KR102079240B1 - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel heterocyclic compound and an organic light emitting device using the same.

Description

Novel hetero-cyclic 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, the organic light emitting phenomenon refers to a phenomenon that converts 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, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The 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. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of 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 two electrodes in the structure of the organic light emitting device, holes are injected at the anode and electrons are injected at the cathode, and excitons are formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

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

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano, nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Substituted or unsubstituted C _6-60 arylamine; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,

n and r are independently an integer from 0 to 8,

t and m are independently integers from 0 to 4.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. do.

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

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

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

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

And

Means a linkage to another substituent.

The term "substituted or unsubstituted" in this specification is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" 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 connected.

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

In the present specification, the oxygen of the ester group may be substituted with a straight chain, 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, the number of carbon atoms of the imide group is not particularly limited, but is preferably 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 is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron 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 straight chain or branched chain, and 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 are 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, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. 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, steelbenyl 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 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 is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a 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 combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it 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 heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol 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, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl 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, isooxazolyl group, tiadiia A sleepy group, a phenothiazinyl group and a dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described alkyl group. In the present specification, the description of the heteroaryl group among heteroarylamines may be applied. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. 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 heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and a description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

Preferably, the formula 1 may be a compound represented by the following 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,

L ₁ to L ₆ are each independently a direct bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene comprising any one or more hetero atoms selected from the group consisting of N, O, S and Si,

Ar ₁ to Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; C _2-60 heteroaryl including one or more of substituted or unsubstituted O, N, Si, and S, or Ar ₁ to Ar ₄ may combine with adjacent groups to form a condensed ring.

Preferably, Ar ₁ to Ar ₄ may be any one selected from the group consisting of each independently.

R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano, nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or C _2-60 heteroaryl including one or more of substituted or unsubstituted O, N, Si, and S.

Preferably, L ₁ to L ₆ may be any one selected from the group consisting of each independently.

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

The compound represented by Chemical Formula 1-1 may be prepared by, for example, a manufacturing method as shown in Reaction Scheme 1 below, and the compound represented by Chemical Formula 1-2 may be prepared by a manufacturing method as shown in Reaction Scheme 2 as an example. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, L ₁ , L ₂ , L ₃ , Ar ₁ and Ar ₂ are as defined in Chemical Formula 1.

The compound represented by Chemical Formula 1 may be prepared by appropriately replacing the starting material according to the structure of the compound to be prepared with reference to Reaction Schemes 1 and 2.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. 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, a hole control layer, a light emitting layer, an electron transport layer, an electron injection layer 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.

Further, the organic material layer may include a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and transport, or a hole control layer, and the hole injection layer, a hole transport layer, and a layer that simultaneously performs hole injection and transport, or The hole control layer includes a compound represented by Chemical Formula 1 above.

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

Further, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron transport and electron injection includes a compound represented by Chemical Formula 1.

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

Further, 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. Further, 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 the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

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

2 is composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a hole control layer (7), a light emitting layer (8), an electron transport layer (9) and a cathode (4) An example of an organic light emitting device is shown. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the hole control 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, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by Chemical 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 application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode 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.

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. 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), and indium zinc oxide (IZO); A combination of metal and oxide 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 negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in a light emitting layer A compound that prevents migration of the excited excitons to the electron injection layer or the electron injection material, and has excellent thin film formation ability 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 matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer by receiving holes, and is a material that can transport holes to the light emitting layer by receiving holes from the anode or the hole injection layer as a hole transport material and has a high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

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

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

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The electron transporting material 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 receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons This is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

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

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

Manufacturing example  One

Manufacturing example  1-1: Synthesis of A1

9-phenanthrenol (22g, 113.8mmol) and 2-bromofluorene (58.9g, 227.7mmol) were added to 1,2-dichlorobenzene (300ml), followed by methanesulphonic acid (10ml), The mixture was heated and stirred at 160 ° C. for 24 hours. After lowering the temperature to room temperature and terminating the reaction, the mixture was extracted with chloroform and water, and then column with tetrahydrofuran and ethyl acetate to prepare the compound A1 (48.7 g, yield 70%).

MS [M + H] ⁺ = 612.54

Manufacturing example  1-2: Synthesis of A2

Compound A2 was synthesized in the same manner as in the synthesis of A1, except that 3-bromofluorene was used instead of 2-bromofluorene.

