KR102633801B1 - 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 using the same.

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.

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

Korean Patent Publication No. 10-2013-073537

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

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

[Formula 1]

In Formula 1,

R' ₁ and R' ₂ are both hydrogen, or are combined with each other to form a single bond,

X ₁ , X ₂ and X ₃ are each independently N; or CH, provided that at least one of X ₁ , X ₂ and X ₃ is N,

L ₁ , L ₂ and L ₃ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,

Ar ₁ and Ar ₂ are each independently adamantyl; 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, provided that at least one of Ar ₁ and Ar ₂ is adamantyl,

R ₁ and R ₂ are hydrogen; heavy hydrogen; or substituted or unsubstituted C _1-60 alkyl,

m is an integer from 0 to 8,

n is an integer from 0 to 7.

In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound of the present invention described above.

The compound represented by the above-mentioned formula 1 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 the above-mentioned formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

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 was done.

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

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

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 heterocyclic groups 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 or 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, 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 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, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic 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, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but is not limited to these.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine 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 the heterocyclic group 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 the heterocyclic group 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 the heterocyclic group described above can be applied, except that the heterocycle is not a monovalent group and is formed by combining two substituents.

Preferably, the compound represented by Formula 1 is a compound represented by the following Formulas 1-1 to 1-6:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,

X ₁ , X ₂ , X ₃ , L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , m and n are as defined in claim 1.

Preferably, L ₁ , L ₂ and L ₃ are each independently a single bond; phenylene; biphenylylene; Or naphthylene. Preferably, L ₁ , L ₂ and L ₃ are each independently a single bond; phenylene; It is biphenylylene. Or, L ₁ is a single bond; phenylene; or biphenylylene, and L ₂ and L ₃ are each independently a single bond; Or it is phenylene.

Preferably, Ar ₁ and Ar ₂ are each independently adamantyl; or any one selected from the group consisting of the following, provided that at least one of Ar ₁ and Ar ₂ is adamantyl.

In the above,

R' and R'' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-10 alkyl; or substituted or unsubstituted C _6-12 aryl. Preferably, R' and R'' are each independently methyl.

Preferably, Ar ₁ and Ar ₂ are each independently adamantyl, phenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, provided that at least one of Ar ₁ and Ar ₂ is adamantyl. am.

Preferably, R ₁ and R ₂ are each independently hydrogen; Or deuterium.

Preferably, m and n are each independently 0 or 1.

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

.

.

.

.

The compound represented by Formula 1 according to the present invention has a triazine-based substituent in the spiro[fluorene-9,8'-indolo[3,2,1-de]acridine] and spiro[acridine-9,9'-fluorene] core structures. It is a compound in which (including pyridine, pyrimidine, and triazine) are combined, and has an adamantyl group as one of the additional substituents of the triazine substituent. These compounds can exhibit improved hole-electron bonding and improved thermal stability compared to compounds substituted with a triazine-based substituent that does not have an adamantyl group. As a result, organic light-emitting devices employing the above compounds can exhibit characteristics such as high efficiency, low driving voltage, and long lifespan.

The compound represented by Formula 1 can be prepared through Scheme 1 below.

[Scheme 1]

In Scheme 1, the definitions of substituents other than X are as described above, and X is halogen, preferably bromo or chloro.

Scheme 1 is a Suzuki coupling reaction that is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed according to what is known in the art.

In the compound represented by Formula 1, the position of each substituent can be prepared by referring to Scheme 1 and appropriately changing the structure of the starting material. The method for producing the compound represented by Formula 1 may be more detailed in the production examples to be described later.

Meanwhile, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a compound represented by Formula 1. .

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, a hole blocking layer, etc. as an organic material layer. However, the structure of the organic light emitting 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 Formula 1.

Additionally, the organic material layer may include a hole blocking layer, and the hole blocking layer includes the compound represented by Chemical Formula 1.

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 is an organic material layer that, in addition to the light-emitting layer, further includes a hole injection layer and a hole transport layer between the first electrode and the light-emitting layer, and an electron transport layer and an electron injection layer between the light-emitting layer and the second electrode. It can have a structure that does. However, the structure of the organic light emitting device is not limited to this and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention is 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 where the first electrode is an anode and the second electrode is a cathode. It may be a device. In addition, the organic light emitting device according to the present invention is an inverted type organic device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate where the first electrode is a cathode and the second electrode is an anode. It may be a light emitting device. 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 transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6. In this structure, the compound represented by Formula 1 may be included in the hole transport layer.

