KR20210123664A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 described above can be used as a material for the organic material layer of the organic light emitting device, and can improve efficiency, lower driving voltage and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, and for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. 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.

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,

one of Ar is C _6-60 aryl, the other is hydrogen; heavy hydrogen; or C _6-60 aryl,

Here, when Ar is C _6-60 aryl, Ar may be unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-60} alkyl and C _{6-60 aryl,}

L ₁ and L ₂ are each independently, a single bond; substituted or unsubstituted C _6-60 arylene; _{or C 2-60} heteroarylene containing one or more heteroatoms among substituted or unsubstituted N, O and S;

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;

R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; or substituted or unsubstituted C _6-60 aryl, or _{adjacent two of R 1} to R ₄ and adjacent two of R ₅ to R ₈ are bonded to each other to form a C _6-60 aromatic ring or N, O and S _{A C 2-60} heteroaromatic ring including any one or more heteroatoms selected from the group consisting of may be formed.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. .

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.

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 comprising 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; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more, or substituted or unsubstituted with two or more substituents of the above-exemplified substituents 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, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, 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 alkyl group has 1 to 10 carbon atoms. 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, adamantyl, 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. 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 be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

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 it 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, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, phenothiazinyl group, and dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group is the same as the examples of the aryl group described above. 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 heteroaryl described above 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 heterocycle is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that it is formed by combining two substituents.

(compound)

On the other hand, the present invention provides a compound represented by the above formula (1).

Specifically, the compound represented by Formula 1 is an amine compound in which a carbazole-based core and an amino group are connected by a 1,1'-biphenyl-3,4'-diyl linker, wherein the 1,1'-biphenyl-3; At least one of carbons 4 and 6 of the 4'-diyl linker is substituted with an aryl group, and carbons 2 and 5 are not substituted with a substituent. When the substitution position is indicated in the linker of Formula 1, it is as follows:

[Formula 1]

The compound having a structure in which at least one of the 4th and 6th carbons of the 1,1'-biphenyl-3,4'-diyl linker is substituted with an aryl group is 1,1'-biphenyl-3,4' - Compared to the compound in which the 2nd or 5th carbon of the diyl linker is substituted with an aryl group, it may exhibit improved hole transport ability and improved thermal stability. Accordingly, the organic light-emitting device employing the compound has higher efficiency than an organic light-emitting device employing a compound in which the 2nd or 5th carbon of the 1,1'-biphenyl-3,4'-diyl linker is substituted with an aryl group. , low driving voltage and long lifespan.

In addition, the compound represented by Formula 1 has excellent thermal stability compared to the compound in which an aryl group substituted with the 1,1'-biphenyl-3,4'-diyl linker is substituted with a heteroaryl group such as a carbazolyl group, An organic light emitting device employing the compound may exhibit significantly improved lifespan characteristics compared to an organic light emitting device employing a compound in which an aryl group substituted with the linker is substituted with a heteroaryl group.

Specifically, one of Ar is unsubstituted or _{C 6-60} aryl substituted with one or more substituents selected from the group consisting of _{C 1-10} alkyl and C _6-20 aryl, and the other is hydrogen, or It may be deuterium.

Alternatively, all of Ar may be unsubstituted or _{C 6-60} aryl substituted with one or more substituents selected from the group consisting of _{C 1-10} alkyl and C _{6-20 aryl.}

For example, one of Ar is phenyl, biphenylyl, naphthyl, anthryl, phenanthryl, or fluorenyl, and the other is hydrogen or deuterium;

Here, when Ar is phenyl, biphenylyl, naphthyl, anthryl, phenanthryl, or fluorenyl, Ar may be unsubstituted or substituted with deuterium, methyl, or phenyl.

More specifically, the compound may be represented by the following Chemical Formula 1-1 or 1-2. Specifically, in Chemical Formula 1, the 4th carbon of the 1,1'-biphenyl-3,4'-diyl linker is When substituted with an aryl group, the compound may be represented by the following Chemical Formula 1-1, and in Chemical Formula 1, when carbon 6 of the 1,1'-biphenyl-3,4'-diyl linker is substituted with an aryl group, The compound may be represented by the following formula 1-2:

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

Ar is _{C 6-60} aryl unsubstituted or substituted with 1 or 2 substituents selected from the group consisting of _{C 1-10} alkyl and C _{6-20 aryl;}

L ₁ , L ₂ , Ar ₁ , Ar _{2 ,} and R ₁ to R ₈ are as defined in Formula 1 above.

