KR20200048794A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The compound is represented by chemical formula 1.

Description

Novel compound and organic light emitting device comprising the same}

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

In general, the organic light emitting phenomenon refers to a phenomenon 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 a 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 composed 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 an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows.

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

Meanwhile, an organic light emitting device using a solution process, particularly an inkjet process, has been developed instead of a conventional deposition process to reduce process cost. In the early days, all organic light-emitting device layers were coated with a solution process to develop an organic light-emitting device, but there are limitations in current technology, so only HIL, HTL, and EML are used as a solution process in the form of a regular structure, and the subsequent process is an existing deposition process. A hybrid process that utilizes is being studied.

Accordingly, the present invention provides a material for a novel organic light-emitting device that can be used in an organic light-emitting device and can be used in a solution process at the same time.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

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

L is a substituted or unsubstituted C _6-60 arylene,

A is represented by any one of the following formulas 2 to 4,

[Formula 2] [Formula 3] [Formula 4]

In Chemical Formulas 2 to 4,

Ar ₂ to Ar ₅ are each independently, substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,

Q is a functional group capable of crosslinking by heat or light,

n1 and n2 are each an integer of 1-8.

In addition, the present invention is an anode; A cathode provided opposite the anode; A light emitting layer provided between the anode and the cathode; And a hole transport region provided between the anode and the light emitting layer, wherein the hole transport region includes a compound represented by Chemical Formula 1, and provides an organic light emitting device.

The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light emitting device, and may also be used in a solution process, and may improve efficiency, low driving voltage, and / or life characteristics in an organic light emitting device. have.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 It is shown.
2 is made of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 8 and a cathode 7 An example of an organic light emitting device is shown.

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

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Cyano 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; Ar 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 heteroaryl 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 this 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-butyl dimethyl 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 linear (linear) or branched (branched), 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 a straight chain or a branched chain, 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, styrenyl 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, phenanthrenyl 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, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as heterogeneous elements, and carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl 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, 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, isooxazolyl group, thiadiazolyl Group, phenothiazinyl group, 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, an arylamine group, and an arylsilyl 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 example of the alkyl group. In the present specification, the heteroarylamine of the heteroaryl may be applied to the description of the heteroaryl described above. 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 heteroaryl 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 the 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 above-described heteroaryl may be applied, except that two substituents are formed by bonding.

On the other hand, the present invention provides a fluorene amine compound represented by Chemical Formula 1, substituted with 1,2-dihydrocyclobutabenzene-4-yl group and alkenyl group at position 9.

Materials previously used in the vacuum deposition process, there is a problem that the solubility in a solvent is very low, or it is difficult to be used in a solution process because the solubility is high only in a specific solvent. In addition, when these thin films are formed, solvent resistance is low, and the interlayer materials are mixed in the solvent used for forming the upper layer, and thus the performance of the organic light emitting device has been deteriorated.

However, the compound according to the present invention can be replaced with a specific substituent as described in detail below to form a stable thin film that is completely cured by heat treatment or UV treatment, thereby enabling the implementation of an organic light emitting device exhibiting high efficiency and long life.

(compound)

The compound of the present invention is represented by the formula (1), and includes a 1,2-dihydrocyclobutabenzene-4-yl group, which is a functional group capable of crosslinking by heat or light, and a terminal double bond at the same time, and thus has excellent resistance to solvents. At the same time, it has a high solubility in them and can be used in a solution process when manufacturing an organic light emitting device.

Preferably, in Chemical Formula 1, L is unsubstituted C _6-20 arylene, and more preferably phenylene or biphenyldiyl. Most preferably, L is 1,4-phenylene, or biphenyl-4,4'-diyl.

Preferably, Ar ₁ to Ar ₅ are each independently unsubstituted C _6-20 aryl. More preferably, Ar ₁ to Ar ₅ are each independently phenyl or biphenylyl.

In addition, Q is a functional group capable of crosslinking by heat or light, and means a reactive substituent capable of crosslinking between compounds when exposed to heat and / or light. At this time, the cross-linking may be generated by heat-radiation or light irradiation, carbon-carbon multiple bonds, or radicals formed as the cyclic structure is decomposed and connected.