Figure 2 shows a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and a cathode 6. 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, the hole transport layer, or the electron suppression layer.

The organic light emitting device according to the present invention can 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. Additionally, 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 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 light-emitting device can be made by sequentially depositing a cathode material, an organic material 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 light-emitting 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.

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 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 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. 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 hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. These include organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, 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 an arylamine-based organic material, a conductive polymer, and a block copolymer having both a conjugated and non-conjugated portion may be used, but is not limited thereto. .

The electron blocking layer is formed on the hole transport layer, preferably 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. This refers to the layer that plays a role in improving. The electron blocking layer includes an electron blocking material, and examples of the electron blocking material include the compound represented by Chemical Formula 1, or an arylamine-based organic material, but are not limited thereto.

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 thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material may further include a condensed aromatic ring derivative or a heterocyclic ring-containing compound. 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 hole blocking layer is formed on the light-emitting layer, preferably in contact with the light-emitting layer, to improve the efficiency of the organic light-emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling. It refers to the layer that plays a role. The hole blocking layer includes a hole blocking material. Examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; Oxadiazole derivatives; phenanthroline derivatives; Compounds into which electron-withdrawing groups are introduced, such as phosphine oxide derivatives, may be used, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously performs the roles of an electron transport layer and an electron injection layer, injecting electrons from an electrode and transporting the received electrons to the light-emitting layer, and is formed on the light-emitting layer or the hole blocking layer. As such an electron injection and transport material, a material that can easily inject electrons from the cathode and transfer them to the light emitting layer, and a material with high mobility for electrons, is suitable. Specific examples of electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complex; Triazine derivatives, etc., but are not limited to these. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds. , or a nitrogen-containing 5-membered ring derivative, etc., but is not limited thereto.

The electron injection and transport layer may also be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, an electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds, and nitrogen-containing five-membered ring derivatives can be used.

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.

Preparation Example A: Preparation of intermediate compound A

Dissolve 2-bromobiphenyl (48.07 g, 149.29 mmol) as compound y-1 in 35 ml of THF in a 500 mL round bottom flask under a nitrogen atmosphere, cool it to -78°C, and add tert-butyllithium (t-BuLi). 25.45ml (2.5 M in pentane) was added dropwise and stirred at the same temperature for 40 minutes. 2-Bromo-9H-xanthene-9-one (35.15 g, 135.71 mmol), which is compound x-1, was added to the prepared solution, and then the temperature was gradually raised to room temperature and stirred for 3 hours. Afterwards, the reactant was poured into a mixed solution of 60 ml of diethyl ether and 100 ml of 2N aqueous hydrochloric acid, stirred for 30 minutes, and the resulting solid was filtered, washed with water and diethyl ether, and dried. 55.5 g of the dried solid sample was taken and dissolved in 450 ml of acetic acid, and then a catalytic amount (10 drops) of concentrated sulfuric acid was added and refluxed for 6 hours. Afterwards, the resulting solid compound was filtered, washed with acetic acid, and dried to obtain Compound A-1 (52.48g, yield: 76%), a white solid compound.

Next, mix Chemical Formula A-1 (52.48 g, 103.10mmol), pinacoldiborone (34.04 g, 134.04mmol), and potassium acetate (15.17g, 154.66mmol) in a nitrogen atmosphere, add to 450 ml of dioxane, and stir. It was heated while doing so. In a refluxed state, bis(dibenzylidineacetone)palladium (0.77g, 3.09mmol) and tricyclohexylphosphine (1.51g, 6.17mmol) were added and heated and stirred for 8 hours. After completion of the reaction, the temperature was lowered to room temperature and then filtered. Water was poured into the filtrate, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, it was recrystallized with ethanol to obtain intermediate compound A (39.46 g, yield: 72%).

MS[M+H]+= 532

Preparation Example B: Preparation of intermediate compound B

Intermediate compound B (32.44 g, yield: 44%) was prepared using the same method as Preparation Example A, except that starting material x-2 was used instead of starting material x-1 in Preparation Example A.

