KR20210023254A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound represented by chemical formula 1 and an organic light emitting device using the same. The compound may improve lifespan characteristics of the organic light emitting device.

Description

Novel compound and organic light emitting device using the same {NOVEL COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present invention relates to a novel compound and an organic light emitting device comprising 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 multilayer structure made 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, etc. 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.

On the other hand, in recent years, in order to reduce process cost, an organic light emitting device using a solution process, especially an inkjet process, has been developed instead of a conventional deposition process. In the early days, an attempt was made to develop an organic light-emitting device by coating all organic light-emitting device layers by a solution process, but the current technology has limitations, so only HIL, HTL, and EML are processed as a solution process in the form of a regular structure, and the later process is the existing deposition process. A hybrid process that utilizes is being studied.

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

Korean Patent Publication No. 10-2000-0051826

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,

X is O, S, C(R') ₂ , or Si(R') ₂

At least one of R ₁ is a substituent represented by the following formula (2), and the others are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

R ₂ is hydrogen; Or substituted or unsubstituted C _1-60 alkyl,

R'is substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl,

n is an integer from 0 to 4,

a is an integer of 1 to 2,

b is an integer from 0 to 2,

[Formula 2]

In Chemical Formula 2,

Y is O, or S,

Each R ₃ is independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S, or two adjacent substituents are bonded to form a C _6-60 aromatic ring and,

m is an integer from 0 to 5.

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 comprises a compound represented by Formula 1 to provide.

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 described above can be applied to a solution process, and can 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 light-emitting layer 3, and a cathode 4.
2 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

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, isoxazolyl group, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, 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.

The present invention provides a compound represented by Chemical Formula 1. The compound represented by Formula 1 has an asymmetric structure, and is a polycyclic anti-aromatic compound in which a plurality of aromatic rings are connected with a boron atom and a nitrogen atom, and at least one aromatic ring connected to a ring containing both a boron atom and a nitrogen atom. Including the heteroaryl substituent, the solubility in the solvent used in the solution process is high, and the characteristics of the organic light emitting device using the same can be improved. In particular, the compound represented by Chemical Formula 1 can exhibit better luminescence properties by increasing the rigidity of molecules by using a polycyclic aromatic core connecting a plurality of aromatic rings, thereby improving quantum efficiency and lifespan. I can.

In Formula 1, preferably, X is O, S, C(R') ₂ , or Si(R') ₂ , where R'is a substituted or unsubstituted C _1-4 alkyl. Preferably, R'is methyl. Preferably, X is O, S, CH ₂ , C(CH ₃ ) ₂ , or Si(CH ₃ ) ₂ .

Preferably _{, at least one of R 1} is a substituent represented by Formula 2, and the others are each independently hydrogen; _{C 6-60} aryl unsubstituted or substituted with C _{1-4 alkyl; Or substituted or unsubstituted C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S. Preferably, R ₁ is hydrogen, methyl, phenyl, tert-butyl, 4-(tert-butyl)phenyl, biphenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, or dibenzothiophenyl. In addition, _{at least one of R 1} is benzofuranyl, benzothiophenyl, dibenzofuranyl, or dibenzothiophenyl, more preferably benzofuranyl or dibenzofuranyl.

Preferably, R ₂ is hydrogen or methyl. Preferably, n is 0 or 2. Preferably, a is 1 or 2 and b is 0, 1 or 2.

In Formula 2, preferably, R ₃ is hydrogen.

Preferably, Formula 2 is represented by the following Formula 2-1 or Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, Y is each independently O or S.

Preferably, Y is O. Preferably, m is 0.

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

On the other hand, the compound represented by Formula 1 can be prepared by the same manufacturing method as in Reaction Schemes 1 to 2 below. The manufacturing method may be more specific in the synthesis examples to be described later.

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, X, R ₁ , R ₂ , n, a, b are as defined in Formula 1, and X ₁ and X ₂ are each independently a halogen group, preferably Cl, Br, or I to be.

After preparing the precursor material through Scheme 1, the compound represented by Formula 1 may be finally prepared through Scheme 2.

Specifically, Reaction Scheme 1 utilizes the Buchwald-Hartwig reaction, and under base conditions such as tert-butoxy sodium (NaOtBu), Bis(tri-(tert-butyl)phosphine)palladium(0) (BTP, Pd (t-Bu ₃ P) may be carried out by introducing the palladium catalyst (Pd catalyst) ₂ and the like. the reaction temperature for the above reaction scheme 1 can be carried out at about 70 ℃ to about 110 ℃, or from about 80 ℃ to about 100 ℃ I can.

