KR102630727B1 - 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 according to the present invention can be used as a material for the organic layer of an organic electroluminescent device, and can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.

Description

Novel compounds and organic light-emitting devices using the same {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 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.

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.

Initially, attempts were made to develop organic light-emitting devices manufactured by applying a solution process to the formation of all organic light-emitting device layers, but current technology has limitations. Accordingly, the formation of the hole injection layer (HIL), hole transport layer (HTL), and light emitting layer (EML) in the form of a positive structure is carried out through a solution process, and the other layers are formed by applying the existing deposition process. Research is underway. Additionally, attempts are being made to apply a solution process to the formation of the electron transport layer (ETL).

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

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 applied to a solution process.

Korean Patent Publication No. 10-2000-0051826 (2000.08.16)

The present invention relates to a novel compound that can be used as an organic light-emitting material for solution processing and an organic light-emitting device containing the same.

According to the present invention, a compound represented by the following formula (1) is provided:

[Formula 1]

In Formula 1,

Ar ¹ and Ar ² are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, a C _6-30 aryloxy group, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; or a C _2-60 heteroaryl group containing one or more heteroatoms selected from the group consisting of N, O and S and substituted or unsubstituted with a C _6-30 aryl group,

R ¹ and R ² are each independently a substituted or unsubstituted C _1-30 alkyl group,

n and m are each independently integers from 1 to 4,

p and q are each independently integers of 1 or 2,

L ¹ to L ⁴ are each independently hydrogen; heavy hydrogen; C _1-30 alkyl group; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryloxy group period, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; Or it is a C _2-60 heteroaryl group that contains one or more heteroatoms selected from the group consisting of N, O, and S and is substituted or unsubstituted with a C _6-30 aryl group.

In addition, according to the present invention, an organic light emitting device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode; An organic light-emitting device is provided, wherein at least one of the organic layers includes a compound represented by Formula 1.

The compound represented by Formula 1 according to the present invention can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device. In particular, the compound represented by Formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

The compound according to the present invention contains an alkyl group and can exhibit excellent solubility in organic solvents. In addition, the compound according to the present invention has a structure in which a light emitting group is connected around spirofluorene, and thus can exhibit coating properties suitable for a solution process.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Figure 2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4. It is shown.
Figure 3 is a mass spectrum for Compound C-1 of Preparation Example 1.
Figure 4 is a mass spectrum for Compound B of Preparation Example 2.
Figure 5 is a mass spectrum for Compound D of Preparation Example 3.
Figure 6 is a mass spectrum for Compound E of Preparation Example 4.

Hereinafter, to facilitate understanding of the present invention, compounds according to embodiments of the invention and organic electroluminescent devices containing the same will be described in detail.

Unless explicitly stated herein, terminology is intended to refer only to specific embodiments and is not intended to limit the invention.

As used herein, singular forms include plural forms unless phrases clearly indicate the contrary.

As used herein, the meaning of "comprising" is to specify a specific characteristic, area, integer, step, operation, element, and/or component, and to specify another specific property, area, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of .

According to one embodiment of the invention, a compound represented by the following formula (1) is provided:

[Formula 1]

In Formula 1,

Ar ¹ and Ar ² are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, a C _6-30 aryloxy group, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; or a C _2-60 heteroaryl group containing one or more heteroatoms selected from the group consisting of N, O and S and substituted or unsubstituted with a C _6-30 aryl group,

R ¹ and R ² are each independently a substituted or unsubstituted C _1-30 alkyl group,

n and m are each independently integers from 1 to 4,

p and q are each independently integers of 1 or 2,

L ¹ to L ⁴ are each independently hydrogen; heavy hydrogen; C _1-30 alkyl group; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryloxy group period, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; Or it is a C _2-60 heteroaryl group that contains one or more heteroatoms selected from the group consisting of N, O, and S and is substituted or unsubstituted with a C _6-30 aryl group.

As a result of the present inventors' continued research, the compound represented by Formula 1 shows high solubility in various solvents and has properties suitable for manufacturing organic light-emitting devices through a solution process.

The solution process is a method that allows a layer containing organic light-emitting device materials to be formed in a desired location through inkjet printing, spin coating, etc. The solution process not only reduces the consumption of organic materials compared to the existing vacuum deposition process that vaporizes organic materials in a vacuum chamber, but also has the advantage of low facility investment costs and short process time.

Techniques such as inkjet printing and spin coating are typically used in this solution process. Therefore, the development of organic materials with high solubility in solvents suitable for the solution process is considered important.

