WO2022031020A1 - Novel compound and organic light emitting device comprising same - Google Patents

Abstract

The present invention provides a novel compound, and an organic light emitting device comprising same.

Description

Novel compound and organic light emitting device using same

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0097602 on August 4, 2020 and Korean Patent Application No. 10-2021-0101880 on August 3, 2021, and All content disclosed in the literature is incorporated as a part of this specification.

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

The development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

[Prior art literature]

[Patent Literature]

(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

AL ₁ -BC

In Formula 1,

A is represented by the following formula (2),

[Formula 2]

In Formula 2,

each X is independently N or CH; 2 or more of X is N,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- containing one or more heteroatoms selected from the group consisting of N, O and S ₆₀ heteroaryl; At least one of Ar ₁ and Ar ₂ is substituted or unsubstituted carbazol-9-yl,

L ₁ is a direct bond, substituted or unsubstituted C _6-60 arylene, or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S Ren,

B is represented by the following formula (3),

[Formula 3]

In Formula 3,

Y ₁ is O or S,

Any one of Q ₁ and Q ₂ is bonded to L ₁ of Formula 1, and the rest is CH,

Any one of Z- ₁ to Z ₄ is bonded to C of Formula 1, the rest is CH,

C is represented by the following formula (4),

[Formula 4]

In Formula 4,

D is a C _6-60 aryl ring or a C _2-60 heteroaryl ring comprising any one or more heteroatoms selected from the group consisting of N, O and S;

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted silyl, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted or C _2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S; Adjacent two combine to form a benzene ring, and the remainder is hydrogen or deuterium;

a is an integer from 1 to 58;

The compound represented by Chemical Formula 1 described above may be used as a material for the organic material layer of the organic light emitting device, and may improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.

In particular, the compound represented by the above formula (1) may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole transport layer 3 , a light emitting layer 4 , an electron injection and transport layer 5 , and a cathode 6 .

2 is a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and an example of an organic light-emitting device including a cathode 6 are shown.

Hereinafter, it will be described in more detail to help the understanding of the present invention.

(Definition of Terms)

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

and

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium, a halogen group, a cyano group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amino group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkyl group Thioxy group, arylthioxy group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamine group, aralkylamine substituted or unsubstituted with one or more substituents selected from the group consisting of a group, a heteroarylamine group, an arylamine group, an arylphosphine group, or a heteroaryl group containing at least one of N, O and S atoms; It means substituted or unsubstituted in which two or more substituents among the above-exemplified substituents are connected. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, in the ester group, oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes 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, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

In the present specification, examples of the halogen group 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 an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group 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, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary 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, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, 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, but is not limited thereto.

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 having aromaticity. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may include, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, and the like.

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. Examples of heteroaryl include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group, Carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the above-described aryl group. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description regarding heteroaryl described above may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied, except that arylene is a divalent group. In the present specification, the description of the above-described heteroaryl may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description regarding heteroaryl described above may be applied, except that it is formed by combining two substituents.

(compound)

The present invention provides a compound represented by Formula 1 above.

Hereinafter, Chemical Formula 1 and the compound represented by the Chemical Formula 1 will be described in detail as follows.

In Formula 1, any one of Q ₁ and Q ₂ is bonded to L ₁ of Formula 1, and the rest is CH; Any one of Z ₁ to Z ₄ is bonded to C of Formula 1, and the rest is CH.

Specifically, Formula 1 is the A; L ₁ ; B; and C; depending on the bonding position, it may be of Formula 1-1 or 1-2:

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, D, X, Y ₁ , L ₁ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , and a have the same definitions as described above.

each X is independently N or CH; At least two of X are N.

Specifically, all of X may be N.

Ar ₁ and Ar ₂ are each independently C _6-30 aryl, substituted or unsubstituted, or C _2- containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S ₃₀ heteroaryl.

Specifically, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, naphthyl phenyl, phenanthrenyl, dimethylfluorenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl , dibenzofuranyl, or dibenzothiophenyl. In this case, Ar ₁ and Ar ₂ are unsubstituted; It may be one substituted with one or more deuterium.