In addition, Reaction Scheme 2 may consist of performing a halogen removal reaction (dehalogenation) from the precursor material prepared as described above, and performing a cyclization reaction by introducing a boron compound such as _{BBr 3.} In this case, the halogen removal reaction (dehalogenation) may be performed using tert-butyllithium (t-BuLi). In addition, the cyclization reaction _{can be carried out under a base condition such as N-diisopropylethylamine (EtNiPr 2} ,), and the reaction temperature is from about 100 °C to about 160 °C or from about 120 °C to about 150 °C. You can do it.

Meanwhile, in the present specification, the equivalent (eq.) means a molar equivalent.

In addition, 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 do.

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, 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 above.

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

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons includes the compound represented by Formula 1 above.

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

In addition, the organic light-emitting device according to the present invention may be a normal type organic light-emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light-emitting device according to the present invention may be an 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 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 light-emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 I did it. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer. Specifically, the compound represented by Formula 1 may be included in the emission layer, for example, may be included as a dopant material for the emission 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. In particular, the compound represented by Formula 1 has excellent solubility in a solvent used in the solution coating method, so that it is easy to apply the solution coating method. 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.

Accordingly, the present invention provides a coating composition comprising the compound represented by Chemical Formula 1 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 examples include 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, 1,2-hexanediol, etc. Alcohol and its derivatives; 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-methoxybenzoate; Tetralin; Solvents, such as 3-phenoxy-toluene, are mentioned. In addition, the above-described solvent may be used alone or in combination of two or more solvents.

Further, the viscosity of the coating composition is preferably 1 cP to 10 cP, and coating is easy within the above range. In addition, it is preferable that the concentration of the compound according to the present invention in the coating composition is 0.1 wt/v% to 20 wt/v%.

In addition, the present invention provides a method of forming a functional layer using the above-described coating composition. Specifically, coating the coating composition according to the present invention described above by a solution process; And heat-treating the coated coating composition.

In the heat treatment step, the heat treatment temperature is preferably 150 to 230 °C. 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.

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 light emitting layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, 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.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, 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, and styryltetraamine, but are not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex. Preferably, the compound according to the invention is used as the dopant material.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons 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 can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

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 for the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. 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-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

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

The 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.

[Synthesis Example]

<Synthesis Example 1>

(1) Synthesis of Intermediate 1-1

Phenoxazine (10 g, 1 eq.), 1-bromo-2,3-dichloro-5-methylbenzene (14.4 g, 1.1 eq.), tert-butoxy sodium (NaOtBu, 18.37 g, 3.5 eq.) Was placed in a round bottom flask (two-neck RB) and replaced with nitrogen. At 80 ℃, add 150 mL of toluene and Bis(tri-(tert-butyl)phosphine)palladium(0) (BTP, Pd(t-Bu ₃ P) ₂ , 1.1 g, 5 mol%) overnight. Stir at reflux (overnight). After separating the organic layer by washing with dichloromethane/water (DCM/H _{2 O), MgSO 4} and charcoal (activated carbon, charcoal) were added and stirred for 30 minutes. After passing through a Silica/Celite pad and drying the organic solvent in vacuo, a mixed solvent of dichloromethane:hexane = 1:9 by volume is used as an eluent to be purified by medium pressure liquid chromatography (MPLC). 1-1 was obtained (13.4 g).

(2) Synthesis of Intermediate 1-2

Benzofuran-2-ylboronic acid (15.53 g, 1.1 eq.), 4-bromoaniline (15 g, 1 eq.), tetrakis(triphenylphosphine) palladium(0) (Pd(PPh ₃ ) ₄ , 5 g, 5 mol%) , K ₂ CO ₃ (36.14 g, 3 eq.) was placed in a round bottom flask and replaced with nitrogen. The temperature was raised to 110° C., 250 mL of 1,4-dioxane and _{65 mL of H 2} O were added and stirred under reflux overnight. After washing with DCM/H ₂ O to separate the organic layer, MgSO ₄ and charcoal were added and stirred for 30 minutes. After passing through a Silica/Celite pad, drying the organic solvent in vacuo, purifying by column chromatography (MPLC) with eluent in the ratio of ethyl acetate (EA, ethyl acetate):hexane (Hex) = 1:3 based on volume , ethanol)/Hex precipitation to obtain Intermediate 1-2 (2.3 g).