MS[M+H]+= 532

Preparation Example C: Preparation of intermediate compound C

Intermediate Compound C (28.67 g, yield: 52%) was prepared using the same method as Preparation Example A, except that starting material x-3 was used instead of starting material x-1 in Preparation Example A.

MS[M+H]+= 532

Preparation Example D: Preparation of intermediate compound D

An intermediate compound was prepared using the same method as Preparation A, except that starting material x-2 was used instead of starting material x-1 and starting material y-2 was used instead of starting material y-1. D (34.65g, yield: 63%) was prepared.

MS[M+H]+= 532

Preparation Example E: Preparation of intermediate compound E

Intermediate Compound E (31.22 g, yield: 57%) was prepared using the same method as Preparation Example A, except that starting material y-2 was used instead of starting material y-1.

MS[M+H]+= 532

Preparation Example F: Preparation of intermediate compound F

The same method as Preparation Example A, except that starting material x-3 was used instead of starting material x-1, and starting material y-2 was used instead of starting material y-1. Intermediate compound F (27.76 g, yield: 76%) was prepared using .

MS[M+H]+= 532

Preparation Example 1: Preparation of Compound 1

Compound A (10.49g, 19.76mmol) and a-1 (7.22, 17.96mmol) were completely dissolved in 240ml of tetrahydrofuran in a 500ml round bottom flask under a nitrogen atmosphere, then 2M potassium carbonate aqueous solution (120ml) was added, and tetrakis- After adding (triphenylphosphine)palladium (0.62 g, 0.54 mmol), it was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 ml of tetrahydrofuran to prepare Compound 1 (8.37 g, yield: 60%).

MS[M+H] ⁺ = 771

Preparation Example 2: Preparation of Compound 2

Compound A (7.71 g, 14.52 mmol) and compound a-2 (6.89 g, 13.20 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M aqueous potassium carbonate solution (120 mL). After addition, tetrakis-(triphenylphosphine)palladium (0.46 g, 0.40 mmol) was added and heated and stirred for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 320 mL of ethyl acetate to prepare Compound 2 (7.35 g, yield: 66%).

MS[M+H] ⁺ = 848

Preparation Example 3: Preparation of Compound 3

Compound B (7.42 g, 13.97 mmol) and compound b-1 (6.63 g, 12.70 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M potassium carbonate aqueous solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.44 g, 0.38 mmol), it was heated and stirred for 7 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 mL of tetrahydrofuran to prepare Compound 3 (6.69 g, yield: 62%).

MS[M+H] ⁺ = 848

Preparation Example 4: Preparation of Compound 4

Compound B (6.96 g, 13.11 mmol) and compound b-2 (6.21 g, 11.92 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M potassium carbonate aqueous solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.41 g, 0.36 mmol), it was heated and stirred for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 mL of tetrahydrofuran to prepare Compound 4 (7.39 g, yield: 73%).

MS[M+H] ⁺ = 847

Preparation Example 5: Preparation of Compound 5

Compound C (8.61 g, 16.21 mmol) and compound c-1 (7.25 g, 14.74 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M aqueous potassium carbonate solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.51 g, 0.44 mmol), it was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 mL of tetrahydrofuran to prepare Compound 5 (7.89 g, yield: 62%).

MS[M+H] ⁺ = 862

Preparation Example 6: Preparation of Compound 6

Compound C (8.20 g, 15.44 mmol) and compound c-2 (7.13 g, 14.04 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M potassium carbonate aqueous solution (120 mL). After addition, tetrakis-(triphenylphosphine)palladium (0.49 g, 0.42 mmol) was added and heated and stirred for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 mL of ethyl acetate to prepare Compound 6 (6.99 g, yield: 58%).

MS[M+H] ⁺ = 878

Preparation Example 7: Preparation of Compound 7

Compound D (9.46g, 17.82mmol) and d-1 (8.02, 16.20mmol) were completely dissolved in 240ml of tetrahydrofuran in a 500ml round bottom flask under a nitrogen atmosphere, then 2M potassium carbonate aqueous solution (120ml) was added, and Tetrakis- After adding (triphenylphosphine)palladium (0.56 g, 0.49 mmol), it was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 ml of tetrahydrofuran to prepare Compound 7 (7.16 g, yield: 52%).