However, at least one of Ar ₁ and Ar ₂ is substituted or unsubstituted carbazol-9-yl.

For example, any one of Ar ₁ and Ar ₂ is phenyl, biphenylyl, carbazol-9-yl, dibenzofuranyl, or dibenzothiophenyl unsubstituted or substituted with one or more deuterium; The other one of Ar ₁ and Ar ₂ may be carbazol-9-yl which is unsubstituted or substituted with one or more phenyls.

L ₁ is a direct bond, substituted or unsubstituted C _6-30 arylene, or C _2-30 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S It could be Ren.

For example, L ₁ may be a direct bond, phenylene, biphenylene, naphthylene, carbazol-9-ylene, dibenzofuranylene, or dibenzothiophenylene.

Y ₁ is O or S.

C of Formula 1 is represented by Formula 4, for example, in Formula 4, D is a benzene ring, a naphthalene ring, a phenanthrene ring, a 9-phenyl-9H-carbazole ring, a dimethylfluorene ring, a dibenzofuran ring, or a dibenzothiophene ring.

a is an integer from 1 to 58, for example, may be an integer from 1 to 8.

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted silyl, substituted or unsubstituted C _1-30 alkyl, substituted or unsubstituted C _6-30 aryl, or substituted or unsubstituted or C _2-30 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S; Adjacent two may combine to form a benzene ring, and the remainder may be hydrogen or deuterium.

In addition, R ₁ and R ₂ are each independently deuterium, C _6-60 aryl substituted with one or more deuterium, or one or more heteroatoms selected from the group consisting of N, O and S substituted with one or more deuterium. or C _2-60 heteroaryl; Adjacent two may combine to form a benzene ring, and the remainder may be deuterium.

For example, R ₁ and R ₂ may each independently be hydrogen, deuterium, or phenyl unsubstituted or substituted with one or more deuterium.

As a more specific example, the compound represented by Formula 1 may be any one selected from the group consisting of the following compounds:

In addition, the present invention provides a method for preparing a compound represented by Formula 1 as shown in Scheme 1 below.

[Scheme 1]

Definitions of X, Y ₁ , L ₁ , Ar ₁ , Ar ₂ , D, R ₁ , and R ₂ in Scheme 1 are the same as in Formula 1. Also, in Scheme 1, Z is halogen, preferably fluoro or chloro. In addition, by changing the attachment position of Z in Scheme 1, the position to which the 9-carbazole substituent is attached can be controlled.

Scheme 1 is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

(organic light emitting element)

On the other hand, the present invention provides an organic light emitting device including the compound represented by the formula (1). As an example, the present invention provides an organic light emitting device comprising a first electrode, a second electrode provided to face the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, At least one layer of the organic material layer includes the compound represented by Formula 1, and provides an organic light emitting device.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but 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 may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 The indicated compounds are included.

In addition, the organic material layer may include a light emitting layer, the light emitting layer includes the compound represented by Formula 1 above.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but 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 further comprises a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, and an electron transport layer and an electron injection layer between the light emitting layer and the second electrode in addition to the light emitting layer as an organic layer can have a structure that However, the structure of the organic light emitting device is not limited thereto and may include a smaller number or a larger number of organic layers.

In addition, in the organic light emitting diode according to the present invention, an anode, one or more organic material layers and a cathode are sequentially stacked on a substrate, wherein the first electrode is an anode and the second electrode is a cathode. may be small. In addition, in the organic light emitting device according to the present invention, the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers and an anode are sequentially stacked on a substrate of an inverted type organic structure. It may be a light emitting device. For example, the structure of the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole transport layer 3 , a light emitting layer 4 , an electron injection and transport layer 5 , and a cathode 6 . In such a structure, the compound represented by Formula 1 may be included in the hole transport layer.

2 is a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and an example of an organic light-emitting device including a cathode 6 are shown. In such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the electron suppression layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, 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.

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

In addition, the compound represented by Formula 1 may be formed into an organic material 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), metal oxide such as indium zinc oxide (IZO), ZnO: Al or SnO ₂ : combinations of oxides with metals such as Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole and polyaniline and conductive polymers, such as, but not limited to these.

