KR102495828B1 - 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 using the same {NOVEL COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, 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 are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

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

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Formula 1,

Ar ₁ is a C _6-60 aryl substituted with an adamantane group;

Ar ₂ is a substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

m and n are each independently an integer from 0 to 7;

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 Alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Chemical Formula 1.

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

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 shows an example of an organic light emitting device composed 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 did
3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (9), a light emitting layer (7), a hole blocking layer (10), and an electron transport layer (8). , An example of an organic light emitting device composed of an electron injection layer 11 and a cathode 4 is shown.

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

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

,

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

,

, or

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl 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 heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the ester group may be substituted with an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

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

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

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

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms 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, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

Preferably, Formula 1 is represented by Formula 1-1 below:

[Formula 1-1]

In Formula 1-1,

Ar ₁ , Ar ₂ , m, n, R ₁ and R ₂ are as defined above.

Preferably, Ar ₁ may be C _6-20 aryl substituted with an adamantane group, for example, phenyl substituted with an adamantane group; biphenyl substituted with adamantane group; Or it may be naphthyl substituted with an adamantane group.

Preferably, Formula 1 may be represented by any one of Formulas 2-1 to 2-3 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,

Ar ₂ , m, n, R ₁ and R ₂ are described as defined above.

Preferably, Ar ₂ is a substituted or unsubstituted C _6-20 aryl; Or it may be a substituted or unsubstituted C _5-20 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S, more preferably, phenyl; biphenyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or 9,9-dimethyl-9H-fluorenyl.

Preferably, m and n may each independently be 0 or 1.

Preferably, R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; Or it may be a substituted or unsubstituted C _6-20 aryl, more preferably, each independently hydrogen; heavy hydrogen; or phenyl.

For example, the compound may be selected from the group consisting of:

Meanwhile, the compound represented by Chemical Formula 1 can be prepared by a manufacturing method shown in Reaction Scheme 1 below.

[Scheme 1]

In Scheme 1, T is halogen, preferably bromo or chloro, and other substituents are defined as described above.

Specifically, the compound represented by Chemical Formula 1 is prepared by combining starting materials through a Suzuki coupling reaction. It is preferable to carry out the Suzuki coupling reaction in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

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

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, a layer that simultaneously injects and transports holes, or an electron blocking layer, and the hole injection layer, the hole transport layer, a layer that simultaneously injects and transports holes, or blocks electrons. The layer may include the compound represented by Formula 1 above.

Also, the organic material layer may include a light emitting layer, and the light emitting layer may include the compound represented by Chemical Formula 1. In this case, the compound represented by Formula 1 may be used as a host material in the light emitting layer, and more specifically, the compound represented by Formula 1 may be used as a host used in the light emitting layer of the green organic light emitting device.

In addition, the light emitting layer may include two or more types of hosts, and when the light emitting layer includes two or more types of hosts, one or more of the hosts may be the compound.

In addition, the organic material layer may include a hole blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the hole blocking layer, the electron transport layer, the electron injection layer, or the electron transport and electron injection layer. The layer to be simultaneously injected may include the compound represented by Chemical Formula 1 above.

Also, 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. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 to 3 .

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

2 shows an example of an organic light emitting device composed 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 did In this structure, the compound represented by Formula 1 may be included in at least one layer of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (9), a light emitting layer (7), a hole blocking layer (10), and an electron transport layer (8). , An example of an organic light emitting device composed of an electron injection layer 11 and a cathode 4 is shown. In this structure, the compound represented by Formula 1 may be included in at least one layer of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After 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 depositing a material that can be used as a cathode thereon, it can be prepared. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

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

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode 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, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode 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-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light emitting layer is a material having high hole mobility. this is suitable Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. serves to improve The electron blocking layer includes an electron blocking material, and a material having a stable structure that prevents electrons from leaking out of the light emitting layer is suitable as the electron blocking material. As a specific example, an arylamine-based organic material may be used, but is not limited thereto.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