However, existing organic materials for vacuum deposition have very low solubility in solvents or are soluble only in specific solvents, making them difficult to apply to solution processes.

The compound represented by Formula 1 has high solubility in solvents suitable for inkjet printing and spin coating, making it possible to manufacture organic light-emitting devices through a solution process.

The compound represented by Formula 1 has a high glass transition temperature (T _g ), making it possible to provide high thermal stability to organic light-emitting devices to which it is applied. In particular, the compound has a structure in which a phenylene group substituted with an alkyl group (R ¹ or R ² ) is connected to the left and right sides of a 9,9'-spirobifluorene group, respectively, and thus has low crystallinity. It can exhibit excellent solubility in organic solvents.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile 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 a heteroaryl group 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 alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. 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 this 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 30. 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 of alkenyl groups include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, and 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 this specification, an alkynyl group is a monovalent group obtained by removing 1 hydrogen atom from an alkyne having 2 to 30 carbon atoms or a derivative thereof.

In this specification, the aryl group is not particularly limited, but preferably has 6 to 50 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, biphenyl group, or terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

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

In the present specification, the heteroaryl group is an aryl group having 2 to 30 carbon atoms containing at least one heteroatom selected from the group consisting of N, O, and S as a heteroelement. Examples of heteroaryl groups 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, and 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia These include, but are not limited to, a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group.

In this specification, the above-described description of the aryl group can be applied, except that arylene is a divalent group. The description of the heteroaryl group described above can be applied, except that heteroarylene is a divalent group.

In Formula 1, Ar ¹ and Ar ² are each independently selected from deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C a C 6-50 aryl group substituted or unsubstituted with a _1-30 alkoxy group, a C _6-30 aryloxy group, or _a C _6-30 aryl group; Or it is a C _2-60 heteroaryl group that contains one or more heteroatoms selected from the group consisting of N, O, and S and is substituted or unsubstituted with a C _6-30 aryl group.

Preferably, Ar ¹ and Ar ² are each independently a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, benzofuranyl group, or It may be a fluorenyl group, etc. And, Ar ¹ and Ar ² are each independently substituted with methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, methoxy, ethoxy, propoxy, butoxy, isobutoxy, or neobutoxy. It may be substituted or unsubstituted.

In Formula 1, R ¹ and R ² are each independently a substituted or unsubstituted C _1-30 alkyl group.

As a non-limiting example, R ¹ and R ² are each independently 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- It may be propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc.

Preferably, R ¹ and R ² are each independently a substituted or unsubstituted C _1-10 alkyl group. More preferably, R ¹ and R ² are each independently a substituted or unsubstituted C _1-6 alkyl group.

In Formula 1, n and m are each independently integers of 1 to 4. Preferably, n and m are each 2.

In Formula 1, p and q are each independently integers of 1 or 2. Preferably, p and q are each 1. When p and q are each 2 or more, R ¹ or R ² in the phenylene group repeated two or more times may be the same or different from each other.

In Formula 1, L ¹ to L ⁴ are each independently hydrogen; heavy hydrogen; C _1-30 alkyl group; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryloxy group period, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; Or it is a C _2-60 heteroaryl group that contains one or more heteroatoms selected from the group consisting of N, O, and S and is substituted or unsubstituted with a C _6-30 aryl group.

Preferably, L ¹ to L ⁴ are each independently hydrogen or a C _1-30 alkyl group.

Preferably, the compound represented by Formula 1 may be any one compound selected from the group consisting of compounds with the following structural formula.

Meanwhile, the compound represented by Formula 1 can be prepared by a series of methods as shown in Schemes 1 to 3 below.

[Scheme 1]

[Scheme 2]

[Scheme 3]

In Schemes 1 to 3, Ar ¹ , Ar ² , R ¹ , R ² , L ¹ , L ² , L ³ , L ⁴ , n, m, p, and q are each defined in Formula 1 above.

The compound represented by Formula 1 can be prepared by reacting intermediate A according to Scheme 1 and intermediate B according to Scheme 2 as shown in Scheme 3.

As an example, the synthesis of the asymmetric compound represented by Formula 1 can be carried out through two Suzuki coupling syntheses in which intermediate A of different structures is coupled to both sides of intermediate B, respectively.

The method for producing the compound may be further detailed in the production examples described later.

Meanwhile, the compound represented by Formula 1 may be included in the organic material layer of the organic light-emitting device through a solution process. For this purpose, according to the present invention, a coating composition comprising a compound represented by Formula 1 and a solvent is provided.

