KR102064992B1 - Novel hetero ring 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 hetero ring compound and organic light emitting device comprising the same

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy 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, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. The organic 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, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₂ are hydrogen or connected to each other,

X ₁ to X ₃ are each independently N or CH, provided that at least one of X ₁ to X ₃ is N,

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

Ar ₃ is substituted or unsubstituted C _6-60 aryl; Carbazolyl; 9-phenylcarbazolyl; Dibenzofuranyl; Dibenzothiophenyl; Or a substituent represented by formula (2):

[Formula 2]

In Chemical Formula 2,

Y ₁ and Y ₂ are each independently N or CH, provided that at least one of Y ₁ and Y ₂ is N,

Z is O, or S,

Ar ₄ is substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C 2 _-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,

R is hydrogen; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C 2 _-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,

n is an integer of 1-4.

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 comprises a compound represented by Chemical Formula 1. do.

The compound represented by Chemical Formula 1 may be used as a material of the organic material layer of the organic light emitting diode, and may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. FIG.
FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, O and S atoms, or two or more substituents of the above-described substituents connected or substituted. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, 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 this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, 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, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, 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 chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. 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 is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. 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 one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. 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 are 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 aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, 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,

And so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil 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, isoxazolyl group, thiadia There may be a sleepy group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and 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 alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

In Chemical Formula 1, according to the bonding position, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-4:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,

X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ and Ar ₃ are as defined above.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylflu Orenyl, dibenzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl. More preferably, Ar ₁ and Ar ₂ are each independently phenyl or biphenylyl.

Preferably, Ar ₃ is phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenanthrenyl, anthracenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, 9 -Phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl.

Preferably, in Formula 2, Ar ₄ is phenyl, biphenylyl, naphthyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9-phenylcarba I'm sleepy. Also preferably, in Chemical Formula 2, R is hydrogen.

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

The compound represented by Chemical Formula 1 may be prepared by the same method as in Scheme 1 below.

Scheme 1

In Scheme 1, R ₁ , R ₂ , X ₁ to X ₃ , Ar ₁ , Ar ₂ , and Ar ₃ are as defined above, and X is halogen. Preferably, X is chloro.

Scheme 1 is a Suzuki coupling reaction, in which a compound represented by Chemical Formula 1-a and a compound represented by Chemical Formula 1-b are reacted in the presence of a palladium catalyst and a base to prepare a compound represented by Chemical Formula 1 to be. The manufacturing method may be more specific in the production examples to be described later.

The present invention also provides an organic light emitting device including the compound represented by Chemical Formula 1. In one embodiment, 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 comprises a compound represented by Chemical Formula 1. 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 multilayer 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 and the like as an organic layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic layer may include a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting a hole may be represented by Formula 1 above. It includes a compound represented.

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

In addition, the organic layer may include an electron transport layer, or an electron injection layer, the electron transport layer, or the electron injection layer comprises a compound represented by the formula (1).

In addition, the electron transport layer, the electron injection layer, or a layer for the electron transport and electron injection at the same time includes the compound represented by the formula (1).

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an 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 element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. In addition, 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 physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then, a material that may be used as a cathode may be deposited thereon. In addition to the above 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 layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., 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 on a substrate from a cathode material (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, the second electrode is an anode.

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals 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, and the like, but are not limited thereto.

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

The hole injection layer is a layer for injecting holes from the electrode, and has a capability of transporting holes to the hole injection material, and has a hole injection effect at the anode, an excellent hole injection effect to the light emitting layer or the light emitting material, and is produced in the light emitting layer The compound which prevents the excitons from moving to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. The hole transport layer is a material that can transport holes from an anode or a hole injection layer to a light emitting layer. This is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

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

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can 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 followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer for injecting electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from the cathode, an excellent electron injection effect to the light emitting layer or the light emitting material, and the hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, 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-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided 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.

