WO2022060047A1 - 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 using 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. 10-2020-0120013 on September 17, 2020 and Korean Patent Application No. 10-2021-0121855 on September 13, 2021, 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]

In Formula 1,

Ar ₁ is substituted or unsubstituted C _6-60 aryl, or C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

Two of R ₁ to R ₅ are each independently N(Ar ₂ )(Ar ₃ ), and the remainder are each independently hydrogen or deuterium;

However, except when R ₂ and R ₄ are N(Ar ₂ )(Ar ₃ ) at the same time,

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl, or C _2-60 including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S heteroaryl.

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.

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 transport layer 5, an electron injection layer 6, and a cathode 7 did it

2 is a substrate (1), anode (2), hole injection layer (8), hole transport layer (3), electron blocking layer (9), light emitting layer (4), hole blocking layer (10), electron transport layer (5) , an example of an organic light emitting device comprising an electron injection layer 6 and a cathode 7 is shown.

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

(Definition of Terms)

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. For example, the term "substituted or unsubstituted" means "unsubstituted or at least one selected from the group consisting of deuterium, halogen, C _1-10 alkyl, C _1-10 alkoxy and C _6-20 aryl. , for example, substituted with 1 to 5 substituents. Also, as used herein, the term “substituted with one or more substituents” shall be understood to mean, for example, “substituted with 1 to 5 substituents”, or “substituted with 1 or 2 substituents”. can

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 substituent 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 substituent 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 substituent 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 fluoro, chloro, bromo, or iodo.

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, 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-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1,1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5 -Methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4,4-trimethyl-1-pentyl, 2,4,4- trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 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.

The compound represented by Formula 1 may include fluorene as a core, and aryl or heteroaryl (Ar ₁ ); and phenyl to which two amine-based substituents are bonded; based on a structure each bonded to carbon 9 of the core.

Here, the two amine-based substituents are aryl or heteroaryl present on both sides (N(Ar ₂ )(Ar ₃ )), respectively. However, based on the 9th carbon of the core, when the two amine-based substituents are in meta positions, respectively (ie, R ₂ and R ₄ in Formula 1 are N(Ar ₂ )(Ar ₃ ) )) is excluded.

In particular, the compound represented by Formula 1 may include a compound in which R ₂ and R ₄ are each N(Ar ₂ )(Ar ₃ ); a compound in which only one of R ₁ to R ₅ is N(Ar ₂ )(Ar ₃ ); And any one of R ₁ to R ₅ is N(Ar ₂ )(Ar ₃ ) and N(Ar 2 )(Ar 3 ) is a synergistic effect between the core structure and the amine-based substituent position compared to the compound in which N(Ar ₂ )(Ar ₃ ) is bonded as a substituent of Ar ₁ By this, it is possible to express remarkably excellent ability in terms of hole injection, hole transport and electron suppression.

Accordingly, the organic light emitting device in which the compound represented by Formula 1 is used as a material for an organic layer of the organic light emitting device, for example, a hole transport layer, R ₂ and R ₄ is each N(Ar ₂ ) (Ar ₃ ) compound; a compound in which only one of R ₁ to R ₅ is N(Ar ₂ )(Ar ₃ ); And R ₁ To R ₅ Any one of N(Ar ₂ )(Ar ₃ ) and N(Ar ₂ )(Ar ₃ ) as a substituent of Ar ₁ A driving voltage compared to an organic light-emitting device employing a compound bonded thereto, respectively; It may exhibit excellent properties in terms of both luminous efficiency and lifetime.

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

Preferably, two of R ₁ to R ₅ are each N(Ar ₂ )(Ar ₃ ),

where R ₂ and R ₄ are each N(Ar ₂ )(Ar ₃ ), except when

R ₁ to R ₅ not represented by N(Ar ₂ )(Ar ₃ ) are each independently hydrogen or deuterium.

Preferably, Ar ₁ is substituted or unsubstituted C _6-30 aryl, or C _2-30 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S can be

More preferably, Ar ₁ is C _6-20 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl.

