KR102654810B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same}

The present invention relates to novel compounds and organic light-emitting devices containing them.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

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

Meanwhile, recently, in order to reduce process costs, organic light-emitting devices have been developed using a solution process, especially an inkjet process, instead of the existing deposition process. In the early days, attempts were made to develop organic light emitting devices by coating all organic light emitting device layers using a solution process, but there are limitations to the current technology, so only HIL, HTL, and EML in the form of a fixed structure were performed using a solution process, and the subsequent processes were carried out using the existing deposition process. A hybrid process utilizing is being studied.

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to novel compounds and organic light-emitting devices containing them.

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

[Formula 1]

In Formula 1,

Ar ₁ is substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L is 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 Formulas 2 to 4,

Ar ₂ to Ar ₅ are each independently substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Q is a functional group that can be crosslinked by heat or light,

n1 and n2 are each integers from 1 to 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 the compound represented by Formula 1.

The compound represented by Formula 1 described above can be used as a material for the organic layer of an organic light-emitting device, can also be used in a solution process, and can improve efficiency, low driving voltage, and/or lifespan characteristics in an organic light-emitting device. there is.

Figure 1 shows an example of an organic light emitting device consisting 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), and a cathode (7). It is shown.
Figure 2 shows 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, the present invention will be described in more detail to aid understanding.

In this specification, and means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; 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 of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound with 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-chain, or ring-chain 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 carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited to this.

In the present specification, the boron group specifically includes trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, and phenyl boron group, but is not limited thereto.

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain (linear) or branched (branched), and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, etc., but are not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, Examples include, but are not limited to, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, It can be etc. However, it is not limited to this.

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a heteroelement, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, phenothiazinyl group, and dibenzofuranyl group, but are not limited to these.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above. In this specification, the aralkyl group, alkylaryl group, and alkylamine group are the same as the examples of the alkyl group described above. In the present specification, the description regarding heteroaryl described above may be applied to heteroaryl among heteroarylamines. In this specification, the alkenyl group among the aralkenyl groups is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above can be applied, except that arylene is a divalent group. In the present specification, the description of heteroaryl described above can be applied, except that heteroarylene is a divalent group. In the present specification, the description of the aryl group or cycloalkyl group described above can be applied, except that the hydrocarbon ring is not monovalent and is formed by combining two substituents. In the present specification, the description of heteroaryl described above can be applied, except that the heterocycle is not monovalent and is formed by combining two substituents.

Meanwhile, the present invention provides a fluorene amine compound represented by Formula 1, wherein the 9th position is substituted with a 1,2-dihydrocyclobutabenzen-4-yl group and an alkenyl group.

Previously, materials used in vacuum deposition processes had a problem in that they had very low solubility in solvents or had high solubility only in specific solvents, making them difficult to use in solution processes. In addition, when forming a thin film using them, there has been a problem that the performance of the organic light-emitting device deteriorates as the solvent resistance is low and interlayer materials are mixed by dissolving in the solvent used to form the upper layer.

However, as will be described in detail below, the compound according to the present invention can be substituted with a specific substituent to form a stable thin film that is completely cured by heat treatment or UV treatment, making it possible to implement an organic light-emitting device showing high efficiency and long lifespan.

(compound)

The compound of the present invention is represented by the above formula (1) and contains both a terminal double bond and a 1,2-dihydrocyclobutabenzen-4-yl functional group that can be crosslinked by heat or light, and thus has excellent resistance to solvents. At the same time, they have high solubility, so they can be used in the solution process when manufacturing organic light-emitting devices.

Preferably, in Formula 1, L is unsubstituted C _6-20 arylene, 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 that can be crosslinked by heat or light, and refers to a reactive substituent that can crosslink between compounds when exposed to heat and/or light. At this time, crosslinking may be created by connecting radicals generated when carbon-carbon multiple bonds or cyclic structures are decomposed by heat treatment or light irradiation.

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.

Additionally, 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 Formulas 1-1 to 1-3,

Descriptions of L, Ar ₁ to Ar ₅ , Q, n1 and n2 are the same as those described in Formula 1 above.

이다.Preferably, in Formula 1-2, Q is

am.

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.