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

The hole blocking layer is formed on the light emitting layer, and specifically, the hole blocking layer is provided in contact with the light emitting layer to prevent excessive movement of holes to increase the probability of hole-electron coupling, thereby improving the efficiency of the organic light emitting device. do The hole blocking layer includes a hole blocking material, and a material having a stable structure that prevents holes from leaking out of the light emitting layer is suitable as the hole blocking material. Examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound having an electron withdrawing group such as a phosphine oxide derivative may be used, but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

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

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

[Production Example]

Preparation Example 1: Preparation of Intermediate A

Step 1) Preparation of Intermediate A-1

In a flask, 3-chloro-9H-carbazole (15.0 g, 74.4 mmol), bromobenzene (12.8 g, 81.8 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.5 mmol), sodium tert-butoxide (10.7 g, 111.6 mmol) and toluene (450 ml) were added thereto, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, water was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to obtain intermediate A-1 (15.9 g). (Yield 77%, MS: [M+H] ⁺ = 278)

Step 2) Preparation of Intermediate A-2

In a flask, intermediate A-1 (15.0 g, 54.0 mmol), bis (pinacolato) diboron (15.1 g, 59.4 mmol), bis (dibenzylideneacetone) palladium (0) (0.6 g, 1.1 mmol), tricyclohexylphosphine (0.6 g, 2.2 mmol) ), potassium acetate (10.6 g, 108.0 mmol), and 1,4-dioxane (300 ml) were added, and stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, the reaction solution was transferred to a separatory funnel and extracted with water and ethyl acetate. After drying the extract with MgSO ₄ , filtering and concentrating, the sample was purified by silica gel column chromatography to obtain intermediate A-2 (11.0 g). (Yield 55%, MS: [M+H]+= 369)

Step 3) Preparation of Intermediate A

Intermediate A-2 (15.0 g, 40.6 mmol) and 3-bromo-9H-carbazole (12.0 g, 48.7 mmol) were dissolved in tetrahydrofuran (THF, 300 ml) in a flask, and potassium carbonate (22.5 g, 162.5 mmol) was added to water ( 150 ml) was dissolved in it. Tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2.0 mmol) was added thereto, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . After drying the extract with MgSO ₄ , filtering and concentrating, the sample was purified by silica gel column chromatography to obtain intermediate A (11.8 g). (Yield 71%, MS: [M+H] ⁺ = 409)

Preparation Example 2: Preparation of Intermediate B

Intermediate B was prepared in the same manner as in Intermediate A, except that in Preparation Example 1, bromobenzene was changed to 3-bromo-1,1'-biphenyl. (MS: [M+H] ⁺ = 485)

Preparation Example 3: Preparation of Intermediate C

Intermediate C was prepared in the same manner as in Intermediate A, except that in Preparation Example 1, bromobenzene was changed to 2-bromodibenzo[b,d]thiophene. (MS: [M+H] ⁺ = 515)

Preparation Example 4: Preparation of Intermediate D

Intermediate D was prepared in the same manner as in Intermediate A, except that in Preparation Example 1, bromobenzene was changed to 2-bromodibenzo[b,d]furan. (MS: [M+H] ⁺ = 499)

Preparation Example 5: Preparation of Intermediate E

In Preparation Example 1, Intermediate E was prepared by the same manufacturing method as Intermediate A, except that bromobenzene was changed to 2-bromo-9,9-dimethyl-9H-fluorene. (MS: [M+H] ⁺ = 525)

Preparation Example 6: Preparation of Intermediate F

Intermediate F was prepared in the same manner as in Intermediate A, except that in Preparation Example 1, bromobenzene was changed to 2-bromonaphthalene. (MS: [M+H] ⁺ = 459)

Preparation Example 7: Preparation of Intermediate G

Intermediate G was prepared in the same manner as in Intermediate A, except that in Preparation Example 1, bromobenzene was changed to 4-bromo-1,1'-biphenyl. (MS: [M+H] ⁺ = 485)