In this case, in Formulas 1-1 and 1-2, Ar is phenyl, biphenylyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenyl It may be fluorenyl, but is not limited thereto.

In addition, in Formula 1, L ₁ And L ₂ Each independently, a single bond; Or unsubstituted or deuterium, may be C _1-10 alkyl and C _6-20 renil aryl substituted with one or more substituents selected from the group consisting of C _6-20 aryl.

Specifically, L ₁ and L ₂ may each independently be a single bond, phenylene, biphenyldiyl, naphthylene, or 9,9-dimethylfluorenylene.

More specifically, L ₁ and L ₂ may each independently be a single bond, or any one selected from the group consisting of:

.

.

In addition, in Formula 1, Ar ₁ and Ar ₂ are each independently C _6-30 aryl, dibenzofuranyl, or dibenzothiophenyl;

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl, and C _{6-20 aryl.}

Specifically, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, 9,9'-spirobifluorene nyl, dibenzofuranyl, or dibenzothiophenyl;

wherein Ar ₁ and Ar ₂ are unsubstituted or _{one or more substituents selected from the group consisting of deuterium, C 1-10} alkyl and C _6-20 aryl, for example, deuterium, methyl, ethyl, propyl, and may be substituted with one or more substituents selected from the group consisting of isopropyl, butyl, tert-butyl and phenyl.

More specifically, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, triphenylenyl, 9,9-dimethylfluorenyl, 9,9 -diphenylfluorenyl, 9,9'-spirobifluorenyl, dibenzofuranyl, or dibenzothiophenyl.

More specifically, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of, but are not limited thereto:

.

.

In this case, Ar ₁ and Ar ₂ may be the same as each other. Alternatively, Ar ₁ and Ar ₂ may be different.

Also, both Ar ₁ and Ar ₂ may not be phenyl.

In addition, R ₁ to R ₄ are each independently hydrogen or deuterium, or _{adjacent two of R 1} to R ₄ may combine with each other to form a benzene ring,

R ₅ to R ₈ may each independently be hydrogen or deuterium.

Alternatively, all of R ₁ to R ₈ may be hydrogen.

On the other hand, representative examples of the compound represented by Formula 1 are as follows:

.

Meanwhile, the compound represented by Formula 1 may be prepared by, for example, a preparation method as shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, X is halogen, preferably bromo, or chloro, and definitions of other substituents are as described above.

Specifically, the compound represented by Formula 1 is prepared by combining starting materials SM1 and SM2 through an amine substitution reaction. The amine substitution reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the reaction may be appropriately changed. In addition, the preparation method of the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(organic light emitting element)

Meanwhile, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers 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 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 injects and transports holes at the same time, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 The compounds shown 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 the cathode, one or more organic material layers and the 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 device 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 comprising 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 device 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, spraying, 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 preferable to facilitate hole injection into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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 anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is 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 with respect to 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, polyaniline and polythiophene-based conductive polymers, and the like, 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 probability of hole-electron coupling by increasing the efficiency of the organic light emitting device 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 may be used, 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-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; 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, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type 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, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted derivative. 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 improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the hole-electron coupling probability layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, 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. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

The electron injection and transport layer may also be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and the electron injection material included in the electron injection layer is LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like may be used.

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 top emission type, a back emission type, or a double side emission type depending on the material used.

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 for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of Compound 1

Compound 9-(4''-chloro-[1,1':2',1''-terphenyl]-4'-yl)-9H-carbazole (5.96 g, 13.86 mmol) and compound a1 (6.27 g, 15.25 mmol) were completely dissolved in 280 mL of xylene, and NaOtBu (1.73 g, 18.02 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.24 g, 0.48 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 210 mL of ethyl acetate to prepare compound 1 (6.66 g, yield: 60%).