MS [M + H] ⁺ = 612.54

Manufacturing example  1-3: Synthesis of A3

Compound A3 was synthesized by the same method except that 4-bromofluorene was used instead of 2-bromofluorene in the synthesis of A1.

MS [M + H] ⁺ = 612.54

Manufacturing example  1-4: Synthesis of A4

Compound A4 was prepared by synthesizing in the same manner except that 2,6-bromofluorene was used instead of 2-bromofluorene in the synthesis of A1.

MS [M + H] ⁺ = 691.43

Manufacturing example  1-5: Synthesis of A5

Compound A5 was synthesized in the same manner as in the synthesis of A1, except that 3-bromo-9-hydroxy-phenanthrene and fluorene were used instead of 9-phenanthrenol and 2-bromofluorene.

MS [M + H] ⁺ = 691.43

Manufacturing example  2

Manufacturing example  2-1: Synthesis of B1

A1 (20 g, 32.7 mmol) and 4-chlorophenylboronic acid (5.57 g, 34.3 mmol) were added to tetrahydrofuran (300 ml), followed by addition of a 2M potassium carbonate aqueous solution (150 ml), and tetrakistriphenyl-phos. After adding pinopalladium (793 mg, 2 mol%), the mixture was heated and stirred for 10 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate aqueous solution was removed to separate the layers. After removing the solvent, the white solid was recrystallized from ethyl acetate to prepare the compound B1 (19.8 g, yield 90%).

MS [M + H] ⁺ = 644.18

Manufacturing example  2-2: Synthesis of B2

B2 was synthesized by the same method except that A2 was used instead of A1 in the synthesis of B1.

MS [M + H] ⁺ = 644.18

Manufacturing example  2-3: Synthesis of B3

B3 was synthesized by the same method except that A3 was used instead of A1 in the synthesis of B1.

MS [M + H] ⁺ = 644.18

Manufacturing example  2-4: Synthesis of B4

In the synthesis of B1, A3 was synthesized by the same method except that A3 was used instead of A1 and 2-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid to prepare B4.

MS [M + H] ⁺ = 644.18

Manufacturing example  2-5: Synthesis of B5

B5 was prepared by synthesizing in the same manner except that (4'-chloro- [1,1'-biphenyl] -4-yl) boronic acid was used instead of 4-chlorophenylboronic acid in the synthesis of B1.

MS [M + H] ⁺ = 720.28

Manufacturing example  3

Manufacturing example  3-1: Synthesis of Compound 1

Xylene with A1 (15 g, 23.27 mmol), di ([1,1'-biphenyl] -4-yl) amine (7.63 g, 23.73 mmol), and sodium-t-butoxide (3.13 g, 32.58 mol) And stirred under heating, refluxed, and [bis (tri-t-butylphosphine)] palladium (238 mg. 2 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare compound 1 (16.25 g, 82%).

MS [M + H] ⁺ = 853.03

Manufacturing example  3-2: Synthesis of Compound 2

In the synthesis of Compound 1, 4- (dibenzo [b, d] furan-4-yl) -N-phenylaniline was used instead of di ([1,1'-biphenyl] -4-yl) amine. Was synthesized in the same manner to prepare compound 2.

MS [M + H] ⁺ = 867.03

Manufacturing example  3-3: Synthesis of Compound 3

In the synthesis of Compound 1, A2 is substituted for A1, and N-([1,1'-biphenyl] -4-yl)-[1, instead of di ([1,1'-biphenyl] -4-yl) amine. Compound 3 was synthesized by the same method except that 1'-biphenyl])-2-amine was used.

MS [M + H] ⁺ = 853.03

Manufacturing example  3-4: Synthesis of Compound 4

In the synthesis of Compound 1, Compound 3 was synthesized by the same method except that A3 was used instead of A1.

MS [M + H] ⁺ = 853.03

Manufacturing example  3-5: Synthesis of Compound 5

In the synthesis of Compound 1, A3 was used instead of A1, and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine was used instead of di ([1,1'-biphenyl] -4-yl) amine. Compound 5 was synthesized by the same method except for

MS [M + H] ⁺ = 826.02

Manufacturing example  3-6: Synthesis of Compound 6

Compound 1 was synthesized in the same manner as in Example 1, except that B1 was substituted for A1 and N-phenylnaphthalen-1-amine was used instead of di ([1,1'-biphenyl] -4-yl) amine. Was prepared

MS [M + H] ⁺ = 827.01

Manufacturing example  3-7: Synthesis of Compound 7

B1 instead of A1 in the synthesis of Compound 1, N-([1,1'-diphenyl] -4-yl) instead of di ([1,1'-biphenyl] -4-yl) amine) -9,9 -Compound 7 was synthesized by the same method except that dimethyl-9H-fluoren-2-amine was used.