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

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

[Scheme 1]

In Scheme 1, the description of each substituent is as defined in Formula 1 above. In Scheme 1, step 1-1 involves reacting 3-bromobicyclo[4.2.0]octa-1,3,5-triene and 2-bromo-9H-fluorene-9-one under a strong base to produce a compound. This is a reaction to prepare A1, and step 1-2 is a reaction to prepare compound A2 by introducing a hydrogen group into the compound A1. In addition, steps 1-3 are a reaction for preparing compound A3 into which an alkenyl group is introduced by reacting compound A2 with compound B1 in the presence of a base. Next, steps 1-4 are a reaction to prepare compound 1 by reacting compound A3 with compound B2 under a palladium catalyst. The manufacturing method may be further detailed in the manufacturing examples described later.

(Coating composition)

Meanwhile, the compound according to the present invention can form an organic layer, especially a hole transport region, of an organic light-emitting device through 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 the hole injection layer or the hole transport layer. For this purpose, the present invention provides a coating composition containing the compound represented by the above-described formula (1) and a solvent.

The solvent is not particularly limited as long as it is capable of dissolving or dispersing the compound according to the present invention, and examples include 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 solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyhydric acids such as 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. alcohol and its derivatives; Alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; and amide-based solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; Benzoate-based solvents such as butyl benzoate and methyl-2-methoxybenzoate; tetralin; Solvents such as 3-phenoxytoluene can be mentioned. In addition, the above-mentioned solvents may be used individually or two or more types of solvents may be mixed.

Additionally, the viscosity of the coating composition is preferably 1 cP to 10 cP, and coating is easy within this 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%.

Additionally, the present invention provides a method of forming a hole transport region using the above-described coating composition. Specifically, coating the above-described coating composition according to the present invention on the anode by a solution process; and heat treating or light irradiating the coated coating composition.

The solution process uses the coating composition according to the present invention described above, and includes spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

The hole transport region formed by the above-described method has a stable thin film structure because the 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 dissolving or being morphologically affected and decomposed by the solvent used. Accordingly, it is possible to form a plurality of layers through a solution process, and the stability of the formed layers can be increased, thereby improving the lifespan characteristics of the manufactured organic light-emitting device.

(Organic light emitting device)

Additionally, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention provides 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 the compound represented by 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, and the hole injection layer and/or The hole transport layer includes the compound represented by Formula 1 above.

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

Figure 1 shows an example of an organic light emitting device consisting 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), and a cathode (7). It is shown. In this structure, the compound represented by Formula 1 may be included in the hole injection layer and/or the hole transport layer, and in this case, the electron transport layer may function as an electron injection and transport layer.

Figure 2 shows 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 this structure, the compound represented by 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 manufactured using materials and methods known in the art, except that the hole transport region contains the compound according to the present invention and is manufactured according to the method described above.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited to this.

In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited to this.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode 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); Combinations of metals and oxides 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 are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic 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 are multi-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. Specifically, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. As such a hole injection material, a compound represented by the above-mentioned formula (1) can be used, or commonly used metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrilehexaazatriphenylene-based organic material, and quinar. Quinacridone-based organic materials, perylene-based organic materials, anthraquinone, and polyaniline- and polythiophene-based conductive compounds can be used, but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and has high mobility for holes. The material is suitable. As the hole transport material, a compound represented by Formula 1 may be used, or a commonly used arylamine-based organic material, a conductive compound, and a block copolymer having both a conjugated and a non-conjugated portion may be used. It is not limited to this.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with 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-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

The light emitting layer may include a host material and a dopant material as described above. As a host material, a condensed aromatic ring derivative or a heterocyclic ring-containing compound can be further used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer. The electron transport material is a material that can easily receive electrons from the cathode and transfer them to the light-emitting layer, and is a material with high electron mobility. Suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., 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 conventional materials with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light-emitting layer or a light-emitting material, and hole injection of excitons generated in the light-emitting layer. A compound that prevents movement 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, etc. and their derivatives, metals. Complex compounds and nitrogen-containing five-membered ring derivatives are included, but are not limited thereto.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

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

Additionally, the compound represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

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

Manufacturing example 1: Preparation of Compound 1

1) Preparation of intermediate 1-1

3-bromobicyclo[4.2.0]octa-1,3,5-triene] (7.77 g, 1.1 eq) was added to the flask with THF. After dissolving in 180 mL and stirring at -78°C, n-BuLi (2.5 M Solu., 18.6 mL, 1.2 eq) was added dropwise in N2 atmosphere and stirred for 30 minutes. 2-Bromo-9H-fluoren-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, extraction was performed three times using MC/H ₂ O. After drying and column purification, intermediate 1-1 was obtained, 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