Preferably, Q is any one selected from the group consisting of:

In the above,

T ₁ is hydrogen; Or substituted or unsubstituted C _1-6 alkyl,

T ₂ to T ₄ are each independently substituted or unsubstituted C _1-6 alkyl.

Preferably, n1 and n2 are 3, 4, or 5, respectively.

In addition, the compound may be represented by any one of the following formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3,

The description of L, Ar ₁ to Ar ₅ , Q, n1 and n2 is as described in Chemical Formula 1.

이다.Preferably, in Formula 1-2, Q is

to be.

Preferably, in Formula 1-3, Ar ₁ and Ar ₅ are the same as each other, and n1 and n2 are the same as each other.

Examples of the compound represented by Formula 1 is any one selected from the group consisting of:

On the other hand, the compound represented by the formula (1) may be prepared by the same method as in Scheme 1, for example.

[Scheme 1]

In Reaction Scheme 1, description of each substituent is as defined in Chemical Formula 1. In Reaction Scheme 1, Step 1-1 is a compound by reacting 3-bromobicyclo [4.2.0] octa-1,3,5-triene with 2-bromo-9H-fluoren-9-one under a strong base. A1 is a reaction for preparing, and Step 1-2 is a reaction for preparing Compound A2 by introducing a hydrogen group to Compound A1. In addition, Step 1-3 is a reaction for preparing Compound A3 in which an alkenyl group is introduced by reacting Compound A2 with Compound B1 under a base. Next, steps 1-4 are reactions of preparing Compound 1 by reacting Compound A3 with Compound B2 under a palladium catalyst. The manufacturing method may be more specific in the manufacturing examples to be described later.

(Coating composition)

On the other hand, the compound according to the present invention can form an organic layer of an organic light emitting device, particularly a hole transport region, in a solution process. Specifically, the hole transport region includes a hole injection layer and a hole transport layer, and the compound represented by Formula 1 may be used as a material for a hole injection layer or a hole transport layer. To this end, the present invention provides a coating composition comprising a compound represented by Formula 1 and a solvent.

The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the compound according to the present invention, for example, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o -Chlorine-based solvents such as dichlorobenzene; Ether-based solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon-based solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalent values of ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Alcohols and derivatives thereof; Alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; Benzoate solvents such as butyl benzoate and methyl-2-methoxybenzoate; Tetralin; And solvents such as 3-phenoxytoluene. In addition, the above-described solvent may be used alone or in combination of two or more solvents.

In addition, the viscosity of the coating composition is preferably 1 cP to 10 cP, and the coating is easy in the above range. In addition, the concentration of the compound according to the present invention in the coating composition is preferably 0.1 wt / v% to 20 wt / v%.

In addition, the present invention provides a method of forming a hole transport region using the coating composition described above. Specifically, on the positive electrode, coating the coating composition according to the present invention described above by a solution process; And subjecting the coated coating composition to heat treatment or light irradiation.

The solution process refers to the use of the coating composition according to the present invention described above, which means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

In the heat treatment step, the heat treatment temperature is preferably 150 to 230 ° C. In addition, the heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon and nitrogen.

The hole transport region formed by the above-described method has a stable thin film structure because a plurality of compounds included in the coating composition can be completely cured after crosslinking through the heat treatment and light irradiation steps. Therefore, even if another layer is formed on the hole transport region through a solution process, it can be prevented from being dissolved by a solvent used or decomposed under morphological influence. Accordingly, it is possible to form a plurality of layers through a solution process, and the stability of the formed layers is increased, so that life characteristics of the manufactured organic light emitting device can be improved.

(Organic light emitting element)

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 an anode; A cathode provided opposite the anode; A light emitting layer provided between the anode and the cathode; And a hole transport region provided between the anode and the light emitting layer, wherein the hole transport region provides an organic light emitting device including the compound represented by Chemical Formula 1.

More specifically, the hole transport region includes a hole injection layer and a hole transport layer, the hole injection layer is located adjacent to the anode, the hole transport layer is located adjacent to the light emitting layer, the hole injection layer and / or The hole transport layer includes a compound represented by Chemical Formula 1 above.

Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) 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.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 It is shown. In such a structure, the compound represented by Formula 1 may be included in the hole injection layer and / or the hole transport layer, and the electron transport layer may serve as the electron injection and transport layer.

2 is made of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 8 and a cathode 7 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 the hole injection layer and / or the hole transport layer.

The organic light emitting device according to the present invention can be made of materials and methods known in the art, except that the hole transport region includes the compound according to the present invention and is prepared as described above.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode 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 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 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 usually a material having a large work function 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), and indium zinc oxide (IZO); Metal and oxide combinations such as ZnO: Al or SNO ₂ : Sb; Conductive compounds 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 layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, 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 generated in the light emitting layer. A compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred. Specifically, it is preferable that the high-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. As the hole injection material, a compound represented by Chemical Formula 1 is used, or a metal porphyrin, oligothiophene, arylamine-based organic substance, hexanitrile hexaazatriphenylene-based organic substance, or quina commonly used. A quinacridone-based organic material, a perylene-based organic material, anthraquinone and a polyaniline- and polythiophene-based conductive compound may be used, 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. As the hole transport material, the hole is transported from the anode or the hole injection layer to the hole and is transported to the light emitting layer. The material is suitable. As the hole transporting material, a compound represented by Chemical Formula 1 may be used, or an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion may be used. It is not limited to this.

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 as described above. As the host material, a condensed aromatic ring derivative or a heterocyclic compound or the like can be further used. 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 pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a 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. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport 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 Suitable. 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 according to the prior art. In particular, examples of suitable cathode materials are conventional materials 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, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes 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-naphtolato) 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  1: Preparation of compound 1

1) Preparation of Intermediate 1-1

3-Fromobicyclo [4.2.0] octa-1,3,5-triene [3-bromobicyclo [4.2.0] octa-1,3,5-triene] (7.77 g, 1.1 eq) is THF into the flask. After dissolving in 180 mL, the mixture was stirred at -78 ° C, n-BuLi (2.5 M Solu., 18.6 mL, 1.2 eq) was droppedwise in an N2 atmosphere, followed by stirring for 30 minutes. 2-bromo-9H-fluorene-9-one [2-bromo-9H-fluoren-9-one] (10 g, 1 eq) was added and stirred overnight at room temperature. After completion of the reaction with Dilute HCl, it was extracted 3 times using MC / H ₂ O. After drying, column purification gave intermediate 1-1, which was confirmed by NMR.

1H NMR (500 MHz, CDCl ₃ ) δ (ppm) 7.68 (d, 1H), 7.58 (d, 1H), 7.51 (dd, 1H), 7.42 (d, 1H), 7.39 (m, 1H), 7.29 ( m, 2H), 7.20 (d, 1H), 7.02 (s, 1H), 6.96 (d, 1H), 3.12 (d, 4H), 2.59 (s, 1H).

2) Preparation of Intermediate 1-2

The intermediate 1-1 (13 g, 1 eq) was dissolved in MC in a flask, and then Et ₃ SiH [triethylsilane] (6.24 g, 1.5 eq) was dropwise and stirred for 5 minutes. CF ₃ COOH [trifluoroacetic acid] was added, and the mixture was heated to room temperature and stirred overnight. After completion of the reaction, extraction was performed three times using MC / H ₂ O, followed by column purification to obtain Intermediate 1-2, which was confirmed by NMR.

1H NMR (500 MHz, CDCl ₃ ) δ (ppm) 7.80 (d, 1H), 7.69 (d, 1H), 7.51 (d, 1H), 7.42-7.38 (m, 2H), 7.29 (d, 1H), 6.98 (q, 2H), 6.65 (s, 1H), 5.02 (s, 1H), 3.13 (dd, 4H).

3) Preparation of Intermediate 1-3

Dissolve intermediate 1-2 (9.5 g, 1 eq) and TBAB [Tetrabutylammonium bromide] (0.88 g, 0.1 eq) in toluene in a NaOH solution (16.4 g, 15 eq, in 33 ml H ₂ O), bromopentene (4.9 g, 1.2 eq) was dropped every 30 minutes and refluxed overnight. After confirming the presence or absence of the reaction by NMR, the mixture was extracted three times with EA / H ₂ O and dried to purify the column to obtain a yellow viscous material, which was confirmed by NMR.