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that can transport holes from the anode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. material is suitable. As the hole transport material, the compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .

The electron suppression layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, adjusts hole mobility, prevents excessive movement of electrons, and increases the hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving The electron blocking layer includes an electron blocking material, and as an example of the electron blocking material, a compound represented by Formula 1 or an arylamine-based organic material may be used, but is not limited thereto.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compound, dimerized styryl compound, BAlq, 10-hydroxybenzoquinoline-metal compound, benzoxazole, benzthiazole and benz There are imidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but is not limited thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material may further include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two 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, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to control electron mobility and prevent excessive movement of holes to increase the hole-electron coupling probability, thereby improving the efficiency of the organic light emitting device layer that plays a role. The hole blocking layer includes a hole blocking material. Examples of the hole blocking material include an electron withdrawing group such as an azine derivative including triazine, a triazole derivative, an oxadiazole derivative, a phenanthroline derivative, and a phosphine oxide derivative. compounds may be used, but the present invention is not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As the electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples of the electron injection and transport material include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex including Alq ₃ , an organic radical compound, a hydroxyflavone-metal complex, and a triazine derivative. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

Examples of the metal complex compound 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. The present invention is 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 light emitting device, and in particular, may be a bottom emission device requiring relatively high luminous efficiency.

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

[Production Example 1]

Preparation Example 1-1: Preparation of compound sub A-3

In a nitrogen atmosphere, 2-bromo-6-iodophenol (50 g, 167.9 mmol) and (3-chloro-2-fluorophenyl) boronic acid (29.2 g, 167.9 mmol) were dissolved in tetrahydrofuran (1000 ml). added, stirred and refluxed. Thereafter, potassium carbonate (69.6 g, 503.6 mmol) was dissolved in water (70 ml), and after sufficient stirring, tetrakis (triphenylphosphine) palladium (0) (5.8 g, 5 mmol) was added. After reaction for 1 hour, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (2518 mL), 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 prepare a gray solid compound A-1 (26.2 g, yield 52%, MS: [M+H] ⁺ = 300.9).

Next, put A-1 (30 g, 100 mmol) and bis (pinacolato) diboron (26.7 g, 100 mmol) in dimethylformamide (150 ml) in a nitrogen atmosphere, potassium carbonate was added, and stirred and Heated to 140 °C. After 4 hours of reaction, the mixture was cooled to room temperature and then water was added. After this, the formed solid was filtered. This was again put in chloroform (280 mL) to dissolve, 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 purified through a silica column using chloroform and ethyl acetate to prepare a white solid compound A-2 (18.8 g, yield 67%, MS: [M+H] ⁺ = 280.9).

Then, A-2 (15 g, 53.6 mmol) and bis (pinacolato) diboron (13.7 g, 58.9 mmol) were added to dioxane (300 ml) in a nitrogen atmosphere, stirred and refluxed. After that, potassium acetate (15.5 g, 160.8 mmol) was added, and after sufficient stirring, bis (dibenzylideneacetone) palladium (0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. was put in. After the reaction for 5 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again added to chloroform (176 mL) to dissolve, 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 ethanol to prepare a gray solid compound A-3 (15.8 g, yield 90%, MS: [M+H] ⁺ = 329.1).

Preparation 1-2: Preparation of compound sub B-3

In a nitrogen atmosphere, 2-bromo-6-iodophenol (50 g, 167.9 mmol) and (4-chloro-2-fluorophenyl) boronic acid (29.2 g, 167.9 mmol) were added to tetrahydrofuran (1000 ml). Stirred and refluxed. Thereafter, potassium carbonate (69.6 g, 503.6 mmol) was dissolved in water (70 ml), and after sufficient stirring, tetrakis (triphenylphosphine) palladium (0) (5.8 g, 5 mmol) was added. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (3501 mL), 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 prepare a gray solid compound B-1 (54.6 g, yield 78%, MS: [M+H] ⁺ = 418.1).