After dissolving Intermediate 1-1 (13 g, 1 eq) in MC in a flask, Et ₃ SiH [triethylsilane] (6.24 g, 1.5 eq) was added dropwise and stirred for 5 minutes. CF ₃ COOH [trifluoroacetic acid] was added, the temperature was raised to room temperature, and the mixture was stirred overnight. After completion of the reaction, extraction was performed three times using MC/H ₂ O and column purification was performed 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 intermediates 1-3

Intermediate 1-2 (9.5 g, 1 eq) and TBAB [Tetrabutylammonium bromide] (0.88 g, 0.1 eq) were dissolved in toluene in a flask, followed by NaOH solution (16.4 g, 15 eq, in 33 ml H ₂ O) and bromopentene. (4.9 g, 1.2 eq) was added at 30-minute intervals and then refluxed overnight. The presence of reaction was confirmed by NMR, and the extract was extracted three times with EA/H ₂ O, dried, and column purified to obtain a yellow viscous substance, 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

Intermediate 1-3 (6.8 g, 2.2 eq), N,N'-diphenylbenzidine (2.5 g, 1 eq), and NaOt-Bu (2.63 g, 4 eq) were added to toluene in a flask, then Pd(t-Bu) ₃ P) ₂ (237 mg, 6 mol%) was added 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 and precipitated in ethanol. As a result of TLC, it was confirmed that intermediate 2-3 and N,N'-daphenylbenzidine were removed. . This was column-purified, concentrated, and precipitated 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. Compound 1 was confirmed through LC/MS.

MS: [M+H]+ = 1005.7.

Manufacturing example 2: Preparation of Compound 2

1) Preparation of intermediate 2-1

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

MS: [M+H]+ = 591.2.

2) Preparation of intermediate 2-2

CH ₃ PPh ₃ Br (21.3 g, 2 eq) and KOtBu (6.7 g, 2 eq) were dissolved in THF in a flask, and then stirred with ice-filled acetone in an atmosphere of -10 degrees Celsius for 20 minutes. Intermediate 2-1 (17.62 g, 1 eq) dissolved in THF was slowly added dropwise and the color change to red was observed. After 1 h of reaction, TLC changes were observed and extracted with MC and water. After passing it through a silica pad, it was recrystallized with MC/Hexane to obtain Intermediate 2-2 as a white solid, which was confirmed by LC-MS.

MS: [M+H]+ = 589.2.

3) Preparation of Compound 2

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 the temperature was raised to 80°C. After 30 minutes, NaOtBu (1.96 g, 1.5 eq) was added and the temperature was raised to 110°C. Afterwards, Pd(PtBu ₃ ) ₂ (347.3 mg, 0.05 eq) was added in portions to proceed with the reaction. After 20 minutes, it was confirmed by LC-MS that the starting material had disappeared and the reaction was terminated. After cooling, the cake obtained by precipitating in EtOH was dissolved in MC, extracted, and separated by column purification. Compound 2 was obtained by reprecipitation in EtOH, and the substance was confirmed by LC-MS.

MS: [M+H]+ = 923.7.

Manufacturing example 3: Preparation of Compound 3

1) Preparation of Intermediate 3-1

Intermediate 1-2 (9.5 g, 1 eq) and TBAB (0.88 g, 0.1 eq) prepared in Preparation Example 1 were dissolved in toluene in a flask, and NaOH solution (16.4 g, 15 eq, in 33 ml H ₂ O) was added. Bromoheptene (5.8 g, 1.2 eq) was added at 30-minute intervals and then refluxed overnight. The presence of reaction was confirmed by NMR, and the extract was extracted three times with EA/H ₂ O, dried, and column purified to obtain a yellow viscous substance, 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

Intermediate 3-1 (7.3 g, 2.2 eq), N,N'-diphenylbenzidine (2.5 g, 1 eq), and NaOt-Bu (2.63 g, 4 eq) were added to toluene to the flask, then Pd(t-Bu) ₃ P) ₂ (237 mg, 6 mol%) was added at 10-minute intervals and reacted at 85°C for 1 hour. After confirming the completion of the reaction by TLC, the reaction solution extracted with EA/H2O was concentrated and precipitated in ethanol. As a result of TLC, it was confirmed that intermediate 2-3 and N,N'-diphenylbenzidine were removed. This was purified by column, concentrated, and precipitated 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. Compound 3 was confirmed through LC/MS.

MS: [M+H]+ = 1061.7.