(3) Synthesis of Intermediate 1-3

Intermediate 1-2 (5 g, 1 eq.) and 4-bromo-4'-(tert-butyl)-2,5-dimethyl-1,1'-biphenyl (8.7 g, 1.15 eq.), NaOtBu ( 8.04 g, 3.5 eq.) was added to the two-neck RB and replaced with nitrogen. The temperature was raised to 80° C., 250 mL of toluene and BTP (0.61 g, 5 mol%) were added and stirred under reflux. After 1 hour, the organic layer was separated by washing with _{DCM/H 2 O, and MgSO 4} and charcoal were added thereto, followed by stirring for 30 minutes. After passing through a Silica/Celite pad, the organic solvent was dried in vacuo, and purified by column chromatography (MPLC) with eluent in a ratio of dichloromethane:hexane=1:4 by volume, and 99.45% purity intermediate 1-3 was obtained (7.38) g, white powder).

(4) Synthesis of Precursor 1

Intermediate 1-1 (2 g, 1 eq.), Intermediate 1-3 (1.689 g, 1.1 eq.), and NaOtBu (1.5 g, 3.5 eq.) were added to a two-neck RB and replaced with nitrogen. The temperature was raised to 80° C., 80 mL of toluene and BTP (0.1 g, 5 mol%) were added and stirred under reflux overnight. After washing with DCM/H ₂ O to separate the organic layer, MgSO ₄ and charcoal were added and stirred for 30 minutes. After passing through a Silica/Celite pad and drying the organic solvent in vacuo, MPLC purification was performed with an eluent of dichloromethane:hexane = 1:4 to obtain a precursor 1 (0.66 g, white powder).

(5) Synthesis of Compound 1

In a 50 mL round bottom flask (two-neck 50 mL RB), the precursor 1 (0.66 g, 1 eq.) was dissolved in 20 mL of anhydrous tert-butylbenzene, and the bath temperature was -30 °C. After cooling by furnace, it stirred. 1.7 M tert-butyllithium (t-BuLi, 1.7 mL) was slowly added dropwise to the reaction product, and the color of the solution turned yellow. After raising the bath temperature from -30 °C to 60 °C (the solution turned red), the mixture was stirred for 3 hours. After drying under reduced pressure for 10 minutes using a handy pump to remove the organic solvent (pentane) used in the reaction, the bath temperature was cooled to -30 °C, BBr ₃ (0.1 mL) was slowly added, followed by stirring for 1 hour. After raising the bath temperature from -30 ℃ to 0 ℃, after 10 minutes, N,N-diisopropylethylamine (EtNiPr ₂ , 0.3 mL) was added dropwise, stirred at room temperature until the heat was cooled, and then the bath temperature was set to 150 ℃. The temperature was raised and the mixture was stirred under reflux for 3 hours. The reaction product was _{washed with toluene/NH 4} Cl (aq.) to separate the organic layer, and then MgSO ₄ was used, and the organic solvent was removed by drying under reduced pressure. The final product, Compound 1, was obtained through MPLC purification. MS: [M+H] ⁺ =724.33

<Synthesis Example 2>

After intermediate 2-1 was synthesized in the same manner as in Synthesis Example 1 (1), in Synthesis Example 1 (4) instead of Intermediate 1-3, Intermediate 2-3, that is, bis(4-(benzofuran- Using 2-yl)phenyl)amine, a final product, Compound 2 was obtained in the same manner as in Synthesis Example 1, except that the intermediate 2-1 and the intermediate 2-3 were reacted. MS: [M+H]+=680.23

<Synthesis Example 3>

After intermediate 3-1 was synthesized in the same manner as in Synthesis Example 1 (1), in Synthesis Example 1 (4) instead of Intermediate 1-3, Intermediate 3-3, that is, bis(4-(dibenzofuran-) Using 3-yl)phenyl)amine, a final product, Compound 3, was obtained in the same manner as in Synthesis Example 1, except that the intermediate 3-1 and the intermediate 3-3 were reacted. MS: [M+H]+=780.26

[Example]

<Example 1>

A glass substrate on which a thin film of ITO (indium tin oxide) was deposited to a thickness of 500 Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, as a detergent, a product made by Fisher Co. was used, and as distilled water, distilled water secondarily filtered by a filter manufactured by Millipore Co. was used. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water was finished, ultrasonic cleaning was performed with acetone, distilled water, and isopropyl alcohol solvent, followed by drying, to prepare a cleaned ITO transparent electrode.