Preparation of the compound represented by Chemical Formula 1 and an organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Production Example  One

In a 500 mL round bottom flask under nitrogen atmosphere, Compound A (7.68 g, 11.23 mmol), and Compound a1 (3.67 g, 10.70 mmol) were completely dissolved in 240 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (120 mL). Tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) was added thereto, followed by heating and stirring for 3 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 240 mL of ethyl acetate to prepare Preparation Example 1 (7.69 g, 83%).

MS [M + H] ⁺ = 865

Production Example  2

In a 500 mL round bottom flask in nitrogen atmosphere, Compound B (12.30 g, 16.20 mmol), and Compound a2 (4.12 g, 15.43 mmol) were completely dissolved in 220 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (110 mL). Tetrakis- (triphenylphosphine) palladium (0.53 g, 0.46 mmol) was added thereto, followed by heating and stirring for 2 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 320 mL of ethyl acetate to prepare Preparation Example 2 (10.08 g, 76%).

MS [M + H] ⁺ = 865

Production Example  3

In a 500 mL round bottom flask under nitrogen atmosphere, Compound C (10.57 g, 13.96 mmol), and Compound a2 (3.55 g, 13.30 mmol) were completely dissolved in 200 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (100 mL). Tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) was added thereto, followed by heating and stirring for 4 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 180 mL of tetrahydrofuran to prepare Preparation Example 3 (9.95 g, 87%).

MS [M + H] ⁺ = 863

Production Example  4

In a 500 mL round bottom flask in nitrogen atmosphere, Compound D (10.47 g, 15.02 mmol), and Compound a2 (3.82 g, 14.31 mmol) were completely dissolved in 260 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (130 mL). Tetrakis- (triphenylphosphine) palladium (0.50 g, 0.43 mmol) was added thereto, 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 280 mL of ethyl acetate to prepare Preparation Example 4 (8.44 g, 73%).

MS [M + H] ⁺ = 803

Production Example  5

In a 500 mL round bottom flask in nitrogen atmosphere, Compound E (12.23 g, 17.15 mmol), and Compound a2 (4.36 g, 16.33 mmol) were completely dissolved in 280 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (140 mL). Tetrakis- (triphenylphosphine) palladium (0.57 g, 0.49 mmol) was added and the mixture was heated and stirred for 3 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 250 mL of ethyl acetate to prepare Preparation Example 5 (10.27 g, 77%).

MS [M + H] ⁺ = 819

Production Example  6

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.05 g, 10.32 mmol), and Compound a3 (3.37 g, 9.83 mmol) were completely dissolved in 200 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (100 mL). Tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) was added thereto, followed by heating and stirring for 3 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 240 mL of ethyl acetate to prepare Preparation Example 6 (6.49 g, 81%).

MS [M + H] ⁺ = 865

Production Example  7

In a 500 mL round bottom flask under nitrogen atmosphere, Compound A (7.05 g, 10.32 mmol), and Compound a4 (3.37 g, 9.83 mmol) were completely dissolved in 200 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (100 mL). Tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) was added thereto, followed by heating and stirring for 3 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 240 mL of ethyl acetate to prepare Preparation Example 7 (6.49 g, 81%).

MS [M + H] ⁺ = 787

Production Example  8

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (9.00 g, 13.17 mmol), and Compound a5 (4.29 g, 12.54 mmol) were completely dissolved in 240 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (120 mL). Tetrakis- (triphenylphosphine) palladium (0.43 g, 0.38 mmol) was added thereto, followed by 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 240 mL of ethyl acetate to prepare Preparation Example 8 (7.77 g, 72%).

MS [M + H] ⁺ = 864

Production Example  9

In a 500 mL round bottom flask in nitrogen atmosphere, Compound F (11.26 g, 15.53 mmol), and Compound a2 (3.95 g, 14.79 mmol) were completely dissolved in 240 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (120 mL). Tetrakis- (triphenylphosphine) palladium (0.51 g, 0.44 mmol) was added thereto, followed by heating and stirring for 4 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 280 mL of ethyl acetate to prepare Preparation Example 9 (8.11 g, 66%).