MS [M + H] ⁺ = 969.21

Manufacturing example  3-8: Synthesis of Compound 8

In the synthesis of Compound 1, B2 was used instead of A1, and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine was used instead of di ([1,1'-biphenyl] -4-yl) amine. Compound 8 was synthesized by the same method except for

MS [M + H] ⁺ = 883.11

Manufacturing example  3-9: Synthesis of Compound 9

In the synthesis of Compound 1, B3 was used instead of A1, and N-phenyldibenzo [b, d] thiophen-2-amine was used instead of di ([1,1'-biphenyl] -4-yl) amine. Was synthesized in the same manner to prepare compound 9

MS [M + H] ⁺ = 883.09

Manufacturing example  3-10: Synthesis of Compound 10

In the synthesis of Compound 1, B4 was used instead of A1, and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine was used instead of di ([1,1'-biphenyl] -4-yl) amine. Compound 10 was synthesized by the same method except

MS [M + H] ⁺ = 883.11

Manufacturing example  3-11: Synthesis of Compound 11

In the synthesis of Compound 1, B5 was synthesized in the same manner except that A5 was used instead of A1, and diphenylamine was used instead of di ([1,1'-biphenyl] -4-yl) amine.

MS [M + H] ⁺ = 853.05

Manufacturing example  3-12: Synthesis of Compound 12

A1 (20g, 32.7mmol) and 4- (9H-carbazole-9-yl) phenyl) boronic acid (9.58g, 33.35mmol) were added to dioxane (300ml) followed by 2M potassium carbonate aqueous solution (150ml) Then, tetrakistriphenyl-phosphino palladium (756mg, 2mol%) was added, followed by heating and stirring for 10 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate aqueous solution was removed to separate the layers. After removal of the solvent, the white solid was recrystallized from tetrahydrofuran and ethyl acetate to prepare the compound 12 (18.75g, yield 85%).

MS [M + H] ⁺ = 674.82

Manufacturing example  3-13: Synthesis of Compound 13

Compound 13 was synthesized in the same manner as in the synthesis of Compound 12, except that dibenzo [b, d] furan-2ylboronic acid was used instead of 4- (9H-carbazol-9-yl) phenyl) boronic acid. Prepared

MS [M + H] ⁺ = 599.70

Manufacturing example  3-14: Synthesis of Compound 14

A4 (15g, 21.72mmol), 4- (tert-butyl) -N-phenylaniline (9.88g, 43.88mmol), sodium-t-butoxide (6.26g, 65.16mol) was added to xylene, heated and stirred. Reflux and add [bis (tri-t-butylphosphine)] palladium (333 mg. 3 mmol%). After the temperature was lowered to room temperature and the reaction was terminated, compound 14 (15.79 g, 75%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] ⁺ = 980.28

Manufacturing example  3-15: Synthesis of Compound 15

Compound 15 was synthesized in the same manner as in the synthesis of Compound 14, except that N-phenyl- [1,1'-biphenyl] -4-amine was used instead of 4- (tert-butyl) -N-phenylaniline. Prepared

MS [M + H] ⁺ = 1020.26

Manufacturing example  3-16: Synthesis of Compound 16

Compound 16 was synthesized in the same manner as in the synthesis of compound 14, except that N-phenyldibenzo [b, d] furan-4-amine was used instead of 4- (tert-butyl) -N-phenylaniline. .

MS [M + H] ⁺ = 1048.23

Manufacturing example  3-17: Synthesis of Compound 17

Compound A was synthesized in the same manner as in Example 14, except that A5 and N-phenyldibenzo [b, d] furan-4-amine were used instead of A4 and 4- (tert-butyl) -N-phenylaniline. 17 was prepared.