Manufacturing example 4: Preparation of Compound 4

Intermediate 2-2 (8 g, 1 eq) prepared in Preparation Example 2 and Intermediate 3-1 (6.33 g, 1.05 eq) prepared in Preparation Example 3 were dissolved in toluene in a flask, and the temperature was raised to 80°C. . After 30 minutes, NaOtBu (1.96 g, 1.5 eq) was added and the temperature was raised to 110°C. Afterwards, Pd(PtBu ₃ ) ₂ (347.3 mg, 0.05 eq) was added in portions to proceed with the reaction. After 20 minutes, it was confirmed by LC-MS that the starting material had disappeared and the reaction was terminated. After cooling, the cake obtained by precipitating in EtOH was dissolved in MC, extracted, and separated by column purification. Compound 4 was obtained by reprecipitation in EtOH, and the substance was confirmed by LC-MS.

MS: [M+H]+ = 951.8.

Example 1: Manufacturing of organic light emitting device

A glass substrate on which ITO (indium tin oxide) was deposited as a thin film to a thickness of 1500 Å was placed in distilled water with a detergent dissolved in it and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, the substrate was ultrasonic cleaned with solvents such as isopropyl alcohol and acetone for 30 minutes each, dried, and then transported to a glove box.

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

After transferring to the glove box, Compound 1 prepared in Preparation Example 1 was dissolved in a toluene solution at a concentration of 2 wt% to form a hole transport layer of 200 Å on the hole injection layer. The coating composition was cured on a hot plate for 30 minutes.

Next, the following host compound A and dopant compound B (8 wt%) were vacuum deposited on the hole transport layer to a thickness of 300 Å to form a light emitting layer. Compound C below was vacuum deposited on the light emitting layer to a thickness of 200 Å to form an electron injection and transport layer. A cathode was formed by depositing LiF to a thickness of 0.5 nm and aluminum to a thickness of 100 nm on the electron injection and transport layer.

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

Example 2

An organic light emitting device was manufactured in the same manner as Example 1, except that Compound 2 was used instead of Compound 1 in Example 1.

Example 3

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1 in Example 1.

Example 4

An organic light emitting device was manufactured in the same manner as Example 1, except that Compound 4 was used instead of Compound 1 in Example 1.

Comparative example One

An organic light emitting device was manufactured in the same manner as Example 1, except that Compound X below was used instead of Compound 1 in Example 1.

[Compound X]

Comparative example 2

An organic light-emitting device was manufactured in the same manner as Example 1, except that Compound Y below was used instead of Compound 1 in Example 1.

[Compound Y]

Experiment 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 2 were measured. The time (T90) to reach 90% of the initial luminance at a 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/ ^m2 ) 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 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 has higher driving voltage, current efficiency, luminance, and stability than the organic light-emitting device using Comparative Example Compounds X and Y as the hole transport material. It can be confirmed that it exhibits excellent characteristics 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 Formula 1:
[Formula 1]

In Formula 1,
Ar ₁ is unsubstituted C _6-20 aryl,
L is unsubstituted C _6-20 arylene,
A is represented by the following formula 3 or 4,
[Formula 3] [Formula 4]

In Formulas 3 and 4,
Ar ₄ and Ar ₅ are each independently unsubstituted C _6-20 aryl,
Q is a functional group that can be crosslinked by heat or light,
n1 and n2 are each integers from 1 to 8.
According to paragraph 1,
L is phenylene, or biphenyldiyl,
compound.
According to paragraph 1,
Ar ₁ , Ar ₄ and Ar ₅ are each independently phenyl or biphenylyl,
compound.
According to paragraph 1,
Q is any one selected from the group consisting of:
compound:

In the above,
T ₁ is hydrogen; or unsubstituted C _1-6 alkyl,
T ₂ to T ₄ are each independently unsubstituted C _1-6 alkyl.
According to paragraph 1,
n1 and n2 are each 3, 4, or 5;
compound.
According to paragraph 1,
The compound is represented by the following formula 1-2 or 1-3,
compound:
[Formula 1-2]

[Formula 1-3]

In Formulas 1-2 and 1-3,
The descriptions of L, Ar ₁ , Ar ₄ , Ar ₅ , Q, n1 and n2 are as defined in paragraph 1.
According to clause 6,
In Formula 1-2,
Q is

person,
compound.
According to clause 6,
In Formula 1-3,
Ar ₁ and Ar ₅ are identical to each other,
n1 and n2 are equal to each other,
compound.
According to paragraph 1,
The compound is any one selected from the group consisting of the following compounds,
compound:

.
anode; a cathode provided opposite the anode; a light emitting layer provided between the anode and the cathode; and an organic light-emitting device comprising 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. .