For example, Ar ₁ may be phenyl, biphenylyl, naphthyl, phenanthryl, 9,9-dimethylfluorenyl, or dibenzofuranyl.

More specifically, Ar may be any one selected from the group consisting of:

.

Preferably, Ar ₂ and Ar ₃ are each independently selected from the group consisting of substituted or unsubstituted C _6-30 aryl, or substituted or unsubstituted N, O, and S comprising any one or more heteroatoms C _2-30 heteroaryl.

More preferably, Ar ₂ and Ar ₃ are each independently C _6-20 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl.

For example, Ar ₂ and Ar ₃ may each independently be phenyl, biphenylyl, naphthyl, 9,9-dimethylfluorenyl, or dibenzofuranyl.

Preferably, Ar ₂ and Ar ₃ are each independently C _6-20 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl; or

At least one of Ar ₂ and Ar ₃ is unsubstituted or C ₂ comprising one heteroatom of N, O and S substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl _-20 heteroaryl.

For example, Ar ₂ and Ar ₃ are each independently phenyl, biphenylyl, naphthyl, 9,9-dimethylfluorenyl, or dibenzofuranyl; or

At least one of Ar ₂ and Ar ₃ may be dibenzofuranyl.

For example, Formula 1 may be represented by any one of Formulas 1-1 to 1-5 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 to 1-5,

Ar _{21 ,} Ar ₂₂ , Ar ₃₁ and Ar ₃₂ are each independently unsubstituted or substituted with one or more substituents selected from the group consisting of _deuterium and C _1-10 alkyl; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl;

R ₁ To R ₅ are each independently hydrogen or deuterium,

Ar ₁ is as defined in Formula 1 above.

Preferably, in Formulas 1-1 to 1-5, any one of Ar ₂₁ and Ar ₃₁ is the same as Ar ₂₂ , and the other one is the same as Ar ₃₂ .

Preferably, in Formulas 1-1 to 1-5, Ar _{21 ,} Ar ₂₂ , Ar ₃₁ and Ar ₃₂ are each independently phenyl, biphenylyl, naphthyl, 9,9-dimethylfluorenyl, or di It may be benzofuranyl.

Representative examples of the compound represented by Formula 1 are as follows:

.

Among the compounds represented by Formula 1-1, when Ar ₂₁ is the same as Ar ₂₂ and Ar ₃₁ is the same as Ar ₃₂ , for example, it may be prepared using Scheme 1 below.

[Scheme 1]

In Scheme 1, each X is independently halogen, preferably chloro or bromo, and the description of other substituents is as described above.

Specifically, the compound represented by Formula 1-1 is prepared through the amine substitution reaction of starting materials SM1 and SM2. Here, the amine substitution reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art.

In addition, a compound having a structure different from that of Chemical Formula 1-1 among the compounds represented by Chemical Formula 1 may be prepared by appropriately changing the structure of the starting material in Scheme 1 above. 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.

Preferably, the organic material layer including the compound may be a hole transport layer.

In an embodiment, the organic material layer may include a hole transport layer, a light emitting layer, and an electron injection and transport layer, wherein the organic material layer including the compound may be a hole transport layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron injection and transport layer, wherein the organic material layer including the compound may be a hole transport layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer and an electron injection and transport layer, wherein the organic material layer containing the compound may be a hole transport layer.

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 .

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 transport layer 5, an electron injection layer 6, and a cathode 7 did it In such a structure, the compound represented by Formula 1 may be included in the hole transport layer.

2 is a substrate (1), anode (2), hole injection layer (8), hole transport layer (3), electron blocking layer (9), light emitting layer (4), hole blocking layer (10), electron transport layer (5) , an example of an organic light emitting device comprising an electron injection layer 6 and a cathode 7 is 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 blocking 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 blocking layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase 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 compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, 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 transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. Suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material included in the electron injection layer has the ability to transport electrons, and has excellent electron injection effect from the cathode and electron injection for the light emitting layer or the light emitting material. A compound that has an effect, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and is excellent in thin film formation ability is preferred. Specifically, as the electron injection material, LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, phenanthroline, and the like, derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are 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.