1H NMR (500 MHz, CDCl ₃ ) δ (ppm) 7.74 (d, 1H), 7.64 (d, 1H), 7.48 (d, 1H), 7.36-7.28 (m, 3H), 7.17 (d, 1H), 6.96 (d, 1H), 6.90 (d, 1H), 6.90 (s, 1H), 5.74-5.49 (m, 1H), 4.90-4.80 (m, 2H), 3.09 (s, 4H), 2.76-2.12 ( m, 2H), 1.93 (m, 2H), 0.82-0.73 (m, 2H)

4) Preparation of compound 1

In the flask, intermediate 1-3 (6.8 g, 2.2 eq), N, N'-diphenylbenzidine (2.5 g, 1 eq), NaOt-Bu (2.63 g, 4 eq) were added to toluene, and Pd (t-Bu) ₃ P) ₂ (237 mg, 6 mol%) was dropped at 10 minute intervals and reacted at 85 ° C for 1 hour. After confirming the completion of the reaction by thin layer chromatography (TLC), the reaction solution extracted with EA / H ₂ O was concentrated to precipitate in ethanol, and TLC confirmed that intermediate 2-3 and N, N'-polyphenylbenzidine were removed. . This column was purified and concentrated to precipitate again in ethanol, and the obtained solid was filtered by stirring in EA at 65 ° C. After dissolving the obtained solid in THF, it was finally precipitated again in ethanol to confirm Compound 1 through LC / MS.

MS: [M + H] + = 1005.7.

Manufacturing example  2: Preparation of compound 2

1) Preparation of Intermediate 2-1

4- (6-bromo-9-phenyl-9H-carbazol-3-yl) benzaldehyde (15 g, 1 eq) and 4- (6- (4-([1,1'-biphenyl]) in a flask -4-ylamino) phenyl) -9-phenyl-9H-carbazol-3-yl) benzaldehyde (13.62 g, 1.05 eq) was dissolved in 1,4-dioxane, and refluxed at 125 ° C to change the color yellow. It was observed. The 2M concentration of K ₂ CO ₃ aqueous solution was slowly dropwise and stirred for 10 minutes. Then, Pd (PtBu ₃ ) ₂ (536 mg, 0.03 eq) was poured to observe the color change to dark green. After 1 hour, when it was confirmed that the starting material disappeared by high performance liquid chromatography (HPLC), the already produced solid was filtered and washed with EA to remove the dark red color. The filtered material was extracted by dissolving in MC, and recrystallized with MC and EA to obtain a white solid intermediate 2-1 material, which was confirmed by LC-MS.

MS: [M + H] + = 591.2.

2) Preparation of Intermediate 2-2

After dissolving CH ₃ PPh ₃ Br (21.3 g, 2 eq) and KOtBu (6.7 g, 2 eq) in THF in a flask, the mixture was stirred for 20 minutes in an atmosphere of about 10 degrees below zero with acetone with ice. Intermediate 2-1 (17.62 g, 1 eq) dissolved in THF was slowly droppedwise to observe the color change to red. After 1h reaction, TLC change was observed and extracted with MC and water. After passing through the silica pad and recrystallized with MC / Hexane, an intermediate 2-2 material as a white solid was obtained, which was confirmed by LC-MS.

MS: [M + H] + = 589.2.

3) Preparation of compound 2

The intermediate 2-2 (8 g, 1 eq) and intermediate 1-3 (5.93 g, 1.05 eq) prepared in Preparation Example 1 were dissolved in toluene in a flask, and then heated to 80 ° C. After 30 minutes, NaOtBu (1.96 g, 1.5 eq) was added and heated to 110 ° C. Subsequently, Pd (PtBu ₃ ) ₂ (347.3 mg, 0.05 eq) was added in portions to react. After 20 minutes, the reaction was terminated after confirming that the starting material had disappeared by LC-MS. After cooling, the cake obtained by precipitating in EtOH was dissolved in MC, extracted, and purified by column separation. Compound 2 was obtained by reprecipitation in EtOH, and the material was identified by LC-MS.