Next, in a nitrogen atmosphere, B-1 (30 g, 100 mmol) and bis (pinacolato) diboron (26.7 g, 100 mmol) were put in dimethylformamide (150 ml), potassium carbonate was added, and stirred and 140 heated to °C. After 4 hours of reaction, the mixture was cooled to room temperature and then water was added. After this, the formed solid was filtered. This was again put in chloroform (280 mL) to dissolve, 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 purified through a silica column using chloroform and ethyl acetate to prepare a white solid compound B-2 (15.7 g, yield 56%, MS: [M+H] ⁺ = 280.9).

Then, B-2 (15 g, 68.2 mmol) and bis (pinacolato) diboron (19.1 g, 75 mmol) were added to dioxane (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium acetate (19.7 g, 204.5 mmol) was added and sufficiently stirred, bis (dibenzylideneacetone) palladium (0) (1.2 g, 2 mmol) and tricyclohexylphosphine (1.1 g, 4.1 mmol) were added. was put in. After the reaction for 6 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform (224 mL) to dissolve, 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 ethanol to prepare a gray solid compound B-3 (17 g, yield 76%, MS: [M+H] ⁺ = 329.1).

Preparation Example 1-3: Preparation of compound sub C-3

In a nitrogen atmosphere, 2-bromo-6-iodophenol (50 g, 167.9 mmol) and (5-chloro-2-fluorophenyl) boronic acid (29.2 g, 167.9 mmol) were dissolved in tetrahydrofuran (1000 ml). added, stirred and refluxed. Thereafter, potassium carbonate (69.6 g, 503.6 mmol) was dissolved in water (70 ml), and after sufficient stirring, tetrakis (triphenylphosphine) palladium (0) (5.8 g, 5 mmol) was added. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (3501 mL), 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 prepare a gray solid compound C-1 (39.2 g, yield 56%, MS: [M+H] ⁺ = 418.1).

Next, in a nitrogen atmosphere, C-1 (30 g, 100 mmol) and bis (pinacolato) diboron (26.7 g, 100 mmol) were put in dimethylformamide (150 ml), potassium carbonate was added, and stirred and Heated to 140 °C. After 5 hours of reaction, the mixture was cooled to room temperature and then water was added. After this, the formed solid was filtered. This was again put in chloroform (280 mL) to dissolve, 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 purified through a silica column using chloroform and ethyl acetate to prepare a white solid compound C-2 (20.7 g, yield 74%, MS: [M+H] ⁺ = 280.9).

Then, C-2 (15 g, 68.2 mmol) and bis (pinacolato) diboron (19.1 g, 75 mmol) were added to dioxane (300 ml) in a nitrogen atmosphere, and stirred and refluxed. After that, potassium acetate (19.7 g, 204.5 mmol) was added and sufficiently stirred, bis (dibenzylideneacetone) palladium (0) (1.2 g, 2 mmol) and tricyclohexylphosphine (1.1 g, 4.1 mmol) were added. was put in. After the reaction for 5 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform (224 mL) to dissolve, 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 ethanol to prepare a gray solid compound C-3 (11.4 g, yield 51%, MS: [M+H] ⁺ = 329.1).

Preparation Example 1-3: Preparation of compound sub D-3

In a nitrogen atmosphere, 2-bromo-6-iodophenol (50 g, 167.9 mmol) and (6-chloro-2-fluorophenyl) boronic acid (29.2 g, 167.9 mmol) were dissolved in tetrahydrofuran (1000 ml). added, stirred and refluxed. Thereafter, potassium carbonate (69.6 g, 503.6 mmol) was dissolved in water (70 ml), and after sufficient stirring, tetrakis (triphenylphosphine) palladium (0) (5.8 g, 5 mmol) was added. After 2 hours of reaction, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (3635 mL), 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 prepare a gray solid compound D-1 (36.4 g, yield 50%, MS: [M+H] ⁺ = 434.1).

Next, D-1 (30 g, 100 mmol) and bis (pinacolato) diboron (26.7 g, 100 mmol) were put in dimethylformamide (150 ml) in a nitrogen atmosphere, potassium carbonate was added, and stirred and Heated to 140 °C. After the reaction for 7 hours, the mixture was cooled to room temperature and then water was added. After this, the formed solid was filtered. This was again put in chloroform (280 mL) to dissolve, 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 purified through a silica column using chloroform and ethyl acetate to prepare a white solid compound D-2 (15.1 g, yield 54%, MS: [M+H] ⁺ = 280.9).

