KR20210089526A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The present invention provides the novel compound and the organic light emitting device comprising the same. The present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 described above can be used as a material for an organic material layer of the organic light emitting device, and also 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 emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and 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 layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may include, for example, 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 the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

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

Meanwhile, in order to reduce process costs, an organic light emitting diode using a solution process, particularly an inkjet process, has been developed instead of a conventional deposition process. In the early days, it was attempted to develop an organic light emitting device by coating all organic light emitting device layers with a solution process, but current technology has limitations. A hybrid process using

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

Korean Patent Publication No. 10-2013-073537

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

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

[Formula 1]

In Formula 1,

two * are each connected to two adjacent carbons among _{C 1} , C ₂ and C _{3 ,}

two *' are each connected to two adjacent carbons among _{C' 1} , C' ₂ and C' _3,

R ₁ and R ₂ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted unsubstituted C _6-60 aryl, N, O, S and Si _{substituted or unsubstituted C 5-60} heteroaryl containing one or more heteroatoms selected from, or R ₁ and R ₂ are combined with each other to form a C _6-60 spiro ring,

L ₁ , L ₂ , L′ ₁ and L′ ₂ are each independently a direct bond, or a substituted or unsubstituted C _6-60 arylene;

Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ are each independently, substituted or unsubstituted unsubstituted C _6-60 aryl, or at least one hetero selected from the group consisting of N, O, S and Si _{substituted or unsubstituted C 5-60} heteroaryl containing atoms, provided that at least one of Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ is selected from the group consisting of N, O, S and Si _{substituted or unsubstituted C 5-60} heteroaryl containing one or more heteroatoms,

Ar ₃ and Ar′ ₃ are each independently a substituted or unsubstituted unsubstituted C _6-60 aryl.

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 organic material layer includes the compound of the present invention.

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

1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 is an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron injection and transport layer 8, and a cathode 4 will show

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

(Definition of Terms)

는 다른 치환기에 연결되는 결합을 의미한다. 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; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but 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, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic 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 the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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 number of carbon atoms in the alkyl group is 1 to 20. 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, 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 and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 carbon number of the cycloalkyl group is 3 to 20. 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 is not limited thereto.

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

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including 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 from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an 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 group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

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

(compound)

The present invention provides a compound represented by the above formula (1).

Preferably, the compound represented by Formula 1 is represented by the following Formulas 1-1 to 1-9:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In Formulas 1-1 to 1-9,

R ₁ , R ₂ , Ar ₁ , Ar′ ₁ , Ar ₂ , Ar′ ₂ , Ar ₃ , Ar′ ₃ , L ₁ , L′ ₁ , L ₁ and L′ ₁ are as defined above.

,

,

,

또는

의 스피로 고리를 형성하고, 여기서 *는 스피로 결합 위치이다. 상기 페닐 및 스피로 고리는 각각 독립적으로 비치환되거나; 또는 C_1-10 알킬, 페녹시 또는 할로겐으로 하나 이상 치환된다.Preferably, R ₁ and R ₂ are each independently C _1-10 alkyl, phenyl or pyridinyl, or R ₁ and R ₂ are bonded to each other

,

,

,

or

form a spiro ring of , where * is the spiro bond position. the phenyl and spiro rings are each independently unsubstituted; or _{one or more substituted with C 1-10} alkyl, phenoxy or halogen.

Preferably, L ₁ , L ₂ , L′ ₁ and L′ ₂ are each independently a direct bond; phenylene; or naphthylene.

Preferably, Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dimethylbenzo Fluorenyl, diphenylfluorenyl, diphenylbenzofluorenyl, pyridinyl, benzoimidazolyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, benzothiophenyl, dibenzothiophenyl, benzonaph tothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, diphenyltriazine, or dihydroacridinyl;

Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ are each independently unsubstituted; or one or more substituted with _{C 1-10} alkyl, halogen, phenyl, tri(C _1-10 alkyl)silyl or tri(C _{6-30 aryl)silyl,}

provided _{that at least one of Ar 1} , Ar ₂ , Ar′ ₁ and Ar′ ₂ is pyridinyl, benzoimidazolyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, benzothiophenyl, dibenzothiophenyl, benzonaphthothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, diphenyltriazine, or dihydroacridinyl.

Preferably, Ar ₃ and Ar′ ₃ are each independently phenyl, biphenylyl, pyridine, or dimethylfluorenyl,

Ar ₃ and Ar′ ₃ are each independently unsubstituted; or methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.

Representative examples of the compound represented by Formula 1 are as follows:

.

.