MS[M+H] ⁺ = 805

Preparation Example 2: Preparation of compound 2

Compound 9-(4''-chloro-[1,1':2',1''-terphenyl]-4'-yl)-9H-carbazole (6.22 g, 14.47 mmol) and compound a2 (6.54 g, 15.91 mmol) were completely dissolved in 240 mL of xylene, and NaOtBu (1.81 g, 18.80 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.15 g, 0.29 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 230 mL of ethyl acetate to prepare compound 2 (7.13 g, yield: 61%).

MS[M+H] ⁺ = 805

Preparation Example 3: Preparation of compound 3

Compound 9-(4''-chloro-[1,1':2',1''-terphenyl]-4'-yl)-9H-carbazole (6.53 g, 15.19 mmol) and compound a3 (7.05 g, 16.70 mmol) were completely dissolved in 230 mL of xylene, and NaOtBu (1.90 g, 19.74 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.16 g, 0.30 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from ethyl acetate 240 mL to prepare compound 3 (6.82 g, yield: 55%).

MS[M+H] ⁺ = 816

Preparation Example 4: Preparation of compound 4

Compound 9-(4''-chloro-[1,1':2',1''-terphenyl]-4'-yl)-9H-carbazole (8.13 g, 18.91 mmol), and compound a4 (8.78 g, 20.80 mmol) were completely dissolved in 230 mL of xylene, and NaOtBu (2.36 g, 15.43 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.19 g, 0.38 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 250 mL of ethyl acetate to prepare compound 4 (8.76 g, yield: 57%).

MS[M+H] ⁺ = 816

Preparation Example 5: Preparation of compound 5

Compound 9-(4''-chloro-[1,1':4',1''-terphenyl]-2'-yl)-9H-carbazole (6.28 g, 14.60 mmol) and compound a5 (7.52 g, 16.07 mmol) were completely dissolved in 260 mL of xylene, and NaOtBu (1.82 g, 18.99 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.15 g, 0.29 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 260 mL of ethyl acetate to prepare compound 5 (9.08 g, yield: 72%).

MS[M+H] ⁺ = 862

Preparation Example 6: Preparation of compound 6

Compound 9-(4''-chloro-[1,1':4',1''-terphenyl]-2'-yl)-9H-carbazole (9.03 g, 21.00 mmol) and compound a6 (9.89 g, 23.10 mmol) were completely dissolved in 240 mL of xylene, and NaOtBu (2.62 g, 27.30 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.21 g, 0.42 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 260 mL of ethyl acetate to prepare compound 6 (9.88 g, yield: 57%).

MS[M+H] ⁺ = 822

Preparation Example 7: Preparation of compound 7

Compound 9-(4''-chloro-[1,1':4',1''-terphenyl]-2'-yl)-9H-carbazole (8.37 g, 19.47 mmol) and compound 7 (8.78 g, 21.41 mmol) were completely dissolved in 230 mL of xylene, and NaOtBu (2.43 g, 25.30 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.20 g, 0.39 mmol) was added, followed by heating and stirring for 5 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 7 (10.70 g, yield: 68%).

MS[M+H] ⁺ = 804

Preparation 8: Preparation of compound 8

Compound 9-(4''-chloro-[1,1':4',1''-terphenyl]-2'-yl)-9H-carbazole (7.77 g, 18.07 mmol) and compound a8 (9.66 g, 19.88 mmol) were completely dissolved in 250 mL of xylene, and NaOtBu (2.26 g, 23.49 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.18 g, 0.36 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 230 mL of ethyl acetate to prepare compound 8 (8.27 g, yield: 52%).

MS[M+H] ⁺ = 880

Preparation Example 9: Preparation of compound 9

Compound 9-(4'-chloro-6-(naphthalen-1-yl)-[1,1'-biphenyl]-3-yl)-9H-carbazole (9.34 g) in a 500 mL round bottom flask under nitrogen atmosphere , 21.72 mmol), and compound a9 (9.53 g, 23.89 mmol) were completely dissolved in 230 mL of xylene, and then NaOtBu (2.71 g, 28.24 mmol) was added thereto, and bis (tri-tert-butylphosphine) palladium (0) (0.22 g, 0.43 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 250 mL of tetrahydrofuran to prepare compound 9 (9.92 g, yield: 58%).