Then, D-2 (15 g, 68.2 mmol) and bis (pinacolato) diboron (19.1 g, 75 mmol) were added to dioxane (300 ml) in a nitrogen atmosphere, and stirred and refluxed. After that, potassium acetate (19.7 g, 204.5 mmol) was added and sufficiently stirred, bis (dibenzylideneacetone) palladium (0) (1.2 g, 2 mmol) and tricyclohexylphosphine (1.1 g, 4.1 mmol) were added. was put in. After reaction for 6 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform (224 mL) to dissolve, 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 ethanol to prepare a gray solid compound D-3 (15.7 g, yield 70%, MS: [M+H] ⁺ = 329.1).

[Production Example 2]

Preparation Example 2-1: Preparation of compound sub 1

In a nitrogen atmosphere, Q4 (30 g, 121.9 mmol) and 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (43.4 g, 121.9 mmol) were reacted with tetra It was put in hydrofuran (600 ml), stirred and refluxed. After that, potassium carbonate (50.6 g, 365.8 mmol) was dissolved in water (51 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (4.2 g, 3.7 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (1273 mL) to dissolve, 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 prepare a white solid compound sub 1 (35 g, yield 55%, MS: [M+H] ⁺ = 523.1).

Preparation Example 2-2: Preparation of compound sub 2

R-4 (15 g, 61 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (21.7 g, 61 mmol) in nitrogen atmosphere was put in tetrahydrofuran (300 ml), stirred and refluxed. After that, potassium carbonate (25.3 g, 182.9 mmol) was dissolved in water (25 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 1.8 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (637 mL) to dissolve, 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 prepare a white solid compound sub 2 (19.4 g, yield 61%, MS: [M+H] ⁺ = 523.1).

Preparation 2-3: Preparation of compound sub 3

T-4 (15 g, 61 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (21.7 g, 61 mmol) in nitrogen atmosphere was put in tetrahydrofuran (300 ml), stirred and refluxed. Thereafter, potassium carbonate (25.3 g, 182.9 mmol) was dissolved in water (25 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 1.8 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (637 mL) to dissolve, 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 prepare a white solid compound sub 3 (23.6 g, yield 74%, MS: [M+H] ⁺ = 523.1).

Preparation Example 2-4: Preparation of compound sub 4

K-4 (15 g, 61 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (21.7 g, 61 mmol) in nitrogen atmosphere was put in tetrahydrofuran (300 ml), stirred and refluxed. After that, potassium carbonate (25.3 g, 182.9 mmol) was dissolved in water (25 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 1.8 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (637 mL) to dissolve, 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 prepare a white solid compound sub 4 (16.9 g, yield 53%, MS: [M+H] ⁺ = 523.1).

Preparation Example 2-5: Preparation of compound sub 5

A-3 (15 g, 48.1 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (17.1 g, 48.1 mmol) in nitrogen atmosphere was put in tetrahydrofuran (300 ml), stirred and refluxed. Thereafter, potassium carbonate (19.9 g, 144.2 mmol) was dissolved in water (20 ml), and after sufficient stirring, tetrakis (triphenylphosphine) palladium (0) (1.7 g, 1.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (502 mL) to dissolve, 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 prepare a white solid compound sub 5 (12.5 g, yield 50%, MS: [M+H] ⁺ = 523.1).

Preparation Example 2-6: Preparation of compound sub 6

B-3 (15 g, 61 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (21.7 g, 61 mmol) in nitrogen atmosphere was put into tetrahydrofuran (300 ml), stirred and refluxed. After that, potassium carbonate (25.3 g, 182.9 mmol) was dissolved in water (25 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 1.8 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (637 mL) to dissolve, 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 prepare a white solid compound sub 6 (18.1 g, yield 57%, MS: [M+H] ⁺ = 523.1).

