative Examples 1 to 5, and the voltage, efficiency, luminescent color, and lifespan (T ₉₅ ) were measured, and the results are shown in Table 1 below. At this time, the voltage and efficiency were measured by applying a current density of 10 mA/cm ² , and T ₉₅ means the time (hr) until the initial luminance decreases to 95% at a current density of 10 mA/cm ² .

division luminescent layer compound Voltage (V)
(@10mA/cm ² ) Efficiency (cd/A)
(@10mA/cm ² ) Fluorescent color T ₉₅ (hr)
(@10mA/cm ² ) Example 1 Compound GH1 3.51 91.7 green 274 Example 2 Compound GH2 3.50 92.0 green 312 Example 3 Compound GH3 3.47 88.7 green 308 Example 4 Compound GH4 3.44 89.1 green 289 Example 5 Compound GH5 3.38 92.3 green 323 Example 6 Compound GH6 3.43 93.5 green 310 Example 7 Compound GH7 3.41 90.9 green 281 Example 8 Compound GH8 3.49 92.5 green 263 Comparative Example 1 Compound GH9 3.55 87.1 green 220 Comparative Example 2 Compound GH10 3.53 88.3 green 235 Comparative Example 3 Compound GH11 3.55 75.1 green 240 Comparative Example 4 Compound GH12 3.52 80.1 green 189 Comparative Example 5 Compound GH13 3.48 88.1 green 233

As shown in Table 1 above, it was confirmed that the organic light-emitting device of one embodiment is superior to the organic light-emitting device including compounds GH9, GH10, GH12, or GH13 that are not substituted with deuterium in terms of voltage, efficiency, and lifespan. In addition, even when deuterium is substituted, such as in compound GH11 in which a substituent other than carbazole is substituted with deuterium, if the substitution position is not carbazole, the voltage, efficiency, and lifespan are all inferior to the organic light-emitting device of one embodiment.

Therefore, as shown in Table 1 above, when the compound represented by Chemical Formula 1 is used as a host for an organic light-emitting device, it can be confirmed that the characteristics of low voltage, high efficiency, and long life are exhibited.

[Explanation of symbols]

1: Substrate 2: Anode

3: Emitting layer 4: Cathode

5: Hole injection layer 6: First hole transport layer

7: Second hole transport layer 8: Electron blocking layer

9: Hole-blocking layer 10: Electron injection and transport layer

Claims (14)

A compound represented by the following chemical formula 1: [Chemical Formula 1]

In the above chemical formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, L ₁ and L ₂ are each independently a single bond; a substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, Ar ₃ is a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, X ₁ to X ₃ are each independently N or CR, R is hydrogen; deuterium; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, D is deuterium, a and c are each independently an integer from 0 to 3, b and d are each independently an integer from 0 to 4, At least one of a to d is greater than or equal to 1. In the first paragraph, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, or dibenzofuranyl, The above phenyl, biphenylyl, or dibenzofuranyl is unsubstituted or substituted with at least one deuterium, compound. In the first paragraph, Ar ₁ and Ar ₂ are each independently phenyl, phenyl substituted with 5 deuterium atoms, biphenylyl, or dibenzofuranyl, compound. In the first paragraph, At least one of Ar ₁ and Ar ₂ is phenyl or phenyl substituted with 5 deuterium atoms, compound. In the first paragraph, L ₁ and L ₂ are each independently a single bond, or phenylene which is unsubstituted or substituted with at least one deuterium, compound. In the first paragraph, L ₁ and L ₂ are each independently a single bond or phenylene, compound. In the first paragraph, At least one of L ₁ and L ₂ is a single bond, compound. In the first paragraph, Ar ₃ is phenyl or biphenylyl, The above phenyl or biphenylyl is unsubstituted or substituted with at least one deuterium, compound. In the first paragraph, Ar ₃ is phenyl, phenyl substituted with 5 deuterium atoms, biphenylyl, or biphenylyl substituted with 9 deuterium atoms, compound. In the first paragraph, X ₁ to X ₃ are each N, compound. In the first paragraph, a and c are 3 each, b and d are 4 each, compound. In the first paragraph, The compound represented by the above chemical formula 1 is one selected from the group consisting of: compound:

. An organic light-emitting device comprising a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers comprises a compound according to any one of claims 1 to 12. Organic light emitting diode. In Article 13, The above organic layer is a light-emitting layer, Organic light emitting diode.

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