MS: [M + H] + = 923.7.

Manufacturing example  3: Preparation of compound 3

1) Preparation of Intermediate 3-1

Dissolve the intermediate 1-2 (9.5 g, 1 eq) and TBAB (0.88 g, 0.1 eq) prepared in Preparation Example 1 in toluene in a flask and NaOH solution (16.4 g, 15 eq, in 33 ml H ₂ O), Bromoheptene (5.8 g, 1.2 eq) was dropped every 30 minutes and refluxed overnight. After confirming the presence or absence of the reaction by NMR, extraction was performed three times with EA / H ₂ O and dried to purify the column to obtain a yellow viscous material, which was confirmed by NMR.

1H NMR (500 MHz, CDCl ₃ ) δ (ppm) 7.75 (d, 1H), 7.65 (d, 1H), 7.49 (d, 1H), 7.36-7.29 (m, 3H), 7.17 (d, 1H), 6.95 (d, 1H), 6.91 (d, 1H), 6.89 (s, 1H), 5.74-5.48 (m, 1H), 4.90-4.80 (m, 2H), 3.10 (s, 4H), 2.46-2.01 ( m, 4H), 0.88-0.72 (m, 6H)

2) Preparation of compound 3

In the flask, intermediate 3-1 (7.3 g, 2.2 eq), N, N'-diphenylbenzidine (2.5 g, 1 eq), NaOt-Bu (2.63 g, 4 eq) were added to toluene, and then Pd (t-Bu) ₃ P) ₂ (237 mg, 6 mol%) was dropped every 10 minutes to react at 85 ° C for 1 hour. After confirming the completion of the reaction by TLC, the reaction solution extracted with EA / H2O was concentrated to precipitate in ethanol, and TLC confirmed that intermediate 2-3 and N, N'-diphenylbenzidine were removed. This column was purified and concentrated to precipitate again in ethanol, and the obtained solid was filtered by stirring in EA at 65 ° C. The obtained solid was dissolved in THF and precipitated again in ethanol to obtain the final product, and the compound 3 was identified by LC / MS.

MS: [M + H] + = 1061.7.

Manufacturing example  4: Preparation of compound 4

The intermediate 2-2 (8 g, 1 eq) prepared in Preparation Example 2 and the intermediate 3-1 (6.33 g, 1.05 eq) prepared in Preparation Example 3 were dissolved in toluene in a flask, and then heated to 80 ° C. . After 30 minutes, NaOtBu (1.96 g, 1.5 eq) was added and heated to 110 ° C. Subsequently, Pd (PtBu ₃ ) ₂ (347.3 mg, 0.05 eq) was added in portions to react. After 20 minutes, the reaction was terminated after confirming that the starting material had disappeared by LC-MS. After cooling, the cake obtained by precipitating in EtOH was dissolved in MC, extracted, and purified by column separation. Compound 4 was obtained by reprecipitation in EtOH, and the material was identified by LC-MS.

MS: [M + H] + = 951.8.

Example  1: Preparation of organic light emitting device

The glass substrate on which ITO (indium tin oxide) was thinned to a thickness of 1500 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. After washing the ITO for 30 minutes, the ultrasonic cleaning was repeated 10 times with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol and acetone for 30 minutes each, and after drying, the substrate was transferred to a glove box.

The PEDOT: PSS was spin-coated on the prepared ITO transparent electrode to form a hole injection layer having a thickness of 300 mm 3, and the coating composition was cured for 1 hour in a hot plate in air.

Then, after transferring to the glove box, the compound 1 prepared in Preparation Example 1 was dissolved in a toluene solution at a concentration of 2 wt% on the hole injection layer to form a hole transport layer at 200 Pa. This was allowed to cure the coating composition for 30 minutes on a hot plate.