Preparation Example 2-7: Preparation of compound sub 7

C-3 (15 g, 61 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (21.7 g, 61 mmol) in nitrogen atmosphere was put in tetrahydrofuran (300 ml), stirred and refluxed. After that, potassium carbonate (25.3 g, 182.9 mmol) was dissolved in water (25 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (2.1 g, 1.8 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (637 mL) to dissolve, 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 prepare a white solid compound sub 7 (20.7 g, yield 65%, MS: [M+H] ⁺ = 523.1).

Preparation Example 2-8: Preparation of compound sub 8

D-3 (15 g, 61 mmol) and 9- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (21.7 g, 61 mmol) in nitrogen atmosphere was put in tetrahydrofuran (300 ml), stirred and refluxed. After that, potassium carbonate (25.3 g, 182.9 mmol) was dissolved in water (25 ml), and after stirring sufficiently, tetrakis(triphenylphosphine)palladium (2.1 g, 1.8 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform (637 mL) to dissolve, 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 prepare a white solid compound sub 8 (20.1 g, yield 63%, MS: [M+H] ⁺ = 523.1).

[Example]

Example 1: Preparation of compound 1

In a nitrogen atmosphere, Sub 1 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-d6 (3.2 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After reaction for 1 hour, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 1 (7.3 g, yield 59%, MS: [M+H] ⁺ = 660.3).

Example 2: Preparation of compound 2

In a nitrogen atmosphere, Sub 1 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-d6 (3.3 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (373 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 2 (7.3 g, yield 59%, MS: [M+H] ⁺ = 662.3).

Example 3: Preparation of compound 3

Sub 2 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-d6 (3.2 g, 18.8 mmol) in xylene (200 ml) in a nitrogen atmosphere, stirred and refluxed did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After reaction for 1 hour, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 3 (8.4 g, yield 68%, MS: [M+H] ⁺ = 660.3).

Example 4: Preparation of compound 4

In a nitrogen atmosphere, Sub 3 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (3.2 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 4 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 4 (7.1 g, yield 57%, MS: [M+H] ⁺ = 660.3).

Example 5: Preparation of compound 5

Sub 4 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (3.2 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, stirred and refluxed did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 2 hours of reaction, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 5 (9.8 g, yield 79%, MS: [M+H] ⁺ = 660.3).

Example 6: Preparation of compound 6

In a nitrogen atmosphere, Sub 5 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (3.2 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After reaction for 1 hour, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 6 (9 g, yield 73%, MS: [M+H] ⁺ = 660.3).

Example 7: Preparation of compound 7

In a nitrogen atmosphere, Sub 5 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (3.3 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 2 hours of reaction, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (373 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 7 (7.8 g, yield 63%, MS: [M+H] ⁺ = 662.3).

Example 8: Preparation of compound 8

In a nitrogen atmosphere, Sub 6 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (3.2 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 8 (7.9 g, yield 64%, MS: [M+H] ⁺ = 660.3).

Example 9: Preparation of compound 9

In a nitrogen atmosphere, Sub 7 (10 g, 18.8 mmol) and 9H-carbazole-1,3,4,5,6,8-D6 (3.2 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. did Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (372 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 9 (8.7 g, yield 70%, MS: [M+H] ⁺ = 660.3).

Example 10: Preparation of compound 10

Sub 8 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 10 (6.8 g, yield 55%, MS: [M+H] ⁺ = 655.2).

Example 11: Preparation of compound 11

In a nitrogen atmosphere, Sub 1 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml), stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After reaction for 1 hour, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 11 (8 g, yield 65%, MS: [M+H] ⁺ = 655.2).

Example 12: Preparation of compound 12

Sub 2 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours of reaction, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 12 (7.4 g, yield 60%, MS: [M+H] ⁺ = 655.2).

Example 13: Preparation of compound 13

Sub 3 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 4 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 13 (6.1 g, yield 50%, MS: [M+H] ⁺ = 655.2).

Example 14: Preparation of compound 14

Sub 4 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were placed in xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 14 (8 g, yield 65%, MS: [M+H] ⁺ = 655.2).

Example 15: Preparation of compound 15

Sub 5 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were placed in xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 15 (7.3 g, yield 59%, MS: [M+H] ⁺ = 655.2).

Example 16: Preparation of compound 16

Sub 6 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 4 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 16 (7.7 g, yield 63%, MS: [M+H] ⁺ = 655.2).