The solvent is not particularly limited as long as it is capable of dissolving or dispersing the compound represented by Formula 1.

For example, the solvent includes chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-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 isoamyl benzoate, methyl benzoate, ethyl benzoate, butyl benzoate, and methyl-2-methoxybenzoate; tetralin; Solvents such as 3-phenoxy-toluene may be mentioned. In addition, the above-mentioned solvents may be used individually or two or more types of solvents may be mixed.

As a non-limiting example, the boiling point of the solvent may be 40 to 350 °C, preferably 80 to 330 °C.

As a non-limiting example, the viscosity of the single or mixed solvent may be 1 to 10 CP, preferably 3 to 8 CP.

As a non-limiting example, the concentration of the coating composition may be 0.1 to 20 wt/v%, preferably 0.5 to 10 wt/v%.

Meanwhile, according to another embodiment of the invention, an organic light-emitting device containing the compound represented by Formula 1 is provided.

For example, according to the present invention, an organic light-emitting device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode. ; An organic light-emitting device is provided, wherein at least one of the organic layers includes a compound represented by Formula 1.

The organic material layer of the organic electroluminescent device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked.

For example, the organic electroluminescent device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as organic layers. However, the structure of the organic electroluminescent device is not limited to this and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, the hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 Contains the indicated compounds.

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

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

Additionally, the electron transport layer, the electron injection layer, or the layer that simultaneously performs electron transport and electron injection includes the compound represented by Formula 1.

Additionally, the organic layer includes a light-emitting layer and an electron transport layer, and the light-emitting layer may include the compound represented by Formula 1.

Additionally, the organic electroluminescent device according to the present invention may be a normal type organic electroluminescent device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate.

Additionally, the organic electroluminescent device according to the present invention may be an inverted type organic electroluminescent device in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic electroluminescent device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

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

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

In the structure shown in FIG. 2, the compound represented by Formula 1 is one or more of the hole injection layer, hole transport layer, light emitting layer, and electron transport layer; Preferably, it may be included in the light emitting layer.

Meanwhile, the organic electroluminescent device according to the present invention can be manufactured using materials and methods known in the art, except that one or more of the organic layers includes the compound represented by Formula 1 above.

Additionally, when the organic electroluminescent device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic electroluminescent device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode 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 electroluminescent device can be made by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.

Additionally, the compound represented by Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic electroluminescent device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

Additionally, according to an embodiment of the invention, a method of forming a light-emitting layer using the above-described coating composition is provided.

Specifically, coating the light-emitting layer on the anode or on the hole transport layer formed on the anode by a solution process; and drying the coated coating composition.

The drying step may be performed in a nitrogen, argon atmosphere, or air, but is not limited thereto.

The drying step may be performed through heat treatment, and the heat treatment temperature is 85°C to 250°C, preferably 100°C to 150°C.

The heat treatment time of the heat treatment and drying step is 1 minute to 2 hours, preferably 1 minute to 30 minutes.

In addition to this method, an organic electroluminescent device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003/012890).

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 polymers 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, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

The hole injection material is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes and has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and is generated in the light-emitting layer. 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.

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.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrilehexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. There are conductive polymers of the series such as organic materials, anthraquinone, polyaniline, and polythiophene, 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. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable.

Specific examples of the hole transport material include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

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 of the light-emitting material include 8-hydroxy-quinoline aluminum complex (Alq3); 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. Host materials include condensed aromatic ring derivatives or heterocyclic ring-containing compounds.

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 material 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 has high mobility for electrons. This is suitable.

Specific examples of the electron transport material include Al complex of 8-hydroxyquinoline; Complex containing Alq3; 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 electron injection effect from the cathode, has an excellent electron injection effect to the light-emitting layer or light-emitting material, and injects holes 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.

Specific examples of the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, and anthrone. and their derivatives, metal complex compounds, and nitrogen-containing five-membered ring derivatives, etc., but are not limited thereto.

The metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and 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. , but is not limited to this.

The organic electroluminescent 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 applied to organic solar cells or organic transistors in addition to organic electroluminescent devices.

Below, preferred embodiments are presented to aid understanding of the invention. However, the following examples are only for illustrating the invention and do not limit the invention to these only.