MS [M + H] ⁺ = 831

Production Example  10

In a 500 mL round bottom flask in nitrogen atmosphere, Compound G (13.97 g, 18.36 mmol), and Compound a6 (4.65 g, 17.48 mmol) were completely dissolved in 220 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (110 mL). Tetrakis- (triphenylphosphine) palladium (0.61 g, 0.52 mmol) was added thereto, followed by heating and stirring for 2 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 250 mL of ethyl acetate to prepare Preparation Example 10 (10.9 6g, 72%).

MS [M + H] ⁺ = 866

Production Example  11

In a 500 mL round bottom flask in nitrogen atmosphere, Compound H (10.57 g, 13.96 mmol), and Compound a2 (3.55 g, 13.30 mmol) were completely dissolved in 200 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (100 mL). Tetrakis- (triphenylphosphine) palladium (0.37 g, 0.32 mmol) was added thereto, followed by heating and stirring for 4 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 180 mL of tetrahydrofuran to prepare Preparation 11 (8.96 g, 87%).

MS [M + H] ⁺ = 865

Production Example  12

In a 500 mL round bottom flask in nitrogen atmosphere, Compound I (10.47 g, 15.02 mmol), and Compound a2 (3.82 g, 14.31 mmol) were completely dissolved in 260 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (130 mL). Tetrakis- (triphenylphosphine) palladium (0.50 g, 0.43 mmol) was added thereto, 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 280 mL of ethyl acetate to prepare Preparation 12 (7.60 g, 65%).

MS [M + H] ⁺ = 821

Production Example  13

In a 500 mL round bottom flask in nitrogen atmosphere, Compound J (12.23 g, 17.15 mmol), and Compound a2 (4.36 g, 16.33 mmol) were completely dissolved in 280 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (140 mL). Tetrakis- (triphenylphosphine) palladium (0.57 g, 0.49 mmol) was added and the mixture was heated and stirred for 3 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 250 mL of ethyl acetate to prepare Preparation 13 (9.25 g, 69%).

MS [M + H] ⁺ = 805

Production Example  14

In a 500 mL round bottom flask in nitrogen atmosphere, Compound F (9.37 g, 12.92 mmol), and Compound a3 (4.22 g, 12.30 mmol) were completely dissolved in 240 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (120 mL). Tetrakis- (triphenylphosphine) palladium (0.43 g, 0.37 mmol) was added thereto, 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 220 mL of tetrahydrofuran to prepare Preparation 14 (9.15 g, 86%).

MS [M + H] ⁺ = 907

Production Example  15

In a 500 mL round bottom flask under nitrogen atmosphere, Compound K (11.07 g, 15.20 mmol), and Compound a2 (4.51 g, 16.89 mmol) were completely dissolved in 280 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (140 mL). Tetrakis- (triphenylphosphine) palladium (0.59 g, 0.51 mmol) was added thereto, followed by heating and stirring for 3 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 250 mL of ethyl acetate to prepare Preparation 15 (8.17 g, 55%).

MS [M + H] ⁺ = 882

Production Example  16

In a 500 mL round bottom flask in nitrogen atmosphere, Compound L (11.74 g, 15.78 mmol), and Compound a2 (4.68 g, 17.53 mmol) were completely dissolved in 280 mL of tetrahydrofuran, followed by adding 2M aqueous potassium carbonate solution (140 mL). Tetrakis- (triphenylphosphine) palladium (0.61 g, 0.53 mmol) was added thereto, followed by heating and stirring for 3 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 250 mL of ethyl acetate to prepare Preparation 16 (9.12 g, 58%).