MS[M+H] ⁺ = 850

Preparation Example 8: Preparation of Compound 8

Compound D (6.52g, 12.27mmol) and d-2 (6.37, 11.16mmol) were completely dissolved in 240ml of tetrahydrofuran in a 500ml round bottom flask under a nitrogen atmosphere, then 2M potassium carbonate aqueous solution (120ml) was added, and tetrakis- After adding (triphenylphosphine)palladium (0.39 g, 0.33 mmol), it was heated and stirred for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 ml of tetrahydrofuran to prepare Compound 8 (6.34 g, yield: 61%).

MS[M+H] ⁺ = 926

Preparation Example 9: Preparation of Compound 9

Compound E (8.65 g, 16.28 mmol) and compound e-1 (7.46 g, 14.80 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M aqueous potassium carbonate solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.51 g, 0.44 mmol), it was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 mL of tetrahydrofuran to prepare Compound 9 (5.16 g, yield: 42%).

MS[M+H] ⁺ = 830

Preparation Example 10: Preparation of Compound 10

Compound E (8.26 g, 15.55 mmol) and compound e-2 (7.11 g, 14.14 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M aqueous potassium carbonate solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.49 g, 0.42 mmol), it was heated and stirred for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 mL of ethyl acetate to prepare Compound 10 (7.09 g, yield: 61%).

MS[M+H] ⁺ = 829

Preparation Example 11: Preparation of Compound 11

Compound F (12.34 g, 23.23 mmol) and compound f-1 (8.11 g, 21.12 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M potassium carbonate aqueous solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.73 g, 0.63 mmol), it was heated and stirred for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 290 mL of tetrahydrofuran to prepare Compound 11 (8.79 g, yield: 55%).

MS[M+H] ⁺ = 756

Preparation Example 12: Preparation of Compound 12

Compound F (14.31 g, 26.95 mmol) and compound f-2 (9.36 g, 24.50 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under a nitrogen atmosphere, and then added to 2M aqueous potassium carbonate solution (120 mL). After adding tetrakis-(triphenylphosphine)palladium (0.85 g, 0.74 mmol), it was heated and stirred for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 mL of tetrahydrofuran to prepare Compound 12 (11.69 g, yield: 63%).

MS[M+H] ⁺ = 754

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1,000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent manufactured by Fischer Co. was used, and distilled water filtered secondarily using a filter manufactured by 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, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode, which is the anode prepared in this way, the compounds of the following compound HI1 and the following compound HI2 were thermally vacuum deposited to a thickness of 100 Å at a ratio of 98:2 (molar ratio) to form a hole injection layer. A hole transport layer was formed by vacuum depositing a compound (1150 Å) represented by the following chemical formula HT1 on the hole injection layer. Subsequently, the compound of EB1 was vacuum deposited with a film thickness of 50 Å on the hole transport layer to form an electron blocking layer. Next, a compound represented by the following formula BH and a compound represented by the following formula BD were vacuum deposited on the electron blocking layer to a film thickness of 200 Å at a weight ratio of 25:1 to form a light emitting layer. A hole blocking layer was formed by vacuum depositing the compound represented by Compound 1 synthesized in Preparation Example 1 with a film thickness of 50 Å on the light emitting layer. Next, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 310 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic matter was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3Å/sec, and the deposition rate of aluminum was maintained at 2Å/sec, and the vacuum degree during deposition was 2x10 ^-7 ~ An organic light emitting device was manufactured by maintaining 5×10 ^-6 torr.

Example 1-2 to Example 1-12

An organic light-emitting device was manufactured in the same manner as Example 1-1, except that the compounds listed in Table 1 below were used instead of the compounds of Preparation Example 1.

Comparative Examples 1-1 to 1-5

An organic light-emitting device was manufactured in the same manner as Example 1-1, except that the compounds shown in Table 1 below were used instead of the compounds of Preparation Example 1. The compounds HB1 to HB5 used in Table 1 below are as follows.