The compound represented by Formula 1 and the preparation of an organic light emitting device including the same will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of Compound 1

Compound A (7.5 g, 19.36 mmol) and compound a1 (6.59 g, 38.92 mmol) were completely dissolved in 290 mL of Xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and then NaOtBu (5.58 g, 58.09 mmol) was added, and Bis (tri- tert -butylphosphine) palladium (0) (0.49 g, 0.97 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 250 mL of ethyl acetate to prepare Compound 1 (10.05 g, yield: 79%).

MS[M+H] ⁺ = 653

Preparation Example 2: Preparation of compound 2

Compound B (8.20 g, 21.17 mmol) and compound a2 (10.44 g, 42.56 mmol) were completely dissolved in 310 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (6.10 g, 63.52 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.54 g, 1.06 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 250 mL of ethyl acetate to prepare Compound 2 (11.02 g, yield: 65%).

MS[M+H] ⁺ = 805

Preparation Example 3: Preparation of compound 3

Compound C (7.35 g, 18.98 mmol) and compound a3 (12.26 g, 38.14 mmol) were completely dissolved in 285 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (5.47 g, 56.93 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.48 g, 0.95 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 250 mL of ethyl acetate to prepare Compound 3 (13.45 g, yield: 74%).

MS[M+H] ⁺ = 957

Preparation Example 4: Preparation of compound 4

Compound D (8.05 g, 20.78 mmol) and compound a4 (11.25 g, 41.78 mmol) were completely dissolved in 312 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (5.99 g, 62.35 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.53 g, 1.04 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 270 mL of ethyl acetate to prepare compound 4 (12.55 g, yield: 71%).

MS[M+H] ⁺ = 853

Preparation Example 5: Preparation of compound 5

Compound E (7.40 g, 19.11 mmol) and compound a5 (8.42 g, 38.40 mmol) were completely dissolved in 287 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (5.51 g, 57.32 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.49 g, 0.96 mmol) was added, and the mixture was heated and stirred for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 280 mL of ethyl acetate to prepare compound 5 (10.23 g, yield: 71%).

MS[M+H] ⁺ = 753

Preparation Example 6: Preparation of compound 6

Compound F (7.30 g, 18.85 mmol) and compound a6 (6.41 g, 37.89 mmol) were completely dissolved in 283 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (5.43 g, 56.55 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.48 g, 0.94 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 280 mL of ethyl acetate to prepare compound 6 (10.04 g, yield: 82%).

MS[M+H] ⁺ = 653

Preparation Example 7: Preparation of compound 7

Compound G (7.55 g, 16.29 mmol) and compound a7 (8.03 g, 32.75 mmol) were completely dissolved in 240 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (4.70 g, 48.88 mmol) was added, and Bis (tri- tert -butylphosphine) palladium (0) (0.42 g, 0.81 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 230 mL of ethyl acetate to prepare compound 7 (10.78 g, yield: 75%).

MS[M+H] ⁺ = 881

Preparation 8: Preparation of compound 8

Compound H (8.15 g, 18.63 mmol) and compound a8 (6.34 g, 37.46 mmol) were completely dissolved in 280 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (5.37 g, 55.90 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.48 g, 0.93 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from ethyl acetate 240 mL to prepare Compound 8 (10.80 g, yield: 82%).

MS[M+H] ⁺ = 703

Preparation Example 9: Preparation of compound 9

Compound I (8.10 g, 16.97 mmol) and compound a9 (5.77 g, 34.10 mmol) were completely dissolved in 255 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (4.89 g, 50.90 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.43 g, 0.85 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from ethyl acetate 240 mL to prepare compound 9 (7.70 g, yield: 61%).

