KR102444279B1 - 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.

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 using 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 layer is often formed of a multi-layered 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, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, 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 It lights up when it falls back to the ground state.

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

Korean Patent Publication No. 10-2013-073537

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,

R ₁ is each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring;

R ₂ and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring,

R ₄ and R ₅ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may be bonded to each other with a substituent to form a ring,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 including one or more heteroatoms selected from the group consisting of N, O and S heteroaryl, provided that at least one of Ar ₁ and Ar ₂ is substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or substituted or unsubstituted carbazolyl,

m is an integer from 0 to 9,

n and o are each independently an integer of 0 to 3.

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 of the present invention.

The compound represented by Chemical Formula 1 described above may be used as a material for the organic 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 Formula 1 described above may be used as a material for the electron blocking layer.

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

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile 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 aryl phosphine 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 a heterocyclic group containing one or more, or substituted or unsubstituted, in which two or more substituents of 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, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably from 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 a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.

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, 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 anthracenyl 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, the heterocyclic group is a heterocyclic group including 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 the heterocyclic group 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, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example 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, the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the above-described alkenyl groups. 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 heterocyclic group 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 of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

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

[Formula 1]

In Formula 1,

R ₁ is each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring;

R ₂ and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring,

R ₄ and R ₅ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may be bonded to each other with a substituent to form a ring,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 including one or more heteroatoms selected from the group consisting of N, O and S heteroaryl, provided that at least one of Ar ₁ and Ar ₂ is substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, or substituted or unsubstituted carbazolyl,

m is an integer from 0 to 9,

n and o are each independently an integer of 0 to 3.

Preferably, the compound represented by Formula 1 may be any one selected from compounds represented by Formulas 2 to 10:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 2 to 10,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Ar ₁ , Ar ₂ , m, n and o are as defined above.

Preferably, each R ₁ may independently be hydrogen.

Preferably, R ₂ and R ₃ may each independently be hydrogen.

Preferably, R ₄ and R ₅ may each independently be methyl or phenyl.

Preferably, Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of, provided that at least one of Ar ₁ and Ar ₂ is dibenzofuranyl, dibenzothiophenyl, carbazolyl or 9 -phenyl-9H-carbazolyl:

In the above formula, a may be an integer of 0 to 5.

Preferably, m may be an integer of 0 to 4, and more preferably 0 or 1.

Preferably, n and o may each independently be 0 or 1.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:

.

.

The compound represented by Formula 1 may be prepared through the following Schemes a-1 and a-2.

[Scheme a-1]

[Scheme a-2]

In Schemes a-1 and a-2, definitions other than X ₁ and X ₂ are the same as defined above, and X ₁ and X ₂ are each independently halogen, preferably bromo or chloro. Scheme a-1 is a Suzuki coupling reaction, in which an intermediate compound is synthesized by reacting it with a palladium catalyst in the presence of a base.

Next, Scheme a-2 is an amine substitution reaction, which is a reaction for preparing a compound represented by Formula 1 of the present application by reacting it with a palladium catalyst in the presence of a base. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). 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. do.

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, an electron suppression layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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

In addition, the organic layer may include an electron blocking layer, and the electron blocking layer includes the compound represented by Formula 1 above.

In addition, the organic layer may include an emission layer, and the emission layer includes the compound represented by Formula 1 above.

In addition, the organic layer may include an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the electron transport layer, the electron injection layer, or a layer that simultaneously transports and injects electrons is represented by the above formula The compound represented by 1 is included.

In addition, the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer and a light emitting layer, and any one or more selected from the group consisting of the hole injection layer, the hole transport layer and the electron blocking layer is a compound represented by Formula 1 may include

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

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

2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron suppression layer (7), light emitting layer (3), electron transport layer (8), electron injection layer (9) and an example of an organic light emitting device including a cathode 4 . In such a structure, the compound represented by Formula 1 may be included in at least one of the hole injection layer, the hole transport layer, the electron suppression layer, the light emitting layer, the electron transport layer, and the electron injection 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 as 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 the above 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; 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 multi-layered 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 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 preferred. 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. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. A material with high hole mobility. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The electron blocking layer is a layer placed between the hole transport layer and the emission layer in order to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the emission layer, and is also called an electron blocking layer. A material having a lower electron affinity than the electron transport layer is preferable for the electron suppressing layer.