Experimental Example 1

When current was applied to the organic light-emitting devices manufactured in the examples and comparative examples, the voltage, efficiency, color coordinate, and lifespan were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nit) to 95%.

division compound
(hole blocking layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 1-1 Manufacturing Example 1 4.53 6.41 (0.147, 0.045) 250 Example 1-2 Production example 2 4.52 6.42 (0.146, 0.046) 255 Example 1-3 Production example 3 4.64 6.31 (0.145, 0.045) 235 Example 1-4 Production example 4 4.69 6.23 (0.146, 0.045) 235 Examples 1-5 Production example 5 4.77 6.26 (0.145, 0.045) 240 Example 1-6 Production example 6 4.68 6.34 (0.146, 0.046) 255 Example 1-7 Production example 7 4.51 6.35 (0.146, 0.045) 250 Examples 1-8 Production example 8 4.60 6.31 (0.146, 0.045) 245 Example 1-9 Production example 9 4.63 6.23 (0.145, 0.046) 250 Examples 1-10 Production example 10 4.64 6.32 (0.145, 0.045) 255 Example 1-11 Production example 11 4.62 6.33 (0.145, 0.046) 245 Examples 1-12 Production example 12 4.62 6.31 (0.147, 0.046) 240 Comparative Example 1-1 HB1 5.25 5.85 (0.145, 0.046) 160 Comparative Example 1-2 HB2 5.01 5.94 (0.145, 0.047) 145 Comparative Example 1-3 HB3 5.43 5.71 (0.145, 0.045) 125 Comparative Example 1-4 HB4 6.12 5.34 (0.145, 0.046) 80 Comparative Example 1-5 HB5 6.33 5.12 (0.146, 0.045) 65

As shown in Table 1, the organic light-emitting device using the compound of the present invention as a hole blocking layer showed excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.

In Examples 1-1 to 1-12, organic light-emitting devices using the compounds of the present invention include spiro[fluorene-9,8'-indolo[3,2,1-de]acridine] and spiro[acridine-9,9. Compared to the organic light emitting devices of Comparative Examples 1-1, 1-2, and 1-3 manufactured using materials of HB1, HB2, and HB3 in which the triazine group containing one or more adamantyl groups in the '-fluorene core structure is not substituted, It exhibited characteristics of low voltage, high efficiency, and long lifespan.

In addition, the lightness of Comparative Examples 1-4 and 1-5, which were prepared using HB4 and HB5 materials in which a triazine group containing an adamantyl group was substituted on the acridine side of the spiro-bonded core, was compared to the organic example. The efficiency and driving voltage of the light emitting device decreased, and in particular, the lifespan characteristics decreased significantly.

1: Substrate 2: Anode
3: hole transport layer 4: light emitting layer
5: Electron injection and transport layer 6: Cathode
7: hole injection layer 8: electron suppression layer
9: Hole blocking layer

Claims (7)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
R' ₁ and R' ₂ are both hydrogen, or are combined with each other to form a single bond,
X ₁ , X ₂ and X ₃ are each independently N; or CH, provided that at least one of X ₁ , X ₂ and X ₃ is N,
L ₁ , L ₂ and L ₃ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,
Ar ₁ and Ar ₂ are each independently adamantyl; 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, provided that at least one of Ar ₁ and Ar ₂ is adamantyl,
R ₁ and R ₂ are hydrogen; heavy hydrogen; or substituted or unsubstituted C _1-60 alkyl,
m is an integer from 0 to 8,
n is an integer from 0 to 7.
According to clause 1,
The compound represented by Formula 1 is a compound represented by the following Formulas 1-1 to 1-6:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,
X ₁ , X ₂ , X ₃ , L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , m and n are as defined in claim 1.
According to clause 1,
L ₁ , L ₂ and L ₃ are each independently a single bond; phenylene; biphenylylene; or naphthylene, a compound.
According to clause 1,
Ar ₁ and Ar ₂ are each independently adamantyl; or any one selected from the group consisting of, provided that at least one of Ar ₁ and Ar ₂ is adamantyl:

In the above,
R' and R'' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-10 alkyl; Or substituted or unsubstituted C _6-12 aryl.
According to clause 1,
R ₁ and R ₂ are each independently hydrogen; or deuterium, a compound.
According to paragraph 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.

.
first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 6. An organic light-emitting device.