The compound represented by Formula 1 according to the present invention may be used as a material for an organic layer of an organic light emitting device, and may improve efficiency, low driving voltage and/or lifespan characteristics in an organic light emitting device. In addition, compared to conventional materials, it has an emission profile for optimal device performance and has an advantage in that processability is improved by increasing solubility. In particular, the compound represented by the above formula (1) can be applied to a solution process, and can be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

The compound represented by Formula 1 may be prepared through the following Reaction Scheme A.

[Scheme A]

In Scheme A, definitions of other substituents except for X and X' are the same as those described above, and X and X' are halogen, and preferably each independently represent bromo or chloro.

Scheme A is an amination reaction, preferably performed in the presence of a palladium catalyst and a base, and the catalyst, solvent, etc. for the reaction can be changed as known in the art.

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

(Coating composition)

The compound according to the present invention may form an organic material layer of an organic light emitting device, particularly a light emitting layer, by a solution process. To this end, the present invention provides a coating composition comprising the above-described compound according to the present invention and a solvent.

The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the compound according to the present invention, and for example, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o - Chlorine solvents, such as dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, and 1,2-hexanediol alcohols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; benzoate solvents such as butyl benzoate and methyl-2-methoxy benzoate; tetralin; and solvents such as 3-phenoxy-toluene. In addition, the above-mentioned solvents may be used alone or as a mixture of two or more solvents.

In addition, the viscosity of the coating composition is preferably 1 cP to 10 cP, and coating is easy in the above range.

In addition, the present invention provides a method of forming a light emitting layer using the above-described coating composition. Specifically, on the positive electrode, or on the hole transport layer formed on the positive electrode, coating the above-described coating composition according to the present invention in a solution process; and heat-treating the coated coating composition.

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

The heat treatment temperature in the heat treatment step is preferably 150 to 230 ℃. In addition, the heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen. In addition, it may further include the step of evaporating the solvent between the coating step and the heat treatment step.

(organic light emitting element)

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1).

In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 according to the present invention. provides

Preferably, at least one layer of the organic material layer further includes a compound represented by the following formula (2) in addition to the compound represented by the formula (1):

[Formula 2]

In Formula 2,

L and L' are each independently a direct bond, a substituted or unsubstituted C _6-60 arylene, or a substituted or unsubstituted C _5-60 heteroarylene,

Ar and Ar' are each independently substituted or unsubstituted unsubstituted C _6-60 aryl, or substituted or unsubstituted containing one or more heteroatoms selected from the group consisting of N, O, S and Si C _5-60 heteroaryl.

Preferably, the organic material layer may be a light emitting layer, wherein the compound represented by Formula 1 may be used as a dopant material, and the compound represented by Formula 2 may be used as a host material, but is not limited thereto.

Preferably, L and L' are each independently a direct bond, phenylene, naphthylene, dibenzofuranylene, or dibenzothiophenylene.

Preferably, Ar and Ar' are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenalthrenyl, dibenzofuranyl, benzonaphthofuranyl, dibenzothiophenyl or benzonaphthothiophenyl to be.

Representative examples of the compound represented by Formula 5 are as follows:

.

.

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

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

2 is an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron injection and transport layer 8, and a cathode 4 will show In such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the light emitting layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except for using the compound according to the present invention.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and 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 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.

In addition to this 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.

In one 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 generally preferable to facilitate hole injection into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SNO _{2 :Sb;} conductive compounds such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect with respect to the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. Preferably, the highest occupied molecular orbital (HOMO) 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 the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive compounds, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that can transport holes from the anode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion together.

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

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

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

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

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

[Example]

Example 1-1) Preparation of Intermediate 1

9,9-dimethylfluorene-2,7-diboronic acid (13 g, 46 mmol), 1-bromo-4-chloro-2-nitrobenzene (26 g, 11 mmol) in a 500 mL round-bottom flask under nitrogen atmosphere ), tetrakis (triphenylphosphine) palladium (2.7 g, 2.3 mmol), potassium carbonate (19.1 g, 138 mmol) were added, and 1,4-dioxane 300 mL and water 60 mL were added. The temperature of the reactor ^{was raised to 100 o} C and stirred for 24 hours. When the reaction is complete, the temperature is lowered to room temperature, water is added to precipitate a solid, and the solid is filtered. Ethanol is added to the filtered solid and stirred to dissolve only impurities and filter. The solid insoluble in ethanol was dissolved in tetrahydrofuran, and then Intermediate 1 (20.2 g, yield 80%) was obtained through crystallization with ethanol.