MS[M+H] ⁺ = 743

Preparation 10: Preparation of compound 10

Compound J (7.80 g, 16.00 mmol) and compound a10 (5.44 g, 32.17 mmol) were completely dissolved in 240 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (4.61 g, 48.01 mmol) was added thereto, and Bis (tri- tert -butylphosphine) palladium (0) (0.41 g, 0.80 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from ethyl acetate 240 mL to prepare Compound 10 (8.50 g, yield: 71%).

MS[M+H] ⁺ = 753

Preparation 11: Preparation of compound 11

Compound K (6.50 g, 16.78 mmol) and compound a11 (8.75 g, 33.73 mmol) were completely dissolved in 240 mL of Xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and then NaOtBu (4.89 g, 50.35 mmol) was added, and Bis (tri- tert -butylphosphine) palladium (0) (0.43 g, 0.84 mmol) was added, followed by heating and stirring for 8 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from ethyl acetate 240 mL to prepare compound 11 (9.25 g, yield: 66%).

MS[M+H] ⁺ = 833.0

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, 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 thermally vacuum-depositing the compound of the following compound HI-1 and the compound of the following compound HI-2 to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on the prepared ITO transparent electrode. Compound 1-1 (1150 Å) prepared in Preparation Example 1, which is a material for transporting holes, was vacuum deposited on the hole injection layer to form a hole transport layer. Then, the following compound EB-1 was vacuum-deposited to a thickness of 50 Å on the hole transport layer to form an electron blocking layer.

Then, the compound represented by the following formula BH and the compound represented by the following formula BD to a thickness of 200 Å on the electron blocking layer were vacuum-deposited in a weight ratio of 25:1 to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB-1 to a thickness of 50 Å on the light emitting layer. Then, on the hole blocking layer, the following compound ET-1 and the following compound LiQ (Lithium Quinolate) were vacuum-deposited in a weight ratio of 1:1 to form an electron transport layer to a thickness of 300 Å. On the electron transport layer, lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 Å were sequentially deposited to form an electron injection layer and a cathode, respectively.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2 x 10 ^- By maintaining ⁷ to 5 x 10 ^-6 torr, an organic light emitting diode was manufactured.

The compounds used in Example 1 above were as follows:

.

Examples 2 to 11

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

Comparative Examples 1 to 5

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 of Preparation Example 1. The compounds of the comparative examples used in Table 1 below are as follows:

.

Experimental Example 1

When a current of 20 mA/cm ² was applied to the organic light emitting diodes prepared in Examples and Comparative Examples, the driving voltage, luminous efficiency, and color coordinates were measured, and the time (T95) at which it became 95% of the initial luminance was measured. did The results are shown in Table 1 below. T95 denotes a time required for the luminance to decrease from the initial luminance (1600 nit) to 95%.

	compound (hole transport layer)	Voltage (V @20mA/cm 2 )	efficiency (cd/A @20mA/cm 2 )	color coordinates (x,y)	T95 (hr)
Example 1	compound 1	3.60	6.72	(0.146, 0.046)	340
Example 2	compound 2	3.55	6.72	(0.146, 0.046)	355
Example 3	compound 3	3.60	6.75	(0.146, 0.046)	335
Example 4	compound 4	3.56	6.76	(0.147, 0.045)	348
Example 5	compound 5	3.56	6.75	(0.147, 0.045)	352
Example 6	compound 6	3.55	6.75	(0.147, 0.045)	360
Example 7	compound 7	3.57	6.72	(0.147, 0.045)	350
Example 8	compound 8	3.56	6.76	(0.147, 0.045)	350
Example 9	compound 9	3.56	6.72	(0.147, 0.045)	372
Example 10	compound 10	3.57	6.80	(0.146, 0.045)	340
Example 11	compound 11	3.45	6.98	(0.146, 0.045)	345
Comparative Example 1	HT-1	3.88	6.20	(0.146, 0.047)	318
Comparative Example 2	HT-2	3.95	6.12	(0.146, 0.046)	305
Comparative Example 3	HT-3	4.22	6.15	(0.147, 0.045)	270
Comparative Example 4	HT-4	4.30	6.10	(0.146, 0.046)	275
Comparative Example 5	HT-5	4.15	5.85	(0.145, 0.045)	255

