KR20210046484A - 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. A compound represented by chemical formula 1 can be used as a material for an organic layer of the organic light emitting device, and can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and 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 and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an 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 excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

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 an organic light emitting device comprising the novel compound.

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

[Formula 1]

In Formula 1,

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 a substituted or unsubstituted C _6-60 arylene,

Ar ₁ and Ar ₂ are each independently adamantyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of _{Ar 1} and Ar _{2 is adamantyl,}

R ₁ , R ₂ , and R ₃ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl,

m, n and o are each independently an integer of 0 to 7.

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 of the present invention.

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 in the organic light-emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

1 shows an example of an organic light-emitting device comprising 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.
2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and a cathode 6 are shown as an example of an organic light-emitting device.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy 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 it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In 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 a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of 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 it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group 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, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary 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, and the like, but are not limited thereto.

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

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

Can be, 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 a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl Group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present 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 the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example 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 aforementioned heterocyclic group 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 bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other and formed.

Preferably, the compound represented by Formula 1 is a compound represented by Formula 1-1 or Formula 1-2:

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

X ₁ , X ₂ , X ₃ , L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , R ₃ , m, n and o are as previously defined.

Preferably, L ₁ , L ₂ and L ₃ are each independently a single bond; Phenylene; Biphenylylene; Or naphthylene.

Preferably, 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:}

Above,

R _'1 and R' ₂ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-10 alkyl; Or a substituted or unsubstituted C _6-12 aryl,

p is an integer from 0 to 5.

Preferably, R ₁ , R ₂ and R ₃ are each independently hydrogen; Or deuterium.

Preferably, m, n and o 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 is dispyro[fluorene-9,9'-anthracene-10',9''-fluorene] (dispiro[fluorene-9,9'-anthracene-10',9 ''-fluorene]) is a compound in which a triazine substituent (including pyridine, pyrimidine, and triazine) is bonded to the core of the structure, and has an adamantyl group as one of the additional substituents of the triazine substituent. These compounds may exhibit improved hole transport ability and improved thermal stability compared to compounds substituted with triazine-based substituents having no adamantyl group. Accordingly, the organic light-emitting device employing the compound can exhibit characteristics such as high efficiency, low driving voltage, and long life.

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

[Scheme 1]

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

Scheme 1 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction may be changed as known in the art.

In the compound represented by Formula 1, the position of each substituent can be prepared by appropriately changing the structure of the starting material with reference to Scheme 1. The method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

Meanwhile, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above. For 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 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, but may have a multilayer 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, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.

In addition, the organic material layer may include an emission layer, and the emission layer includes a compound represented by Formula 1.

In addition, the organic material layer may include a hole blocking layer, and the hole blocking layer includes a compound represented by Formula 1 above.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the emission layer, and an electron transport layer and an electron injection layer between the emission layer and the second electrode in addition to the emission layer as an organic material layer. It can have a structure to do. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number or a larger number of organic layers.

In addition, in the organic light emitting device according to the present invention, the first electrode is an anode and the second electrode is a cathode, and an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). It may be a device. In addition, in the organic light emitting device according to the present invention, the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. 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.

1 shows an example of an organic light-emitting device comprising 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 such a structure, the compound represented by Formula 1 may be included in the hole transport layer.

2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and a cathode 6 are shown as an example of an organic light-emitting device. In such a 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 may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, 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, it can be prepared by depositing a material that can be used as a cathode thereon. 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 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

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

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material 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;} Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, 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 holes to the emission layer.The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission 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 a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .

The electron suppression 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. It refers to the layer that plays a role in improving the value. The electron-suppression layer includes an electron-blocking material, and examples of such an electron-blocking material may include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in a visible light region by transporting 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 of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As described above, the emission layer may include a host material and a dopant material. The host material may further include a condensed aromatic ring derivative or a heterocyclic 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, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The hole blocking layer is formed on the emission layer and is preferably provided in contact with the emission layer to improve the efficiency of the organic light-emitting device by increasing the probability of hole-electron bonding by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As such an electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or nitrogen-containing 5-membered cyclic derivatives may be used together, but the present invention 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 emission 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, the 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, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited thereto.