Example 1-2) Preparation of intermediates 2-1 to 2-3

Intermediate 1 (20.2 g, 40 mmol) and triphenylphosphine (52.5 g, 0.2 mol) were placed in a 500 mL round-bottom flask in a nitrogen atmosphere, and 300 mL of dichlorobenzene was added. The temperature of the reactor ^{was raised to 180 o} C and stirred for 24 hours. When the reaction is complete, the temperature is lowered to room temperature and passed through a Celite filter using a tetrahydrofuran solvent. The filtered filtrate was concentrated and crystallized with hexane to obtain a solid, and intermediates 2-1, 2-2, and 2-3 (56% mixed yield) were each prepared in a ratio of 1:1:2 using hexane/ethyl acetate chromatography separation method. obtain

Example 1-3) Preparation of Intermediate 3-1

Intermediate 2-1 (2.5 g, 5.6 mmol), iodobenzene (8.1 g, 39.8 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.1 mmol), sodium tertbutoxide ( 3.3 g, 33.9 mol) and 200 mL of toluene were added and stirred at 80° C. for 14 hours. Upon completion of the reaction, the mixture was cooled to room temperature and filtered through a celite layer using toluene. After concentrating the filtrate, ethanol is added to the obtained organic material to dissolve only impurities. It was recrystallized using tetrahydrofuran/hexane to obtain Intermediate 3-1 (2.6 g, yield 77%).

Example 1) Preparation of compound BD 1

Intermediate 3-1 (2.6 g, 4.3 mmol), 4-benzofuran-2-N-(4-(tert-butyl)phenyl)aniline (3.2 g, 9.5 mmol), bis(tri -tert-butylphosphine)palladium(0) (0.23 g, 0.4 mmol), sodium tert-butoxide (0.9 g, 9.5 mmol) and 150 mL of toluene were added and stirred at 105° C. for 20 hours. Upon completion of the reaction, after cooling to room temperature, water is added, the precipitate is filtered, and then washed with methanol and toluene to obtain an organic material. The produced organic material is dissolved in dichloromethane, passed through acid alumina and celite filter, and then concentrated. After purification by column chromatography separation using normal hexane and dichloromethane, the solvent was removed to obtain compound BD 1 (2.6 g, yield 51%). MS[M+H] ⁺ = 1202.55

Example 2) Preparation of compound BD 2

In the synthesis of Intermediate 1, 9,9-diphenylfluorene-2,7-diboronic acid was used instead of 9,9-dimethylfluorene-2,7-diboronic acid, and in the synthesis method of Intermediate 3, 4- instead of iodobenzene Compound BD 2 (3.7 g, yield 59%) was obtained in the same manner as in the preparation of Compound BD 1, except that (tert-butyl)iodobenzene was used.

MS[M+H] ⁺ = 1438.71

Example 3) Preparation of compound BD 3

The same method as for the preparation of compound BD 1, except that N-phenyldibenzofuran-4-amine was used instead of 4-(benzofuran-2-)-N-(4-(tert-butyl)phenyl)aniline. to obtain compound BD 3 (3.1 g, yield 69%).

MS[M+H] ⁺ = 1038.39

Example 4) Preparation of compound BD 4

In the synthesis of Intermediate 3-1, 4-(tert-butyl)iodobenzene was used instead of iodobenzene, and 4-(benzofuran-2-)-N-(4-(tert-butyl)phenyl)aniline was replaced with 6- Compound BD 4 (1.7 g, yield 65%) in the same manner as in the preparation method of Compound BD 1, except that benzofuran-2-N-(4-(tert-butyl)phenyl)naphthalen-2-amine was used. got

MS[M+H] ⁺ = 1276.52

Example 5) Preparation of compound BD 5

In the synthesis of Intermediate 1, 9,9-diphenylfluorene-2,7-diboronic acid was used instead of 9,9-dimethylfluorene-2,7-diboronic acid, and 4-benzofuran-2-N- (4 Preparation of compound BD 1, except that N-(3-(carbazole-9)-phenyl)-[1,1'-biphenyl]-4-amine was used instead of -(tert-butyl)phenyl)aniline Compound BD 5 (3.8 g, yield 61%) was obtained by the same method as the method.

MS[M+H] ⁺ = 1464.58

Example 6) Preparation of compound BD 6

In the synthesis of Intermediate 1, 9,9'-spirobifluorene-2,7-diboronic acid was used instead of 9,9-dimethylfluorene-2,7-diboronic acid, and 4-benzofuran-2-N-( Except for using N-(4-(benzofuran-2)-phenyl)-[1,1'-biphenyl]-3-amine instead of 4-(tert-butyl)phenyl)aniline, Compound BD 6 (3.6 g, yield 62%) was obtained in the same manner as in the preparation method.