Manufacturing example One

(Preparation of intermediate compound C-1)

(10-(Naphthalen-2-yl)anthracen-9-yl)boronic acid 7 g (20.10 mmol, 1.0 eq), 1,4-dibromo-2,5-dihexylbenzene 8.9 g (22.02 mmol, 1.1 eq), K ₂ Add 8.3 g (60.06 mmol, 3 eq) of CO ₃ and 0.93 g (0.80 mmol, 0.04 eq) of Pd(PPh ₃ ) ₄ into a 500 mL two-neck round-bottom flask and charge with nitrogen. Add 200 mL of THF and 45 mL of H ₂ O, stir, raise the temperature to 80°C, and react overnight. Extract with dichloromethane/H ₂ O, separate the organic layer, add MgSO ₄ and charcoal, stir for 30 minutes, and pass through a silica pad. The solvent of the filtrate was removed, and the intermediate compound C-1 (9.3 g, yield 74%) was obtained as a white solid by column purification using dichloromethane/hexane.

The mass spectrum for Compound C-1 of Preparation Example 1 is shown in Figure 3.

MS: [M+H] ⁺ =628.1

Manufacturing example 2

(Preparation of intermediate compound B)

2,2'-dibromo-9,9'-spirobi[fluorene] 10 g (21.09 mmol, 1.0 eq), 4,4,4',4',5,5,5',5'-octamethyl-2, Add 13.4 g (52.77 mmol, 2.5 eq) of 2'-bi(1,3,2-dioxaborolane) and 12.4 g (126.34 mmol, 6.0 eq) of KOAc to a 500 mL two-neck round-bottom flask and replace with nitrogen atmosphere. . Add 150 mL of dioxane and stir at 70°C for 30 minutes. Add 1.2 g (1.64 mmol, 0.08 eq) of catalyst PdCl ₂ (dppf) and react with stirring at 60°C overnight. The organic layer was separated by extraction with dichloromethane/H ₂ O, MgSO ₄ and charcoal were added, stirred for 30 minutes, and passed through a silica pad. The solvent of the filtrate was removed and recrystallized with ethyl alcohol to obtain the intermediate compound B (8.7 g, yield 73%).

The mass spectrum for Compound B of Preparation Example 2 is shown in Figure 4.

MS: [M+H] ⁺ =569.1

Manufacturing example 3

(Preparation of Compound D)

3.34 g (5.32 mmol, 2.2 eq) of the intermediate compound C-1 according to Preparation Example 1, 1.37 g (2.41 mmol, 1.0 eq) of the intermediate compound B according to Preparation Example 2, 0.27 g (0.23 g) of Pd(PPh ₃ ) ₄ mmol, 0.1 eq), and 2.0 g (14.47 mmol, 6.0 eq) of K ₂ CO3 were added to a 250 mL two-neck round-bottom flask and charged with nitrogen. Add 100 mL of toluene and 13 mL of H ₂ O, stir, raise the temperature to 110°C, and react overnight. Extracted with dichloromethane/H ₂ O, separated the organic layer, added MgSO ₄ and charcoal, stirred for 30 minutes, and passed through a silica pad. The solvent of the filtrate was removed and column purification was performed using dichloromethane/hexane to obtain Compound D (2.2 g, yield 65%) as a white solid.

The mass spectrum for Compound D of Preparation Example 3 is shown in Figure 5.

MS: [M+H] ⁺ =1411.0

Manufacturing example 4

(Preparation of Compound E)

Preparation Example 3 and Compound E was obtained in the same manner.

The mass spectrum for Compound E of Preparation Example 4 is shown in Figure 6.

MS: [M+H] ⁺ =1129.8

Manufacturing example 5

(Preparation of Compound F)

Instead of the intermediate compound A-1, the intermediate compound f-1 (9-(4-bromo-2,5-dimethylphenyl)-2,6-di-tert-butyl-10-(naphthalen-1-yl)anthracene) Compound F was obtained in the same manner as in Preparation Example 3, except that it was used.

MS: [M+H] ⁺ =1353.9

Test Example 1 (Solubility Experiment)

The compounds D to F and the following compound BH-1 were each added to toluene and stirred at 1500 rpm for 30 minutes at room temperature (25°C). Afterwards, a laser was passed through the solution to check whether a precipitate was formed through the Tyndall effect and the amount dissolved was measured, and the results are shown in Table 1 below.

solute Solubility (wt%) Example 1 Compound D 7 Example 2 Compound E 3 Example 3 Compound F 8 Comparative Example 1 Compound BH-1 < 1

Referring to Table 1, it can be seen that the compounds D to F each have significantly higher solubility in toluene than the compound BH-1.

Example 4 (Manufacture of organic light emitting device)

A glass substrate on which ITO (indium tin oxide) was deposited as a thin film to a thickness of 500 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent from Fisher Co. was used, and distilled water filtered secondarily through a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, the cleaned ITO glass substrate was prepared by ultrasonic cleaning with acetone, distilled water, and isopropyl alcohol solvent and drying.