Preparation Example 8: Preparation of Intermediate H

In Preparation Example 1, 3-chloro-9H-carbazole was changed to 2-chloro-9H-carbazole and bromobenzene was changed to 4-bromo-1,1'-biphenyl, except for using the same method for preparing Intermediate A. Intermediate H was prepared by the manufacturing method. (MS: [M+H] ⁺ = 485)

Preparation Example 9: Preparation of Intermediate I

In Preparation Example 1, 3-chloro-9H-carbazole was changed to 4-chloro-9H-carbazole and 3-bromo-9H-carbazole was changed to 4-chloro-9H-carbazole, except for the method for preparing intermediate A. Intermediate I was prepared by the same preparation method as above. (MS: [M+H] ⁺ = 409)

[Example]

Example 1: Preparation of Compound 1

In a flask, intermediate A (15.0 g, 36.7 mmol), intermediate a (11.8 g, 40.4 mmol), bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol), sodium tert-butoxide (5.3 g, 55.1 mmol), and toluene (300 ml) were added, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. After the reaction was completed, after cooling to room temperature, water was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography, and compound 1 (7.3 g) was obtained through sublimation purification. (Yield 32%, MS: [M+H] ⁺ = 619)

Example 2: Preparation of Compound 2

In Example 1, Compound 2 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate B and used. (MS: [M+H] ⁺ = 695)

Example 3: Preparation of Compound 3

In Example 1, Compound 3 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate C. (MS: [M+H] ⁺ = 725)

Example 4: Preparation of Compound 4

In Example 1, Compound 4 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate D and Intermediate a was changed to Intermediate b. (MS: [M+H] ⁺ = 709)

Example 5: Preparation of Compound 5

In Example 1, Compound 5 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate E and Intermediate a was changed to Intermediate b. (MS: [M+H] ⁺ = 735)

Example 6: Preparation of Compound 6

In Example 1, Compound 6 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate F and Intermediate a was changed to Intermediate b. (MS: [M+H] ⁺ = 669)

Example 7: Preparation of compound 7

In Example 1, Compound 7 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate G and Intermediate a was changed to Intermediate c. (MS: [M+H] ⁺ = 695)

Example 8: Preparation of Compound 8

In Example 1, Compound 8 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate H. (MS: [M+H] ⁺ = 695)

Example 9: Preparation of compound 9

In Synthesis Example 10, Compound 9 was prepared in the same manner as in Compound 1, except that Intermediate A was changed to Intermediate I and Intermediate a was changed to Intermediate b. (MS: [M+H] ⁺ = 619)

[Experimental example]

Experimental Example 1

A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

On the prepared ITO transparent electrode, the following HT-A compound and 5% by weight of the following PD compound were thermally vacuum deposited to a thickness of 100 Å, and then only the HT-A compound was deposited to a thickness of 1150 Å to form a hole transport layer. The following HT-B compound was thermally vacuum deposited thereon to a thickness of 450 Å as an electron blocking layer. Subsequently, a host was formed by using Compound 1 prepared in Example 1 as a first host and the following NGH compound as a second host in a weight ratio of 60:40, and 15% by weight of the host as a dopant with the GD compound 400 It was vacuum deposited to a thickness of Å. Then, as a hole blocking layer, the following compound ET-A was vacuum deposited to a thickness of 50 Å. Subsequently, as an electron transport and injection layer, the following ET-B compound and the following Liq compound were thermally vacuum deposited at a ratio of 2:1 to a thickness of 250 Å, followed by vacuum deposition of LiF and magnesium at a ratio of 1:1 at a thickness of 30 Å. did An organic light emitting device was manufactured by depositing magnesium and silver to a thickness of 160 Å at a ratio of 1:4 on the electron injection layer to form a cathode.

Experimental Examples 2 to 9 and Comparative Experimental Examples 1 to 3

Experimental Examples 2 to 9 and Comparative Experimental Examples 1 to 3 were fabricated in the same manner as in Experimental Example 1, except that the first host material was changed as shown in Table 1 below.