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

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

Preparation of the compound represented by 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 for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation A: Preparation of intermediate compound A

In a 500 mL round bottom flask in a nitrogen atmosphere, 2-bromobiphenyl (2.68 g, 11.5 mmol) of the compound y-1 was dissolved in 35 ml of THF, cooled to -78°C, and tert-butyllithium (t-BuLi) 16.9 ml (1.7 M in pentane) was added dropwise and then stirred at the same temperature for 40 minutes. After adding 2-bromoanthraquinone, compound x-1, to the prepared solution, the temperature was gradually raised to room temperature and stirred for 3 hours. Thereafter, the reactant was poured into a mixed solution of 15 ml of diethyl ether and 25 ml of 2N hydrochloric acid aqueous solution, and then stirred for 30 minutes to filter the resulting solid, washed with water and diethyl ether, and dried. 2.5 g of the dried solid sample was taken and dissolved in 50 ml of acetic acid, and then a catalytic amount (10 drops) of concentrated sulfuric acid was added and refluxed for 3 hours. Thereafter, the resulting solid compound was filtered, washed with acetic acid, and dried to obtain a white solid compound A-1 (2.2 g, yield: 79%).

Next, formula A-1 (2.2g, 3.93mmol), pinacol diboron (1.1g, 4.33mmol), potassium acetate (2.71g, 11.8mmol) were mixed in a nitrogen atmosphere, added to 120 ml of dioxane, and stirred while Heated. In a refluxed state, bis(dibenzylidineacetone)palladium (0.06g, 0.12mmol) and tricyclohexylphosphine (0.06g, 0.24mmol) were added, followed by heating and stirring for 12 hours. After the reaction was completed, 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 an intermediate compound A (1.54 g, yield: 65%).

MS[M+H] ⁺ = (607)

Preparation B: Preparation of intermediate compound B

In Preparation Example A, an intermediate compound was used in the same manner as in Preparation Example A, except that the starting material x-2 was used instead of the starting material x-1, and the starting material y-2 was used instead of the starting material y-1. Prepared B.

MS[M+H] ⁺ = 607

Preparation C: Preparation of intermediate compound C

In Preparation Example A, an intermediate compound was used in the same manner as in Preparation Example A, except that the starting material x-2 was used instead of the starting material x-1, and the starting material y-3 was used instead of the starting material y-1. Prepared C.

MS[M+H] ⁺ = 607

Preparation D: Preparation of intermediate compound D

In Preparation Example A, an intermediate compound was used in the same manner as in Preparation Example A, except that starting material x-2 was used instead of starting material x-1, and starting material y-4 was used instead of starting material y-1. D was prepared.

MS[M+H] ⁺ = 607

Preparation Example 1: Preparation of Compound 1

Compound A (9.90g, 16.34mmol), a-1 (5.97, 14.85mmol) was completely dissolved in 240ml of tetrahydrofuran in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120ml) was added, and tetrakis- (Triphenylphosphine) palladium (0.51g, 0.45mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 ml of tetrahydrofuran to prepare compound 1 (8.87g, 71%).

MS[M+H] ⁺ = 847

Preparation Example 2: Preparation of compound 3

Compound A (8.11 g, 13.39 mmol) and compound a-2 (6.34 g, 12.17 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.42 g, 0.37 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 390 mL of ethyl acetate to prepare compound 2 (6.44 g, 57%).

MS[M+H] ⁺ = 923

Preparation Example 3: Preparation of compound 3

Compound A (8.64 g, 14.25 mmol) and compound a-3 (6.75 g, 12.96 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.45 g, 0.39 mmol) was added, followed by heating and stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 340 mL of tetrahydrofuran to prepare compound 3 (8.89 g, 74%).

MS[M+H] ⁺ = 923

Preparation Example 4: Preparation of compound 4

Compound A (8.35 g, 13.77 mmol) and compound a-4 (6.51 g, 12.52 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.43 g, 0.38 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 mL of tetrahydrofuran to prepare compound 4 (7.46 g, 65%).

MS[M+H] ⁺ = 922

Preparation Example 5: Preparation of compound 5

Compound A (8.34 g, 13.76 mmol) and compound a-5 (6.69 g, 12.50 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.43 g, 0.38 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 290 mL of tetrahydrofuran to prepare compound 5 (7.23 g, 62%).

MS[M+H] ⁺ = 937

Preparation Example 6: Preparation of compound 6

Compound A (8.60 g, 14.19 mmol) and compound a-6 (7.11 g, 12.90 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.45 g, 0.39 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 mL of ethyl acetate to prepare compound 6 (6.92 g, 56%).

MS[M+H] ⁺ = 953

Preparation Example 7: Preparation of compound 7

Compound A (8.80g, 14.53mmol), a-7 (6.88, 13.21mmol) was completely dissolved in 240ml of tetrahydrofuran in a nitrogen atmosphere in a 500ml round bottom flask, and then 2M aqueous potassium carbonate solution (120ml) was added, and tetrakis- (Triphenylphosphine) palladium (0.46g, 0.40mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 ml of tetrahydrofuran to prepare compound 7 (8.88g, 73%).