MS[M+H] ⁺ = 689

Preparation 10: Preparation of compound 10

Compound 9-(4'-chloro-6-(naphthalen-2-yl)-[1,1'-biphenyl]-3-yl)-9H-carbazole (8.76 g) in a 500 mL round bottom flask under nitrogen atmosphere , 20.37 mmol), and compound a10 (8.94 g, 22.41 mmol) were completely dissolved in 230 mL of xylene, and NaOtBu (2.55 g, 26.48 mmol) was added thereto, and bis (tri-tert-butylphosphine) palladium (0) (0.21 g, 0.41 mmol) was added, followed by heating and stirring for 4 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 tetrahydrofuran to prepare compound 10 (11.05 g, yield: 68%).

MS[M+H] ⁺ = 763

Preparation Example 11: Preparation of compound 11

Compound 9-(4''-chloro-[1,1':4',1''-terphenyl]-2'-yl)-9H-carbazole (5.78 g, 14.34 mmol) and compound a11 (7.44 g, 16.49 mmol) were completely dissolved in 250 mL of xylene, and NaOtBu (2.55 g, 26.48 mmol) was added thereto, followed by bis (tri-tert-butylphosphine) palladium (0) ( 0.21 g, 0.41 mmol) was added, followed by heating and stirring for 5 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 11 (9.16 g, yield: 51%).

MS[M+H] ⁺ = 878

Preparation 12: Preparation of compound 12

Compound 9-(4'-chloro-6-(phenanthren-9-yl)-[1,1'-biphenyl]-3-yl)-9H-carbazole (8.11) in a 500 mL round bottom flask under nitrogen atmosphere g, 15.30 mmol), and compound a12 (13.73 g, 16.83 mmol) were completely dissolved in 240 mL of xylene, and NaOtBu (1.91 g, 19.89 mmol) was added thereto, followed by bis(tri-tert-butylphosphine) palladium (0). ) (0.16 g, 0.31 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and recrystallized from 260 mL of ethyl acetate to prepare compound 12 (7.87 g, yield: 59%).

MS[M+H] ⁺ = 816

Example 1-1

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, dried, and then 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 a compound of the following compound HI1 and a compound of the following compound HI2 to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on the prepared anode, ITO transparent electrode. A hole transport layer was formed by vacuum-depositing a compound (1150 Å) represented by the following formula HT1 on the hole injection layer. Then, the compound 1 prepared in Preparation Example 1 was vacuum-deposited to a film thickness of 50 Å on the hole transport layer to form an electron blocking layer.

Then, the compound represented by the following Chemical Formula BH and the compound represented by the following Chemical 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 a compound represented by the following Chemical Formula HB1 to a film thickness of 50 Å on the light emitting layer. Then, on the hole blocking layer, the compound represented by the formula ET1 and the compound represented by the formula LiQ were vacuum-deposited in a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 310 Å.

A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

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

Examples 1-2 to Examples 1-12

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

Comparative Examples 1-1 to 1-4

An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1 prepared in Preparation Example 1. The compounds of EB1, EB2, EB3 and EB4 used in Comparative Examples of Table 1 are as follows.

Experimental Example 1

When a current was applied to the organic light emitting diodes prepared in Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and 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
(electron suppression layer) Voltage
(V
@10mA/cm ² ) efficiency
(cd/A
@10mA/cm ² ) color coordinates
(x,y) T95
(hr) Example 1-1 compound 1 4.42 6.71 (0.145, 0.045) 265 Example 1-2 compound 2 4.54 6.63 (0.144, 0.044) 250 Examples 1-3 compound 3 4.56 6.66 (0.146, 0.045) 255 Examples 1-4 compound 4 4.57 6.77 (0.145, 0.044) 260 Examples 1-5 compound 5 4.48 6.68 (0.144, 0.044) 265 Examples 1-6 compound 6 4.45 6.71 (0.146, 0.045) 275 Examples 1-7 compound 7 4.69 6.55 (0.145, 0.044) 240 Examples 1-8 compound 8 4.61 6.55 (0.146, 0.045) 255 Examples 1-9 compound 9 4.62 6.51 (0.145, 0.046) 260 Examples 1-10 compound 10 4.59 6.62 (0.146, 0.045) 240 Examples 1-11 compound 11 4.60 6.52 (0.145, 0.046) 250 Examples 1-12 compound 12 4.63 6.57 (0.146, 0.044) 235 Comparative Example 1-1 EB1 5.14 5.90 (0.145, 0.046) 135 Comparative Example 1-2 EB2 4.83 6.24 (0.146, 0.044) 180 Comparative Example 1-3 EB3 4.94 6.14 (0.145, 0.045) 175 Comparative Example 1-4 EB4 5.36 5.47 (0.144, 0.046) 50