MS[M+H] ⁺ = 1364.50

Example 7) Preparation of compound BD 7

Compound BD 7 (3.1 g, yield 55%) was obtained in the same manner as in the preparation of Compound BD 4, except that Intermediate 2-2 was used instead of Intermediate 2-1 in the synthesis of Intermediate 3.

MS[M+H] ⁺ = 1302.58

Example 8) Preparation of compound BD 8

In the synthesis of Intermediate 3, Intermediate 2-3 is used instead of Intermediate 2-1, and 6-benzofuran-2-N-phenylnaphthalene-2 is used instead of benzofuran-2-N-(4-(tert-butyl)phenyl)aniline. - Compound BD 8 (2.6 g, yield 59%) was obtained in the same manner as in the preparation of Compound BD 1, except that an amine was used.

MS[M+H] ⁺ = 1038.39

[Experimental example]

Experimental Example 1)

A glass substrate on which indium tin oxide (ITO) was deposited to a thickness of 1,500 Å was placed in distilled water in which detergent was dissolved, and washed with ultrasonic waves. The ITO was washed for 30 minutes. Then, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing with a solvent of isopropyl alcohol and acetone was performed for 30 minutes each and dried, and then the substrate was transported to a glove box.

A coating composition in which the following compound A and compound IB (p-dopant) were dissolved in cyclohexanone (solvent) at 2 wt% in a weight ratio of 8:2 on the ITO transparent electrode thus prepared was spin-coated to inject a hole having a thickness of 300 Å A layer was formed, and the coating composition was cured at 220° C. and 30 minutes on a hot plate under a nitrogen atmosphere. On the hole injection layer, a composition obtained by dissolving the following compound A in toluene at 1 wt% was spin-coated to form a hole transport layer having a thickness of 400 Å. Thereafter, the coating composition was cured at 230° C. and 30 minutes on a hot plate under a nitrogen atmosphere. On the hole transport layer, a composition in which the following compound B and the previously prepared compound BD 1 were dissolved in toluene at 0.6 wt% (compound B: weight ratio of compound BD 1 = 98:2) was spin-coated to form a 200 Å thick light emitting layer The coating composition was cured at 120° C. and 10 minutes on a hot plate under a nitrogen atmosphere. Thereafter, the following compound G (200 Å), LiF (12 Å), and Al (2000 Å) were sequentially deposited on the light emitting layer by transferring to a vacuum evaporator to prepare an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of LiF of the cathode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 to 5×10 ⁻⁸ torr were maintained.

Experimental Examples 2 to 8)

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of Compound BD 1.

Comparative Experimental Examples 1 to 4)

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of Compound BD 1. Compounds C, D, E and F in Table 1 are as follows, respectively.

For the organic light-emitting devices prepared in the Experimental Examples and Comparative Experimental Examples, the maximum emission wavelength, full width at half maximum, current efficiency and quantum efficiency were measured at a current density of ^{10 mA/cm 2 , and the results are shown in Table 1 below.}

division compound maximum emission wavelength
(nm) half full width
(nm) current efficiency
(cd/A) quantum efficiency
(%) Experimental Example 1 compound BD 1 450 33 5.7 7.36 Experimental Example 2 compound BD 2 455 35 6.4 8.45 Experimental Example 3 compound BD 3 448 33 5.9 7.85 Experimental Example 4 compound BD 4 456 31 6.8 7.98 Experimental Example 5 compound BD 5 455 29 7.8 8.57 Experimental Example 6 compound BD 6 454 28 6.9 7.76 Experimental Example 7 compound BD 7 452 28 7.5 7.68 Experimental Example 8 Compound BD 8 459 33 7.1 8.35 Comparative Experimental Example 1 compound C 441 40 4.5 5.94 Comparative Experimental Example 2 compound D 443 41 4.4 6.21 Comparative Experimental Example 3 compound E 449 39 3.9 6.65 Comparative Experimental Example 4 compound F 443 36 4.6 7.13

As shown in Table 1, it was confirmed that the organic light emitting device using the compound of the present invention as a dopant in the light emitting layer exhibited remarkable effects in terms of maximum emission wavelength, full width at half maximum, current efficiency or quantum efficiency.

The maximum emission wavelength is 450 nm to 460 nm, and the smaller the full width at half maximum, the better the viewing angle is improved in the display device, the better the color purity, and the current efficiency and quantum efficiency in the deep blue region can be increased, when the compound of the present invention is used In the wavelength region, it was confirmed that the full width at half maximum was 35 nm or less.