As shown in Table 1, the organic light emitting device of the embodiment using the compound represented by Formula 1 as a hole transport layer material, R ₂ and R ₄ are N(Ar ₂ )(Ar ₃ ) compounds at the same time (Comparative Example) 1 and 2); a compound in which only one of R ₁ to R ₅ is N(Ar ₂ )(Ar ₃ ) (Comparative Examples 3 and 5); And any one of R ₁ to R ₅ is N(Ar ₂ )(Ar ₃ ) and an organic light-emitting device to which a compound (Comparative Example 4) in which N(Ar ₂ )(Ar ₃ ) is bonded as a substituent of Ar ₁ (Comparative Example 4) is applied. In comparison, excellent characteristics were exhibited in terms of driving voltage, luminous efficiency, and lifetime.

Considering that the luminous efficiency and lifespan characteristics of the organic light emitting device have a trade-off relationship with each other in general, the organic light emitting device employing the compound of the present invention exhibits significantly improved device characteristics compared to the comparative example device. can be known

[Explanation of code]

1: Substrate 2: Anode

3: hole transport layer 4: light emitting layer

5: electron transport layer 6: electron injection layer

7: cathode 8: hole injection layer

9: Electronic blocking layer

10: hole blocking layer

Claims (11)

1. A compound represented by the following formula (1):

   [Formula 1]

   

   In Formula 1,

   Ar ₁ is substituted or unsubstituted C _6-60 aryl, or C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

   Two of R ₁ to R ₅ are each independently N(Ar ₂ )(Ar ₃ ), and the remainder are each independently hydrogen or deuterium;

   However, except when R ₂ and R ₄ are N(Ar ₂ )(Ar ₃ ) at the same time,

   Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl, or C _2-60 including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S heteroaryl.
2. According to claim 1,

   Ar ₁ is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl; C _6-20 aryl; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl;

   compound.
3. According to claim 1,

   Ar ₁ is phenyl, biphenylyl, naphthyl, phenanthryl, 9,9-dimethylfluorenyl, or dibenzofuranyl;

   compound.
4. According to claim 1,

   Ar ₂ and Ar ₃ are each independently C _6-20 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl;

   compound.
5. According to claim 1,

   Ar ₂ and Ar ₃ are each independently phenyl, biphenylyl, naphthyl, 9,9-dimethylfluorenyl, or dibenzofuranyl; or

   At least one of Ar ₂ and Ar ₃ is dibenzofuranylyl,

   compound.
6. According to claim 1,

   The compound is represented by any one of the following formulas 1-1 to 1-5,

   compound:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   [Formula 1-4]

   

   [Formula 1-5]

   

   In Formulas 1-1 to 1-5,

   Ar _{21 ,} Ar ₂₂ , Ar ₃₁ and Ar ₃₂ are each independently unsubstituted or substituted with one or more substituents selected from the group consisting of _deuterium and C _1-10 alkyl; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _1-10 alkyl;

   R ₁ To R ₅ are each independently hydrogen or deuterium,

   Ar ₁ is as defined in claim 1.
7. 7. The method of claim 6,

   any one of Ar ₂₁ and Ar ₃₁ is the same as Ar ₂₂ , and the other is the same as Ar ₃₂ ,

   compound.
8. 7. The method of claim 6,

   Ar _{21 ,} Ar ₂₂ , Ar ₃₁ and Ar ₃₂ are each independently phenyl, biphenylyl, naphthyl, 9,9-dimethylfluorenyl, or dibenzofuranyl;

   compound.
9. According to claim 1,

   The compound is any one selected from the group consisting of the following compounds,

   compound:

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
10. 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 9.
11. 11. The method of claim 10,

    The organic layer containing the compound is a hole transport layer,

    organic light emitting device.

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