A composition obtained by mixing the following compound Z-1 and the following compound Z-2 in a weight ratio of 8:2 was spin-coated on the ITO transparent electrode and cured at 220° C. for 30 minutes on a hot plate under a nitrogen atmosphere to form a 400 Å thick layer. A hole injection layer was formed.

On the hole injection layer, a composition containing the following compound Z-3 dissolved in toluene at a weight ratio of 1% was spin-coated and heat-treated on a hot plate at 200° C. for 30 minutes to form a hole transport layer with a thickness of 200 Å.

On the hole transport layer, a composition of Compound D according to Preparation Example 3 and Compound Z-4 below, dissolved in toluene at a weight ratio of 0.5% at a ratio of 94:6, was spin-coated to form a 200 Å-thick light-emitting layer, and then incubated under N ₂ atmosphere. The coating composition was dried on a hot plate at 120°C for 10 minutes.

Afterwards, it was transferred to a vacuum evaporator and the following compounds Z-5 (350 Å), LiF (10 Å), and Al (1000 Å) were sequentially deposited to produce an organic light-emitting device. In the above process, the deposition rate of LiF, the cathode, was maintained at 0.1 Å/sec, the deposition rate of aluminum (Al) was maintained at 2 Å/sec, and the degree of vacuum during deposition was maintained at 2x10 ^-7 to 5x10 ^-8 torr.

Examples 5-6 and Comparative Example 2

An organic light-emitting device was manufactured in the same manner as Example 4, except that the compound shown in Table 2 below was used instead of Compound D according to Preparation Example 3.

Test Example 2 (Evaluation of characteristics of organic light-emitting device)

When current was applied to the organic light emitting devices according to Examples 4 to 6 and Comparative Example 2, the driving voltage, current efficiency, power efficiency, and lifespan (T90) were measured. The results are shown in Table 2 below.

The lifespan (T90) refers to the time it takes for luminance to decrease to 90% from the initial luminance.

luminescent layer
host driving voltage
(V@10mA
/cm ² ) current efficiency
(cd/A@10mA
/cm ² ) power efficiency
(lm/W) T90(hr)
@20mA/ ^cm2 Example 4 compound D,
Compound 4 4.68 8.15 5.47 38 Example 5 Compound E,
Compound 4 5.01 7.53 4.72 29 Example 6 compound F,
Compound 4 4.97 7.78 4.92 36 Comparative Example 2 Compound BH-1,
Compound 4 5.09 5.43 3.35 13

Referring to Table 2, the organic light-emitting device using the compounds D to F as the host of the light-emitting layer exhibits superior characteristics in terms of driving voltage, current efficiency, and lifespan compared to the organic light-emitting device using the compound BH-1 as the host of the light-emitting layer. It was.

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

Claims (8)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
Ar ¹ and Ar ² are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, a C _6-30 aryloxy group, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; or a C _2-60 heteroaryl group containing one or more heteroatoms selected from the group consisting of N, O and S and substituted or unsubstituted with a C _6-30 aryl group,
R ¹ and R ² are each independently an alkyl group of C _1-30 ,
n and m are each 2,
p and q are each 1,
L ¹ to L ⁴ are each independently hydrogen; heavy hydrogen; C _1-30 alkyl group; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryloxy group period, or a C _6-50 aryl group substituted or unsubstituted with a C _6-30 aryl group; Or it is a C _2-60 heteroaryl group that contains one or more heteroatoms selected from the group consisting of N, O, and S and is substituted or unsubstituted with a C _6-30 aryl group.
delete delete According to claim 1,
Ar ¹ and Ar ² are each independently a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, benzofuranyl group, or fluorenyl group. ,
Ar ¹ and Ar ² are each independently substituted or substituted with methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, methoxy, ethoxy, propoxy, butoxy, isobutoxy, or neobutoxy. rejuvenated,
compound.
According to claim 1,
The compound wherein R ¹ and R ² are each independently a C _1-10 alkyl group.
According to claim 1,
The compound wherein L ¹ to L ⁴ are each independently hydrogen or a C _1-30 alkyl group.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of compounds with the following structural formula.

An organic light emitting device comprising a first electrode, a second electrode provided opposite to the first electrode, and one or more organic material layers provided between the first electrode and the second electrode;
An organic light-emitting device, wherein at least one of the organic layers includes the compound represented by Formula 1 of claim 1.