MS[M+H] ⁺ = 923

Preparation Example 8: Preparation of compound 8

Compound B (9.76g, 16.10mmol), b-1 (6.47, 14.64mmol) was completely dissolved in 240ml of tetrahydrofuran in a 500ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120ml) was added, and tetrakis- (Triphenylphosphine) palladium (0.51g, 0.44mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of tetrahydrofuran to prepare compound 8 (7.46g, 57%).

MS[M+H] ⁺ = 887

Preparation Example 9: Preparation of compound 9

Compound B (8.56 g, 14.12 mmol) and compound b-2 (6.88 g, 12.84 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.44 g, 0.39 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 mL of tetrahydrofuran to prepare compound 9 (7.14 g, 57%).

MS[M+H] ⁺ = 981

Preparation Example 10: Preparation of Compound 10

Compound C (14.01 g, 23.12 mmol) and compound c-1 (8.05 g, 21.02 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.73 g, 0.63 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 mL of ethyl acetate to prepare compound 10 (11.19 g, 64%).

MS[M+H] ⁺ = 828

Preparation Example 11: Preparation of compound 11

Compound D (13.42 g, 22.14 mmol) and compound d-1 (7.69 g, 20.13 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.70 g, 0.60 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 mL of tetrahydrofuran to prepare compound 6 (10.09 g, 60%).

MS[M+H] ⁺ = 829

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

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

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, the deposition rate of aluminum was maintained 2Å / sec, the degree of vacuum upon deposition 2ⅹ10 ^-7 ~ An organic light emitting device was manufactured by maintaining ^{5x10 -6 torr.}

Examples 1-2 to 1-11

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

Comparative Examples 1-1 to 1-3

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1. The compounds of HB1, HB2, and HB3 used in Table 1 are as follows.

Experimental Example 1

When a current was applied to the organic light emitting device prepared in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime 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 retention stratum) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 1-1 Manufacturing Example 1 4.43 6.47 (0.146, 0.046) 260 Example 1-2 Manufacturing Example 2 4.42 6.45 (0.145, 0.045) 265 Example 1-3 Manufacturing Example 3 4.54 6.34 (0.145, 0.045) 245 Example 1-4 Manufacturing Example 4 4.59 6.22 (0.146, 0.046) 245 Example 1-5 Manufacturing Example 5 4.67 6.20 (0.147, 0.045) 230 Example 1-6 Manufacturing Example 6 4.58 6.38 (0.145, 0.046) 245 Example 1-7 Manufacturing Example 7 4.41 6.31 (0.146, 0.047) 260 Example 1-8 Manufacturing Example 8 4.50 6.39 (0.148, 0.045) 255 Example 1-9 Manufacturing Example 9 4.53 6.26 (0.146, 0.045) 240 Example 1-10 Manufacturing Example 10 4.54 6.32 (0.145, 0.046) 245 Example 1-11 Manufacturing Example 11 4.52 6.34 (0.146, 0.045) 255 Comparative Example 1-1 HB1 4.95 5.80 (0.146, 0.046) 175 Comparative Example 1-2 HB2 4.81 5.93 (0.145, 0.047) 160 Comparative Example 1-3 HB3 5.33 5.6 (0.145, 0.045) 115

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

In Examples 1-1 to 1-11, the organic light emitting device using the compound of the present invention dispiro[fluorene-9,9'-anthracene-10',9''-fluorene] at least one adamantane group in the core structure Compared to the organic light-emitting devices of Comparative Examples 1-1, 1-2, and 1-3 prepared using HB1, HB2, and HB3 materials in which the triazine-based substituents contained therein were not substituted, characteristics of lower voltage, high efficiency, and longer life were shown.

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 block

Claims (7)

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

In Formula 1,
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 a substituted or unsubstituted C _6-60 arylene,
Ar ₁ and Ar ₂ are each independently adamantyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of _{Ar 1} and Ar _{2 is adamantyl,}
R ₁ , R ₂ , and R ₃ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl,
m, n and o are each independently an integer of 0 to 7.
The method of claim 1,
The compound represented by Formula 1 is a compound represented by the following Formula 1-1 or Formula 1-2:
[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,
X ₁ , X ₂ , X ₃ , L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , R ₃ , m, n and o are as defined in claim 1.
The method of claim 1,
L ₁ , L ₂ and L ₃ are each independently a single bond; Phenylene; Biphenylylene; Or naphthylene.
The method of claim 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, a compound:

Above,
R _'1 and R' ₂ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-10 alkyl; Or a substituted or unsubstituted C _6-12 aryl,
p is an integer from 0 to 5.
The method of claim 1,
R ₁ , R ₂ and R ₃ are each independently hydrogen; Or deuterium.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
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 according to any one of claims 1 to 6 That is, an organic light emitting device.

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