Example 17: Preparation of compound 17

Sub 7 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound Compound 17 (6.1 g, yield 50%, MS: [M+H] ⁺ = 655.2).

Example 18: Preparation of compound 18

Sub 8 (10 g, 18.8 mmol) and 9H-carbazole (3.1 g, 18.8 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.4 g, 56.4 mmol) was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (369 mL), 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 purified through a silica column using chloroform and ethyl acetate to prepare a pale yellow solid compound 18 (6.8 g, yield 55%, MS: [M+H] ⁺ = 655.2).

[Experimental example]

Experimental Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,300 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

A hole injection layer was formed by thermal vacuum deposition of the following HI-1 compound to a thickness of 50 Å on the ITO transparent electrode prepared as described above. The following HT-1 compound was thermally vacuum-deposited to a thickness of 250 Å on the hole injection layer to form a hole transport layer, and the following HT-2 compound was vacuum-deposited to a thickness of 50 Å on the HT-1 deposited film to form an electron blocking layer. Compound 1 prepared in Example 1 above, the following YGH-1 compound, and phosphorescent dopant YGD-1 as a light emitting layer on the HT-2 deposited film were co-deposited in a weight ratio of 44:44:12 to form a light emitting layer having a thickness of 400 Å. The following ET-1 compound was vacuum deposited on the light emitting layer to a thickness of 250 Å to form an electron transport layer, and the following ET-2 compound and Li were vacuum deposited in a weight ratio of 98:2 on the electron transport layer to form an electron injection layer with a thickness of 100 Å formed. A cathode was formed by depositing aluminum to a thickness of 1000 Å on the electron injection layer.

In the above process, the deposition rate of organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 1×10 ^-7 ~ 5×10 ^-8 torr did

Experimental Examples 2 to 18

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of Compound 1 of Example 1 in Experimental Example 1.

Comparative Experimental Examples 1 to 3

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of Compound 1 of Example 1 in Experimental Example 1. The compounds of CE1 to CE3 in Table 1 below are as follows.

In the Experimental Examples and Comparative Experimental Examples, voltage and efficiency were measured for the organic light emitting device at a current density of 10 mA/cm ² , and lifetimes were measured at a current density of 50 mA/cm ² The results are shown in Table 1 below. . At this time, LT95 means the time to be 95% of the initial luminance.

compound Voltage (V)
(@10mA/cm ² ) Efficiency (Cd/A)
(@10mA/cm ² ) color coordinates
(x,y) Life (h)
(LT ₉₅ at 50mA/cm ² ) Experimental Example 1 compound 1 3.8 85 0.44, 0.54 340 Experimental Example 2 compound 2 3.8 85 0.44, 0.54 350 Experimental Example 3 compound 3 3.7 89 0.44, 0.54 363 Experimental Example 4 compound 4 3.9 87 0.46, 0.54 375 Experimental Example 5 compound 5 4 82 0.46, 0.54 400 Experimental Example 6 compound 6 3.6 90 0.46, 0.53 290 Experimental Example 7 compound 7 3.6 90 0.46, 0.53 300 Experimental Example 8 compound 8 3.7 88 0.46, 0.54 245 Experimental Example 9 compound 9 3.6 89 0.46, 0.54 290 Experimental Example 10 compound 10 3.9 84 0.46, 0.54 290

compound Voltage (V)
(@10mA/cm ² ) Efficiency (Cd/A)
(@10mA/cm ² ) color coordinates
(x,y) Life (h)
(LT ₉₅ at 50mA/cm ² ) Experimental Example 11 compound 11 3.8 85 0.44, 0.54 200 Experimental Example 12 compound 12 3.7 89 0.44, 0.54 212 Experimental Example 13 compound 13 3.9 87 0.46, 0.54 235 Experimental Example 14 compound 14 4 82 0.46, 0.54 250 Experimental Example 15 compound 15 3.6 90 0.46, 0.53 150 Experimental Example 16 compound 16 3.7 88 0.46, 0.54 125 Experimental Example 17 compound 17 3.6 89 0.46, 0.54 170 Experimental Example 18 compound 18 3.9 84 0.46, 0.54 175 Comparative Experimental Example 1 CE1 4.5 75 0.46, 0.54 85 Comparative Experimental Example 2 CE2 4.1 83 0.46, 0.54 125 Comparative Experimental Example 3 CE3 4.2 82 0.46, 0.54 145