Specifically, Experimental Examples 1 to 8 using a compound in which a ring is condensed with fluorene and an amine group including at least one heteroaryl group is bonded to both sides of the light emitting layer has a maximum emission wavelength compared to Comparative Experimental Examples 1 to 4 It increased up to 18 nm, the full width at half maximum decreased up to 13 nm, the current efficiency increased up to about 100%, and the quantum efficiency increased up to about 44%.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron injection and transport layer

Claims (11)

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

In Formula 1,
two * are each connected to two adjacent carbons among _{C 1} , C ₂ and C _{3 ,}
two *' are each connected to two adjacent carbons among _{C' 1} , C' ₂ and C' _3,
R ₁ and R ₂ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted unsubstituted C _6-60 aryl, N, O, S and Si _{substituted or unsubstituted C 5-60} heteroaryl containing one or more heteroatoms selected from, or R ₁ and R ₂ are combined with each other to form a C _6-60 spiro ring,
L ₁ , L ₂ , L′ ₁ and L′ ₂ are each independently a direct bond, or a substituted or unsubstituted C _6-60 arylene;
Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ are each independently, substituted or unsubstituted unsubstituted C _6-60 aryl, or at least one hetero selected from the group consisting of N, O, S and Si _{substituted or unsubstituted C 5-60} heteroaryl containing atoms, provided that at least one of Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ is selected from the group consisting of N, O, S and Si _{substituted or unsubstituted C 5-60} heteroaryl containing one or more heteroatoms,
Ar ₃ and Ar′ ₃ are each independently a substituted or unsubstituted unsubstituted C _6-60 aryl.
According to claim 1,
The compound represented by Formula 1 is a compound represented by the following Formulas 1-1 to 1-9:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In Formulas 1-1 to 1-9,
R ₁ , R ₂ , Ar ₁ , Ar′ ₁ , Ar ₂ , Ar′ ₂ , Ar ₃ , Ar′ ₃ , L ₁ , L′ ₁ , L ₂ and L′ ₂ are as defined in claim 1.
According to claim 1,
R ₁ and R ₂ are each independently C _1-10 alkyl, phenyl or pyridinyl, or R ₁ and R ₂ are bonded to each other

,

,

,

or

form a spiro ring of, where * is the spiro bond position,
the phenyl and spiro rings are each independently unsubstituted; or _{one or more substituted with C 1-10} alkyl, phenoxy or halogen.
According to claim 1,
L ₁ , L ₂ , L′ ₁ and L′ ₂ are each independently a direct bond; phenylene; or naphthylene.
According to claim 1,
Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dimethylbenzofluorenyl, Diphenylfluorenyl, diphenylbenzofluorenyl, pyridinyl, benzoimidazolyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, benzothiophenyl, dibenzothiophenyl, benzonaphthothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, diphenyltriazine, or dihydroacridinyl;
Ar ₁ , Ar ₂ , Ar′ ₁ and Ar′ ₂ are each independently unsubstituted; or one or more substituted with _{C 1-10} alkyl, halogen, phenyl, tri(C _1-10 alkyl)silyl or tri(C _{6-30 aryl)silyl,}
provided _{that at least one of Ar 1} , Ar ₂ , Ar′ ₁ and Ar′ ₂ is pyridinyl, benzoimidazolyl, benzofuranyl, dibenzofuranyl, benzonaphthofuranyl, benzothiophenyl, dibenzothiophenyl, benzonaphthothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, diphenyltriazine, or dihydroacridinyl.
According to claim 1,
Ar ₃ and Ar′ ₃ are each independently phenyl, biphenylyl, pyridine, or dimethylfluorenyl,
Ar ₃ and Ar′ ₃ are each independently unsubstituted; or methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.
According to 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 7 which is an organic light emitting device.
9. The method of claim 8,
The organic material layer is a light emitting layer, an organic light emitting device.
10. The method of claim 9,
The light emitting layer further comprises a compound represented by the following formula (2), an organic light emitting device:
[Formula 2]

In Formula 2,
L and L' are each independently a direct bond, a substituted or unsubstituted C _6-60 arylene, or a substituted or unsubstituted C _5-60 heteroarylene,
Ar and Ar' are each independently substituted or unsubstituted unsubstituted C _6-60 aryl, or substituted or unsubstituted containing one or more heteroatoms selected from the group consisting of N, O, S and Si C _5-60 heteroaryl.
11. The method of claim 10,
The compound represented by Formula 2 is any one selected from the group consisting of:

.

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