Voltage and efficiency were measured by applying a current density of 10 mA/cm ² to the organic light emitting device prepared in the Experimental Examples and Comparative Experimental Examples, heat-treated in an oven at 110° C. for 10 hours, taken out, and re-measured under the same conditions. The results are shown in Table 1 below.

1st host before heat treatment after heat treatment Voltage (V) Efficiency (cd/A) Voltage (V) Efficiency (cd/A) Example 1 compound 1 4.71 54.2 4.76 53.2 Example 2 compound 2 4.73 53.1 4.74 53.0 Example 3 compound 3 4.62 51.6 4.63 51.8 Example 4 compound 4 4.63 51.3 4.66 50.2 Example 5 compound 5 4.72 53.8 4.72 53.8 Example 6 compound 6 4.75 50.7 4.76 50.4 Example 7 compound 7 4.81 53.2 4.82 52.2 Example 8 compound 8 4.94 50.1 4.94 50.0 Example 9 compound 9 4.83 50.6 4.84 50.3 Comparative Example 1 compound A 4.78 51.3 5.78 28.3 Comparative Example 2 compound B 4.67 50.4 7.87 16.4 Comparative Example 3 compound C 4.80 52.8 6.12 31.8

As can be seen from Table 1, when the compound represented by Formula 1 according to the present invention is used as the first host of the light emitting layer of the organic light emitting device, it exhibits characteristics equal to or higher than those of the compounds of Comparative Examples in terms of voltage and efficiency. can know that In particular, it can be confirmed that the device using the compound of the comparative example has reduced voltage and efficiency characteristics after heat treatment, whereas the device using the compound of the present invention maintains equal or better characteristics before and after heat treatment due to excellent thermal characteristics.

This characteristic of the compound represented by Formula 1 according to the present invention is a characteristic that appears by including an adamantane structure. The adamantane structure is a cycloalkyl, but the molecule has a non-planar structure in a single molecular structure rather than an aryl structure. . In general, a non-planar structure such as an alkyl group having a long chain causes energy loss due to motility due to rotational motion or vibrational motion of the molecule, whereas adamantane has a characteristic of lowering crystallinity. Despite being present, they form strong condensed rings three-dimensionally with each other, so they can have high heat resistance by reducing the mobility of molecules, and can also reduce energy loss due to molecular motion. In addition, an aryl structure such as a phenyl structure affects the energy level of a molecule due to its delocalized structure. The adamantane structure does not affect the energy level, but contains a large number of carbon atoms and increases the molecular weight, resulting in a melting point or The high glass transition temperature can also improve thin film stability.

As a result, when the compound represented by Formula 1 according to the present invention is used as a light emitting layer of an organic light emitting device, a device having high heat resistance while exhibiting characteristics of low voltage and high efficiency can be obtained.

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
9: electron blocking layer 10: hole blocking layer
11: electron injection layer

Claims (10)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
Ar ₁ is phenyl substituted with an adamantane group; biphenyl substituted with adamantane group; or naphthyl substituted with an adamantane group,
Ar ₂ is a substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
m and n are each independently an integer from 0 to 7;
R ₁ and R ₂ are each independently hydrogen, deuterium, or phenyl.
According to claim 1,
Formula 1 is represented by the following Formula 1-1,
compound:
[Formula 1-1]

In Formula 1-1,
Ar ₁ , Ar ₂ , m, n, R ₁ and R ₂ are as defined in claim 1.
delete According to claim 1,
Formula 1 is represented by any one of the following Formulas 2-1 to 2-3,
compound:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,
Ar ₂ , m, n, R ₁ and R ₂ are as defined in claim 1.
According to claim 1,
Ar ₂ is phenyl; biphenyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or 9,9-dimethyl-9H-fluorenyl;
compound.
According to claim 1,
m and n are each independently 0 or 1;
compound.
delete According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers is formed according to claims 1, 2, 4 to 6, and 7. An organic light-emitting device comprising the compound according to any one of claims 8 to 10.
According to claim 9,
The organic material layer containing the compound is a light emitting layer,
organic light emitting device.

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