As shown in Table 1, when the compound of the present invention was used as the light emitting layer material, it was confirmed that the efficiency and lifespan were superior to those of the Comparative Experimental Example. It is seen that the electron stability is increased as triazine and carbazole groups are substituted in the dibenzofuran group, which is a core substituent. In particular, when one or more deuterium is substituted in the carbazole group, excellent properties are shown in increasing the lifespan. It is also seen that the electronic stability is increased.

[Explanation of code]

1: Substrate 2: Anode

3: hole transport layer 4: light emitting layer

5: Electron injection and transport layer 6: Cathode

7: hole injection layer 8: electron suppression layer

9: hole blocking layer

Claims (12)

A compound represented by the following formula (1): [Formula 1] AL ₁ -BC In Formula 1, A is represented by the following formula (2), [Formula 2]

In Formula 2, each X is independently N or CH; 2 or more of X is N, Ar ₁ and Ar ₂ are each independently C _6-60 aryl, substituted or unsubstituted, or C _2- containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S ₆₀ heteroaryl; At least one of Ar ₁ and Ar ₂ is substituted or unsubstituted carbazol-9-yl, L ₁ is a direct bond, substituted or unsubstituted C _6-60 arylene, or C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S Ren, B is represented by the following formula (3), [Formula 3]

In Formula 3, Y ₁ is O or S, Any one of Q ₁ and Q ₂ is combined with L ₁ of Formula 1, and the rest is CH, Any one of Z- ₁ to Z ₄ is bonded to C of Formula 1, the rest is CH, C is represented by the following formula (4), [Formula 4]

In Formula 4, D is a C _6-60 aryl ring or a C _2-60 heteroaryl ring containing at least one heteroatom selected from the group consisting of N, O and S, R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted silyl, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted or C _2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S; Adjacent two combine to form a benzene ring, and the remainder is hydrogen or deuterium; a is an integer from 1 to 58; According to claim 1, The following Chemical Formula 1 is that of the following Chemical Formula 1-1 or 1-2, compound: [Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, D, X, Y ₁ , L ₁ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , and a have the same definitions as in claim 1 . According to claim 1, X is all N, compound. According to claim 1, any one of Ar ₁ and Ar ₂ is phenyl, biphenylyl, carbazol-9-yl, dibenzofuranyl, or dibenzothiophenyl unsubstituted or substituted with one or more deuterium; wherein the other one of Ar ₁ and Ar ₂ is carbazol-9-yl which is unsubstituted or substituted with one or more phenyl, compound. According to claim 1, L ₁ is a direct bond, phenylene, biphenylene, naphthylene, carbazol-9-ylene, dibenzofuranylene, or dibenzothiophenylene, compound. According to claim 1, D is a benzene ring, a naphthalene ring, a phenanthrene ring, a 9-phenyl-9H-carbazole ring, a dimethylfluorene ring, a dibenzofuran ring, or a dibenzothiophene ring, compound. According to claim 1, a is an integer from 1 to 8, compound. According to claim 1, R ₁ and R ₂ are each independently hydrogen, deuterium, or phenyl unsubstituted or substituted with one or more deuterium, compound. According to claim 1, R ₁ and R ₂ are each independently deuterium, C _6-60 aryl substituted with one or more deuterium, or C containing one or more heteroatoms selected from the group consisting of N, O and S substituted with one or more deuterium _2-60 heteroaryl; Adjacent two combine to form a benzene ring, the remainder being deuterium; compound. According to claim 1, The compound represented by Formula 1 is, Any one selected from the group consisting of the following compounds, compound:

. An organic light emitting device comprising a first electrode, a second electrode provided to face the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises: The organic light-emitting device comprising the compound according to any one of claims 1 to 10. 12. The method of claim 11, The organic material layer containing the compound is a light emitting layer, organic light emitting device.

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