As shown in Table 1, the organic light emitting device using the compound of the present invention as the electron suppression layer exhibited excellent characteristics in terms of efficiency, driving voltage and stability of the organic light emitting device.

Specifically, an organic compound having an aryl group at the 4th or 6th carbon of the 1,1'-biphenyl-3,4'-diyl linker connecting (N atom of carbazole) and (amino group) is employed The light emitting device is a compound EB1 having no aryl group in the 1,1'-biphenyl-3,4'-diyl linker connecting (N atom of carbazole) and (amino group), and an aryl group at carbon 5 of the linker. Compared to the organic light emitting devices of Comparative Examples 1-1, 1-2 and 1-3, each employing compound EB2 having an aryl group at carbon 2 of the linker and compound EB3 having an aryl group at the 2nd carbon of the linker, excellent characteristics in terms of driving voltage, efficiency and lifespan indicated.

In addition, the organic light emitting device of the above embodiment, the drive voltage is significantly longer than the organic light emitting device of Comparative Examples 1-4 employing the compound EB4 in which the aryl group substituted in the linker is substituted with a heteroaryl group such as a carbazolyl group is lower than that of the organic light emitting device. characteristics were shown.

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 (10)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
one of Ar is C _6-60 aryl, the other is hydrogen; heavy hydrogen; or C _6-60 aryl,
Here, when Ar is C _6-60 aryl, Ar may be unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-60} alkyl and C _{6-60 aryl,}
L ₁ and L ₂ are each independently, a single bond; substituted or unsubstituted C _6-60 arylene; _{or C 2-60} heteroarylene containing one or more heteroatoms among substituted or unsubstituted N, O and S;
Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;
R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; or substituted or unsubstituted C _6-60 aryl, or _{adjacent two of R 1} to R ₄ and adjacent two of R ₅ to R ₈ are bonded to each other to form a C _6-60 aromatic ring or N, O and S _{A C 2-60} heteroaromatic ring including any one or more heteroatoms selected from the group consisting of may be formed.
According to claim 1,
One of Ar is unsubstituted or _{C 6-60} aryl substituted with one or more substituents selected from the group consisting of _{C 1-10} alkyl and C _6-20 aryl, and the other is hydrogen or deuterium;
compound.
According to claim 1,
The compound is represented by the following formula 1-1 or 1-2,
compound:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
Ar is _{C 6-60} aryl unsubstituted or substituted with 1 or 2 substituents selected from the group consisting of _{C 1-10} alkyl and C _{6-20 aryl;}
L ₁ , L ₂ , Ar ₁ , Ar _{2 ,} and R ₁ to R ₈ are as defined in claim 1 .
4. The method of claim 3,
Ar is phenyl, biphenylyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenylfluorenyl;
compound.
According to claim 1,
L ₁ and L ₂ are each independently, a single bond, or any one selected from the group consisting of
compound:

.
According to claim 1,
Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, 9,9'-spirobifluorenyl, di benzofuranyl, or dibenzothiophenyl;
wherein Ar ₁ and Ar ₂ are unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl and C _{6-20 aryl,}
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of
compound:

.
According to claim 1,
R ₁ to R ₄ are each independently hydrogen or deuterium, or _{adjacent two of R 1} to R ₄ may combine with each other to form a benzene ring,
R ₅ to R ₈ are each independently hydrogen or deuterium,
compound.
According to claim 1,
The compound is any one selected from the group consisting of the following compounds:

.
a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 9 which is an organic light emitting device.

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