Subsequently, the following host compound A and dopant compound B (8 wt%) were vacuum-deposited to a thickness of 300 MPa on the hole transport layer to form a light emitting layer. The following compound C was vacuum deposited to a thickness of 200 Pa on the light emitting layer to form an electron injection and transport layer. A cathode was formed by depositing aluminum with a thickness of 0.5 nm and aluminum with a thickness of 0.5 nm on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the LiF of the cathode was maintained at 0.3 Å / sec, and the deposition rate of 2 Å / sec for aluminum, and the vacuum degree during deposition was 2x10 ^-7 to 3x10. ^-5 torr was maintained.

Example  2

An organic light emitting diode was manufactured according to the same method as Example 1 except for using Compound 2 instead of Compound 1 in Example 1.

Example  3

An organic light emitting diode was manufactured according to the same method as Example 1 except for using Compound 3 instead of Compound 1 in Example 1.

Example  4

An organic light emitting diode was manufactured according to the same method as Example 1 except for using Compound 4 instead of Compound 1 in Example 1.

Comparative example  One

An organic light emitting diode was manufactured according to the same method as Example 1 except for using Compound X instead of Compound 1 in Example 1.

[Compound X]

Comparative example  2

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the following compound Y instead of compound 1 in Example 1.

[Compound Y]

Experimental Example : Evaluation of organic light emitting device characteristics

The driving voltage, current efficiency, quantum efficiency (QE) and luminance values of the organic light-emitting devices manufactured in Examples 1 to 4 and Comparative Examples 1 to 2 were measured at a current density of 10 mA / cm ² , and 10 mA / cm. ^The time (T90) of 90% of the initial luminance at the current density of ² was measured. The results are shown in Table 1 below.

device compound
(Hole transport
matter) Driving voltage (V) Current efficiency
(cd / A) QE
(%) Luminance
(Cd / m ² ) T90
(hr
@ 10mA / cm ² ) Example 1 Compound 1 4.86 6.22 7.62 621.53 78 Example 2 Compound 2 5.02 6.17 7.55 617.04 76 Example 3 Compound 3 5.07 6.15 7.50 614.87 70 Example 4 Compound 4 5.08 6.15 7.58 615.22 65 Comparative Example 1 Compound X 5.10 6.13 7.46 613.20 61 Comparative Example 2 Compound Y 5.24 5.89 7.33 588.68 45

As shown in Table 1, the organic light-emitting device using the compound of the present invention as a hole transport material, compared to the organic light-emitting device using Comparative Examples compounds X and Y as a hole transport material, driving voltage, current efficiency, brightness and stability It can be seen that it exhibits excellent properties in all aspects.

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

Claims (10)

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

In Chemical Formula 1,
Ar ₁ is substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
L is a substituted or unsubstituted C _6-60 arylene,
A is represented by any one of the following formulas 2 to 4,
[Formula 2] [Formula 3] [Formula 4]

In Chemical Formulas 2 to 4,
Ar ₂ to Ar ₅ are each independently, substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
Q is a functional group capable of crosslinking by heat or light,
n1 and n2 are each an integer of 1-8.
According to claim 1,
L is phenylene or biphenyldiyl,
compound.
According to claim 1,
Ar ₁ to Ar ₅ are each independently phenyl or biphenylyl,
compound.
According to claim 1,
Q is any one selected from the group consisting of:
compound:

In the above,
T ₁ is hydrogen; Or substituted or unsubstituted C _1-6 alkyl,
T ₂ to T ₄ are each independently substituted or unsubstituted C _1-6 alkyl.
According to claim 1,
n1 and n2 are 3, 4, or 5, respectively,
compound.
According to claim 1,
The compound is represented by any one of the following formulas 1-1 to 1-3,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3,
The description of L, Ar ₁ to Ar ₅ , Q, n1 and n2 is as defined in claim 1.
The method of claim 6,
In Chemical Formula 1-2,
Q is

sign,
compound.
The method of claim 6,
In Chemical Formula 1-3,
Ar ₁ and Ar ₅ are the same as each other,
n1 and n2 are the same as each other.
According to claim 1,
The compound is any one selected from the group consisting of the following compounds:

anode; A cathode provided opposite the anode; A light emitting layer provided between the anode and the cathode; And a hole transport region provided between the anode and the light emitting layer, wherein the hole transport region includes the compound according to any one of claims 1 to 9, .

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