MS [M + H] ⁺ = 1048.23

Example  One

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was put in distilled water in which a dispersing agent was dissolved and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used, and distilled water was used by Millipore Co. Distilled water filtered secondarily was used as a filter of the product. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

On this prepared ITO transparent electrode, hexanitrile hexaazatriphenylene was thermally vacuum-deposited to a thickness of 500 Pa to form a hole injection layer. Compound 1 synthesized in Preparation Example 3-1, which is a material for transporting holes on the hole injection layer, is vacuum-deposited to a thickness of 900 Å to form a hole transport layer, and then vacuum deposition of the following HT2 on the hole transport layer to a thickness of 50 Å. To form a hole control layer. On the hole control layer, a host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Pa to form a light emitting layer. Thereafter, an E1 compound was vacuum deposited on the light emitting layer to a thickness of 300 Pa to form an electron transport layer. An organic light emitting device was manufactured by sequentially depositing 12 µm thick lithium fluoride (LiF) and 2,000 µm aluminum on the electron transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 1Å / sec, the lithium fluoride was 0.2Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7Å / sec.

Example  2, 3 and Comparative example  1 to 3

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 below was used instead of Compound 1 as the hole transport layer.

The currents (20mA / cm ² ) were applied to the organic light emitting devices manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 to measure voltage, efficiency, color coordinates, and lifetime, and the results are shown in Table 1 below.

Hole transport layer Voltage (V) Efficiency (Cd / A) Color coordinate (x, y) Life (T95, h) Example 1 Compound 1 3.78 6.22 (0.135, 0.138) 49.0 Example 2 Compound 2 3.59 6.12 (0.134, 0.137) 50.2 Example 3 Compound 5 3.66 5.99 (0.135, 0.138) 55.2 Comparative Example 1 HT1 4.02 5.12 (0.134, 0.138) 34.5 Comparative Example 2 HT3 4.05 5.28 (0.136, 0.139) 38.2 Comparative Example 3 HT4 4.08 5.22 (0.135, 0.138) 35.1

Example  4

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was put in distilled water in which a dispersing agent was dissolved and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used, and distilled water was used by Millipore Co. Distilled water filtered secondarily was used as a filter of the product. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

On this prepared ITO transparent electrode, hexanitrile hexaazatriphenylene was thermally vacuum-deposited to a thickness of 500 Pa to form a hole injection layer. The following HT1, a material for transporting holes on the hole injection layer, was vacuum-deposited to a thickness of 900 MPa to form a vertical hole transport layer, and then the compound 1 synthesized in Preparation Example 3-1 on the hole transport layer was vacuum-deposited to a thickness of 50 MPa. A hole control layer was formed. On the hole control layer, a host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Pa to form a light emitting layer. Thereafter, the following E1 compound was vacuum-deposited to a thickness of 300 MPa on the light emitting layer to form an electron transport layer. An organic light emitting device was manufactured by sequentially depositing lithium fluoride (LiF) having a thickness of 12 와 and aluminum having a thickness of 2,000 위에 on the electron transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 1Å / sec, the lithium fluoride was 0.2Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7Å / sec.

Example  5 to 16 and Comparative example  4 to 6

An organic light emitting device was manufactured in the same manner as in Example 4, except that the compound shown in Table 2 below was used instead of Compound 1 as the hole control layer.

By applying a current (20mA / cm ² ) to the organic light emitting devices manufactured in Examples 4 to 16 and Comparative Examples 4 to 6, voltage, efficiency, color coordinates, and lifetime were measured and the results are shown in Table 2 below.

Hole control layer Voltage (V) Efficiency (Cd / A) Color coordinate (x, y) Life (T95, h) Example 4 Compound 1 3.58 5.55 (0.135, 0.138) 49.0 Example 5 Compound 2 3.52 5.68 (0.134, 0.137) 50.2 Example 6 Compound 3 3.59 6.11 (0.135, 0.138) 55.2 Example 7 Compound 4 3.66 5.92 (0.134, 0.138) 51.2 Example 8 Compound 5 3.68 5.69 (0.136, 0.139) 48.9 Example 9 Compound 6 3.53 5.99 (0.135, 0.138) 48.5 Example 10 Compound 7 3.52 6.12 (0.133, 0.139) 49.1 Example 11 Compound 8 3.55 6.23 (0.135, 0.138) 50.2 Example 12 Compound 9 3.79 6.22 (0.134, 0.138) 50.1 Example 13 Compound 10 3.78 5.99 (0.136, 0.139) 55.0 Example 14 Compound 11 3.66 6.03 (0.136, 0.139) 53.5 Example 15 Compound 12 3.62 6.21 (0.136, 0.123) 43.2 Example 16 Compound 13 3.77 6.2 (0.136, 0.120) 44.5 Comparative Example 4 HT2 4.11 5.32 (0.135, 0.138) 34.8 Comparative Example 5 HT5 4.05 5.28 (0.133, 0.139) 40.2 Comparative Example 6 HT6 4.21 5.23 (0.135, 0.138) 39.5

According to Tables 1 and 2, the compound derivative of the formula according to the present invention may play a role of hole transport and hole control in an organic electronic device including an organic light emitting device, and the device according to the present invention has efficiency, driving voltage, and stability. It was confirmed that the exhibited excellent properties.