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 emission layer may include a host material and a dopant material. The host material includes 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. 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 electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising 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, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals 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. However, 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 intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Preparation of intermediate compounds

(1) Preparation of intermediate compound A-1

[Scheme A-1]

Compounds a-1 (38.94g, 158.29mmol) and b-1 (60.0g, 150.75mmol) were completely dissolved in 400ml of tetrahydrofuran in a 1000ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (200ml) was added, Tetrakis-(triphenylphosphine)palladium (5.23g, 4.52mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 480 ml of ethyl acetate to prepare Compound A-1 (51.78 g, 69%).

MS[M+H] ⁺ = 473

(2) Preparation of intermediate compound A-2

[Scheme A-2]

In the synthesis of the intermediate compound A-1, the intermediate compound A-2 was synthesized in the same manner except that the b-2 compound was used instead of the b-1 compound.

MS[M+H] ⁺ = 473

(3) Preparation of intermediate compound A-3

[Scheme A-3]

In the synthesis of the intermediate compound A-1, the intermediate compound A-3 was synthesized in the same manner except that the a-2 compound was used instead of the a-1 compound.

MS[M+H] ⁺ = 473

(4) Preparation of intermediate compound A-4

[Scheme A-4]

In the synthesis of the intermediate compound A-1, the intermediate compound A-4 was synthesized in the same manner except that the a-2 compound was used instead of the a-1 compound and the b-2 compound was used instead of the b-1 compound.

MS[M+H] ⁺ = 473

(5) Preparation of intermediate compound A-5

[Scheme A-5]

In the synthesis of the intermediate compound A-1, the intermediate compound A-5 was synthesized in the same manner except that the b-3 compound was used instead of the b-1 compound.

MS[M+H] ⁺ = 597

(6) Preparation of intermediate compound A-6

[Scheme A-6]

In the synthesis of the intermediate compound A-1, the intermediate compound A-6 was synthesized in the same manner except that the a-2 compound was used instead of the a-1 compound and the b-3 compound was used instead of the b-1 compound.

MS[M+H] ⁺ = 597

Example Preparation of compounds

(1) Example 1: Preparation of compound 1

[Scheme 1]

Compound A-1 (9.12 g, 19.32 mmol) and compound a1 (6.80 g, 20.29 mmol) were completely dissolved in 250 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.79 g, 28.97 mmol) was added and , Bis(tri- tert -butylphosphine) palladium(0)(0.20 g, 0.39 mmol) was added, and the mixture was heated and stirred 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 210 mL of ethyl acetate to prepare Compound 1 (10.37 g, yield: 74%).

MS[M+H] ⁺ = 728

(2) Example 2: Preparation of compound 2

[Scheme 2]

Compound A-1 (8.77 g, 18.58 mmol) and compound a2 (6.85 g, 19.51 mmol) were completely dissolved in 220 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.68 g, 27.87 mmol) was added thereto. , Bis(tri- tert -butylphosphine) palladium(0)(0.19 g, 0.37 mmol) was added, and the mixture was heated and stirred for 3 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 2 (8.93 g, yield: 65%).

MS[M+H] ⁺ = 816

(3) Example 3: Preparation of compound 3

[Scheme 3]

After completely dissolving compound A-2 (7.11 g, 15.06 mmol) and compound a3 (6.18 g, 15.82 mmol) in 240 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, NaOtBu (2.17 g, 22.60 mmol) was added and , Bis(tri- tert -butylphosphine) palladium(0) (0.15 g, 0.30 mmol) was added, and the mixture was heated and stirred 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 270 mL of acetate to prepare Compound 3 (6.82 g, yield: 58%).

MS[M+H] ⁺ = 784

(4) Example 4: Preparation of compound 4

[Scheme 4]

Compound A-2 (6.82 g, 14.45 mmol) and compound a4 (5.69 g, 15.17 mmol) were completely dissolved in 260 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.08 g, 21.67 mmol) was added thereto. , Bis(tri- tert -butylphosphine) palladium(0)(0.15 g, 0.29 mmol) was added, and the mixture was heated and stirred for 6 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 4 (5.59 g, yield: 50%).

MS[M+H] ⁺ = 768

(5) Example 5: Preparation of compound 5

[Scheme 5]

Compound A-3 (7.45 g, 15.78 mmol) and compound a5 (5.55 g, 16.57 mmol) were completely dissolved in 260 mL of Xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (2.28 g, 23.68 mmol) was added thereto. , Bis(tri- tert -butylphosphine) palladium(0) (0.16 g, 0.32 mmol) was added, and the mixture was heated and stirred for 6 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 5 (6.77 g, yield: 59%).