On the ITO transparent electrode, a composition obtained by mixing the following compound Z-1 and the following compound Z-2 at a weight ratio of 8:2 was spin-coated and cured under a nitrogen atmosphere at 220 degrees Celsius (℃) on a hot plate for 30 minutes. A hole injection layer having a thickness of 400 angstroms (Å) was formed.

On the hole injection layer, a composition obtained by dissolving the compound Z-1 in toluene at a weight ratio of 1% was spin-coated and cured on a hot plate at 200° C. for 30 minutes to form a hole transport layer having a thickness of 200 angstroms (Å). I did.

On the hole transport layer, the following Compound Z-3 and Compound 1 (Compound 1) prepared in Synthesis Example 1 were dissolved in toluene in a weight ratio of 0.5% (wt%, wt%) in a ratio of 96:4 (based on weight). The coating composition was spin-coated and dried on a hot plate under a nitrogen atmosphere at 120° C. for 10 minutes to form a light emitting layer having a thickness of 200 angstroms (Å).

Then, the following compound Z-4 (thickness: 300 Å), LiF (thickness: 10 Å), and Al (thickness: 1,000 Å) were sequentially deposited to fabricate an organic light emitting device. In the above process, the deposition rate of LiF as the cathode material was maintained at 0.1 angstroms per second (Å/sec), and the deposition rate of aluminum (Al) was maintained at 2 angstroms per second (Å/sec). 2x10 ^-7 torr to 5x10 ^-8 torr were maintained.

<Examples 2 to 4 and Comparative Examples 1 and 2>

Instead of Compound 1 of Synthesis Example 1 as a light emitting layer dopant material in Example 1, Compound 2 to Compound 3 of Synthesis Examples 2 to 3, as shown in Table 1 below, or An organic light-emitting device was manufactured in the same manner as in Example 1, except that the following compounds B-1 to B-2 were used.

<Experimental Example: Evaluation of characteristics of an organic light-emitting device>

When current was applied to the organic light emitting devices according to Examples 1 to 3 and Comparative Examples 1 and 2, the driving voltage, current efficiency, power efficiency, and lifetime (T90) were measured. The measurement results are shown in Table 1 below.

At this time, the lifetime (T90) refers to the time required for the luminance to decrease from the initial luminance to 90%, and the unit is expressed as time (hr).

Light emitting layer
Dopant When 10mA/cm ² current is applied When 20mA/cm ² current is applied Driving voltage
(V) Current efficiency
(cd/A) T90
(hr) Example 1 Compound 1 4.43 5.61 75 Example 2 Compound 2 4.33 5.59 77 Example 3 Compound 3 4.29 5.83 69 Comparative Example 1 Compound B-1 4.50 5.66 32 Comparative Example 2 Compound B-2 4.53 5.65 35

From Table 1 above, it can be seen that when the compounds according to the present invention (Compounds 1 to 3) are used as a dopant for the light emitting layer, the lifetime of the device is much better than that in the case where it is not.

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

Claims (10)

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

In Formula 1,
X is O, S, C(R') ₂ , or Si(R') ₂
At least one of R ₁ is a substituent represented by the following formula (2), and the others are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O, and S,
R ₂ is hydrogen; Or substituted or unsubstituted C _1-60 alkyl,
R'is substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl,
n is an integer from 0 to 4,
a is an integer from 1 to 4,
b is an integer from 0 to 4,
[Formula 2]

In Chemical Formula 2,
Y is O, or S,
Each R ₃ is independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O, and S, or two adjacent substituents are bonded to form a C _6-60 aromatic ring To form,
m is an integer from 0 to 5.
The method of claim 1,
X is O, S, CH ₂ , C(CH ₃ ) ₂ , or Si(CH ₃ ) ₂ ,
compound.
The method of claim 1,
At least one of R ₁ is a substituent represented by Formula 2, and the others are each independently hydrogen; _{C 6-60} aryl unsubstituted or substituted with C _{1-4 alkyl; Or a substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O, and S.
compound.
The method of claim 1,
R ₁ is hydrogen, methyl, phenyl, tert-butyl, 4-(tert-butyl) phenyl, biphenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, or dibenzothiophenyl,
compound.
The method of claim 1,
R ₂ is hydrogen or methyl,
compound.
The method of claim 1,
R ₃ is hydrogen,
compound.
The method of claim 1,
Formula 2 is represented by the following Formula 2-1 or Formula 2-2,
compound:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,
Each Y is independently O or S.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following,
compound:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to any one of claims 1 to 8. That is, an organic light-emitting device.
The method of claim 9,
The organic material layer containing the compound is a light emitting layer,
Organic light emitting device.

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