Example  17

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was put in distilled water in which a dispersing agent was dissolved and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used, and distilled water was used by Millipore Co. Distilled water filtered secondarily was used as a filter of the product. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

On this prepared ITO transparent electrode, hexanitrile hexaazatriphenylene was thermally vacuum-deposited to a thickness of 500 Pa to form a hole injection layer. As a material for transporting holes on the hole injection layer, HT1 below was vacuum-deposited at 900 MPa to form a hole transport layer, and then vacuum-deposited to a thickness of 50 Hz below HT2 on the hole transport layer to form a hole control layer. Thereafter, the compound 14 synthesized in Preparation Example 3-14 with host H1 and dopant on the hole control layer was vacuum-deposited at a ratio of 25: 1 and a thickness of 300 Pa to form a light emitting layer. The following E1 compound (300 Pa) was vacuum-deposited on the light emitting layer to form an electron transport layer. An organic light emitting device was manufactured by sequentially depositing 12 µm thick lithium fluoride (LiF) and 2,000 µm aluminum on the electron transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 1Å / sec, the lithium fluoride was 0.2Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7Å / sec.

Example  18 and 20 and Comparative example  7 to 9

An organic light-emitting device was manufactured in the same manner as in Example 17, except that the compound described in Table 3 below was used instead of the compound 14.

The current (20mA / cm ² ) was applied to the organic light emitting devices manufactured in Examples 17 to 20 and Comparative Examples 7 to 9 to measure voltage, efficiency, color coordinates, and lifetime, and the results are shown in Table 3 below.

Dopant Voltage (V) Efficiency (Cd / A) Color coordinate (x, y) Life (T95, h) Example 17 Compound 14 3.67 6.23 (0.135, 0.138) 51.5 Example 18 Compound 15 3.68 6.12 (0.133, 0.139) 50.5 Example 19 Compound 16 3.77 6.02 (0.135, 0.138) 52.1 Example 20 Compound 17 3.88 6.01 (0.134, 0.138) 49.8 Comparative Example 7 BD1 4.08 5.33 (0.136, 0.139) 35.9 Comparative Example 8 BD2 4.11 5.45 (0.136, 0.139) 34.8 Comparative Example 9 BD3 4.32 5.23 (0.136, 0.123) 41.2

According to Table 3, the compound derivative of the formula according to the present invention may serve as a blue dopant in organic electronic devices including organic light emitting devices, and the device according to the present invention has excellent properties in terms of efficiency, driving voltage, and stability. Was confirmed.

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

Claims (8)

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

In Chemical Formula 1,
R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 arylamine; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,
n, r, t and m are independently 0 or 1.
According to claim 1,
At least one of R ₁ to R ₄ is C _6-60 arylamine, compound.
According to claim 2,
Formula 1 is any one selected from compounds represented by the following Formulas 1-1 to 1-4, the compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,
L ₁ to L ₆ are each independently a direct bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene comprising any one or more hetero atoms selected from the group consisting of N, O, S and Si,
Ar ₁ to Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; C _2-60 heteroaryl containing one or more of substituted or unsubstituted O, N, Si and S, or Ar ₁ to Ar ₄ combine with adjacent groups to form a condensed ring.
According to claim 3,
Ar ₁ to Ar ₄ are Compounds, each independently selected from the group consisting of:

R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano, nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S.
According to claim 3,
L ₁ to L ₆ are each independently a direct bond or any one selected from the group consisting of:

According to claim 1,
Compound represented by Formula 1 is characterized in that any one selected from the group consisting of the following compounds, compounds:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 6. That is, an organic light emitting device.
The method of claim 7,
The organic material layer containing the compound is a hole injection layer; Hole transport layer; A layer for simultaneous hole injection and transport; Hole control layer; Or an organic light-emitting device, characterized in that the light-emitting layer.

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