MS[M+H] ⁺ = 728

(6) Example 6: Preparation of compound 6

[Scheme 6]

Compound A-4 (6.78 g, 14.36 mmol) and compound a6 (6.05 g, 15.08 mmol) were completely dissolved in 280 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.07 g, 21.55 mmol) was added thereto. , Bis(tri- tert -butylphosphine) palladium(0)(0.15 g, 0.29 mmol) was added, and the mixture was heated and stirred 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 210 mL of ethyl acetate to prepare compound 6 (7.21 g, yield: 63%).

MS[M+H] ⁺ = 764

(7) Example 7: Preparation of compound 7

[Scheme 7]

After completely dissolving compound A-5 (10.23 g, 17.16 mmol) and compound a7 (4.67 g, 18.02 mmol) in 220 mL of Xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, NaOtBu (2.47 g, 25.75 mmol) was added, and , Bis(tri- tert -butylphosphine) palladium(0)(0.18 g, 0.34 mmol) was added, and the mixture was heated and stirred 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 280 mL of ethyl acetate to prepare compound 7 (8.92 g, yield: 67%).

MS[M+H] ⁺ = 776

(8) Example 8: Preparation of compound 8

[Scheme 8]

Compound A-6 (9.56 g, 16.04 mmol) and compound a8 (5.47 g, 16.84 mmol) were completely dissolved in 250 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.31 g, 24.06 mmol) was added and , Bis(tri- tert -butylphosphine) palladium(0) (0.16 g, 0.32 mmol) was added, and the mixture was heated and stirred 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 ethyl acetate 240 mL to prepare compound 8 (9.11 g, yield: 67%).

MS[M+H] ⁺ = 842

Experimental example

(1) Experimental 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 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 of 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 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 at 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 the 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.

(2) Experimental Examples 2 to 8

In Experimental Example 1, an organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of the compound of Example 1.

(2) Comparative Experimental Examples 1 and 2

In Experimental Example 1, an organic light emitting diode was manufactured in the same manner as in Experimental Example, except that the compound shown in Table 1 was used instead of the compound of Example 1. The compounds of EB2 and EB3 used in Table 1 are as follows.

division compound
(electron suppression layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) color coordinates
(x,y) T95
(hr) Experimental Example 1 Example 1 4.55 6.35 (0.144, 0.046) 230 Experimental Example 2 Example 2 4.53 6.35 (0.144, 0.045) 235 Experimental Example 3 Example 3 4.48 6.46 (0.144, 0.047) 240 Experimental Example 4 Example 4 4.41 6.47 (0.146, 0.046) 240 Experimental Example 5 Example 5 4.66 6.28 (0.143, 0.045) 255 Experimental Example 6 Example 6 4.66 6.27 (0.144, 0.046) 230 Experimental Example 7 Example 7 4.69 6.27 (0.145, 0.045) 235 Experimental Example 8 Example 8 4.68 6.24 (0.144, 0.046) 245 Comparative Experimental Example 1 EB2 5.43 5.63 (0.144, 0.046) 105 Comparative Experimental Example 2 EB3 5.61 5.21 (0.145, 0.045) 130

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

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: electron transport layer
9: electron injection layer

Claims (11)

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

In Formula 1,
R ₁ is each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring;
R ₂ and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring,
R ₄ and R ₅ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may be bonded to each other with a substituent to form a ring,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 including one or more heteroatoms selected from the group consisting of N, O and S heteroaryl, provided that at least one of Ar ₁ and Ar ₂ is dibenzofuranyl, dibenzothiophenyl, carbazolyl or 9-phenyl-9H-carbazolyl,
m is an integer from 0 to 9,
n and o are each independently an integer of 0 to 3.
The method of claim 1,
The compound represented by Formula 1 is any one selected from compounds represented by the following Formulas 2 to 10, the compound:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 2 to 10,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Ar ₁ , Ar ₂ , m, n and o are as defined in claim 1.
The method of claim 1,
R ₁ is each independently hydrogen.
The method of claim 1,
R ₂ and R ₃ are each independently hydrogen.
The method of claim 1,
R ₄ and R ₅ are each independently methyl or phenyl.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of, provided that at least one of Ar ₁ and Ar ₂ is dibenzofuranyl, dibenzothiophenyl, carbazolyl or 9-phenyl-9H -carbazolyl, compounds:

In the above formula, a is an integer from 0 to 5.
The method of claim 1,
m is an integer from 0 to 4.
The method of claim 1,
n and o are each independently 0 or 1.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
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.
11. The method of claim 10,
The organic material layer is an electron suppression layer, an organic light emitting device.

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