MS [M + H] ⁺ = 899

Example  1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. was used as a detergent, and distilled water was filtered secondly as a filter of Millipore Co. as a distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The compound represented by the following formula HAT was thermally vacuum deposited to a thickness of 150 kPa on the prepared ITO transparent electrode to form a hole injection layer. A compound (1150 kV) represented by the following Chemical Formula HT1, which is a material for transporting holes, was vacuum deposited on the hole injection layer to form a hole transport layer. Subsequently, the electron blocking layer was formed by vacuum depositing a compound represented by the following formula EB1 with a film thickness of 100 kPa on the hole transport layer. Subsequently, on the electron blocking layer, a compound represented by the following formula BH and a compound represented by the following formula BD were deposited under vacuum at a weight ratio of 25: 1 to form a light emitting layer with a film thickness of 200 kPa. A hole blocking layer was formed by vacuum depositing a compound represented by the following formula HB1 with a film thickness of 50 kPa on the light emitting layer. Subsequently, the compound prepared in Preparation Example 1 and the compound represented by LiQ below were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 310 Å. Lithium fluoride (LiF) and aluminum were deposited on the electron injection and transport layer sequentially to a thickness of 12 Å to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 Å / sec, aluminum is 2 Å / sec, the vacuum degree during deposition is 2 × 10 ^An organic light-emitting device was manufactured by maintaining ⁻⁷ to 5 × 10 ⁻⁶ torr.

Example  1-2 to 1-12

The organic light emitting device was manufactured by the same method as Example 1-1, but using the compound shown in Table 1 below instead of the compound prepared in Preparation Example 1.

Comparative example  1-1 to 1-4

The organic light emitting device was manufactured by the same method as Example 1-1, but using the compound shown in Table 1 below instead of the compound prepared in Preparation Example 1. ET1, ET2, ET3, and ET4 used in Table 1 are as follows.

Experimental Example  One

When the current was applied to the organic light emitting diodes manufactured in Examples and Comparative Examples, voltage, efficiency, color coordinate, and lifetime were measured, and the results are shown in Table 1 below. T95 means the time it takes for the luminance to decrease to 95% from the initial luminance (1600 nit).

compound
(Electronic transport layer) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) T95
(hr) Example 1-1 Preparation Example 1 4.23 5.91 (0.140, 0.049) 290 Example 1-2 Preparation Example 4 4.34 5.86 (0.141, 0.046) 285 Example 1-3 Preparation Example 5 4.66 5.52 (0.141, 0.047) 255 Example 1-4 Preparation Example 6 4.37 5.82 (0.142, 0.042) 280 Example 1-5 Preparation Example 7 4.58 5.66 (0.141, 0.045) 250 Example 1-6 Preparation Example 8 4.39 5.89 (0.140, 0.045) 285 Example 1-7 Preparation Example 9 4.21 5.95 (0.142, 0.043) 280 Example 1-8 Preparation Example 12 4.35 5.83 (0.141, 0.050) 290 Example 1-9 Preparation Example 13 4.32 5.81 (0.141, 0.043) 295 Example 1-10 Preparation Example 14 4.51 5.61 (0.141, 0.044) 275 Example 1-11 Preparation Example 15 4.63 5.58 (0.141, 0.044) 310 Example 1-12 Preparation Example 16 4.62 5.59 (0.141, 0.044) 305 Comparative Example 1-1 ET 1 5.28 5.34 (0.141, 0.045) 220 Comparative Example 1-2 ET 2 4.85 5.12 (0.140, 0.043) 235 Comparative Example 1-3 ET 3 4.92 5.23 (0.141, 0.044) 225 Comparative Example 1-4 ET 4 4.73 5.04 (0.141, 0.046) 245

As shown in Table 1, in the case of the organic light emitting device manufactured by using the compound of the present invention as the electron transport layer, it can be seen that it shows excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device. fluorene-9,8-indoloacridine Asymmetrical compounds of the present invention in which an aryl group is linked to position 3 and an electron withdrawing substituent is connected to position 5 are symmetrical compounds of Comparative Examples 1-1 to 1-4 as electron transport layers It showed lower voltage and higher efficiency than the organic light emitting device manufactured by using. As shown in the results of Table 1, it was confirmed that the other compounds in the present invention is excellent in the electron transport ability can be applied to the organic light emitting device.

Comparative example  2-1

Prepared in the same manner as in Comparative Example 1-1, but instead of using BH and BD as a light emitting layer in a film thickness of 350Å vacuum compound of the formula represented by the formula GH1 and the compound represented by the following formula GD in a vacuum ratio of 20: 1 The light emitting layer was formed to manufacture an organic light emitting device.

Comparative example  2-2

The organic light emitting device was manufactured by the same method as Comparative Example 2-1, except for using the compound represented by the following formula GH2 instead of the compound represented by the formula GH1.

Example  2-1 to 2-13

The organic light emitting device was manufactured by the same method as Comparative Example 2-1, but using the compound shown in Table 2 below instead of the compound represented by Formula GH1.

Experimental Example  2

When current was applied to the organic light emitting diodes manufactured in Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 2 below. T95 means the time it takes for the luminance to decrease to 95% from the initial luminance (6000 nit).

compound
Green light emitting layer
Host) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) T95 (hr) Example 2-1 Preparation Example 1 3.75 126.01 (0.255, 0.718) 360 Example 2-2 Preparation Example 2 3.87 121.71 (0.254, 0.718) 355 Example 2-3 Preparation Example 4 3.86 121.63 (0.253, 0.717) 345 Example 2-4 Preparation Example 6 3.88 122.77 (0.256, 0.718) 340 Example 2-5 Preparation Example 7 3.84 123.55 (0.252, 0.717) 345 Example 2-6 Preparation Example 8 3.85 121.42 (0.255, 0.719) 335 Example 2-7 Preparation Example 9 3.84 121.91 (0.255, 0.708) 340 Example 2-8 Preparation Example 10 3.96 119.65 (0.256, 0.707) 330 Example 2-9 Preparation Example 11 3.98 119.81 (0.254, 0.706) 345 Example 2-10 Preparation Example 12 3.97 117.75 (0.255, 0.708) 325 Example 2-11 Preparation Example 13 3.91 116.55 (0.257, 0.695) 325 Example 2-12 Preparation Example 14 3.95 118.46 (0.255, 0.699) 315 Example 2-13 Preparation Example 15 4.95 118.68 (0.255, 0.697) 325 Comparative Example 2-1 GH1 4.12 106.46 (0.251, 0.715) 290 Comparative Example 2-2 GH2 4.28 98.45 (0.254, 0.702) 210

As shown in Table 2, the organic light emitting device manufactured by using the compound of the present invention as a green light emitting layer exhibits excellent characteristics in terms of efficiency, driving voltage, and / or stability of the organic light emitting device. fluorene-9,8-indoloacridine Asymmetric compounds of the present invention in which an aryl group is linked to position 3 and an electron withdrawing substituent is connected to position 5 are organic light emitting devices manufactured using the compound of Comparative Example as a host of the green light emitting layer. It has lower voltage and higher efficiency. As shown in the results of Table 2, it was confirmed that the other compounds in the present invention can be applied to the organic light emitting device excellent in the light emitting ability.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (9)

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

In Chemical Formula 1,
R ₁ and R ₂ are hydrogen or connected to each other,
X ₁ to X ₃ are each independently N or CH, provided that at least one of X ₁ to X ₃ is N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C 2 _-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
Ar ₃ is phenyl; Biphenylyl; Terphenylyl; Quarterphenylyl; Naphthyl; Phenanthrenyl; Anthracenyl; Triphenylenyl; Dimethyl fluorenyl; Diphenylfluorenyl; Carbazolyl; 9-phenylcarbazolyl; Dibenzofuranyl; Dibenzothiophenyl; Or a substituent represented by formula (2):
[Formula 2]

In Chemical Formula 2,
Y ₁ and Y ₂ are each independently N or CH, provided that at least one of Y ₁ and Y ₂ is N,
Z is O, or S,
Ar ₄ is substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C 2 _-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
R is hydrogen; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C 2 _-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
n is an integer of 1-4.
The method of claim 1,
Formula 1 is represented by any one of the following formula 1-1 to 1-4,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,
X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ and Ar ₃ are the same as defined in claim 1, respectively.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, di Benzofuranyl, carbazolyl, 9-phenylcarbazolyl, or dibenzothiophenyl,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently phenyl or biphenylyl,
compound.
delete The method of claim 1,
Ar ₄ is phenyl, biphenylyl, naphthyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9-phenylcarbazolyl,
compound.
The method of claim 1,
R is hydrogen,
compound.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

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 is any one of claims 1 to 4 and 6 to 8. An organic light emitting device comprising the compound according to one claim.

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