KR20210119196A - 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 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 can also be used in a solution process, and can improve efficiency, low driving voltage and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device using the same

The present invention relates to a novel compound and an organic light emitting device comprising 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 material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, and 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. 10-2000-0051826

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,

A ₁ and A ₂ are each a benzene ring fused with two adjacent pentagonal rings,

Ar ₁ and Ar ₂ are each independently, 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,

Ar ₃ and Ar ₄ are each independently represented by Formula 2 or Formula 3,

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

B ₁ and B ₂ are each independently a C _6-60 aromatic ring fused to an adjacent pentacyclic ring; _{Or a C 2-60} heteroaromatic ring containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, provided that B ₁ and B ₂ are each fused with an adjacent pentacyclic ring a benzene ring;

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C _6-60 alkyl; or substituted or unsubstituted C _6-60 aryl, or R ₁ and R ₂ are linked to each other to form a C _3-60 cycloalkane ring,

L is a single bond; O; or Si(R ₃ )(R ₄ ),

R ₃ to R ₄ are each independently hydrogen; heavy hydrogen; or C _1-10 alkyl.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and an emission layer provided between the first electrode and the second electrode, wherein the emission layer includes the compound represented by Formula 1 above.

The compound represented by Chemical Formula 1 described above can be used as a material for an organic material layer of an organic light emitting device, and can also be used in a solution process, and can improve efficiency, low driving voltage and/or lifespan characteristics in an organic light emitting device. have.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , an organic material layer 3 , and a cathode 4 .
2 shows 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, an electron injection layer 9 and a cathode 4 An example of an organic light emitting device is shown.

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

(Definition of Terms)

또는

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano 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 heteroaryl containing one or more, or substituted or unsubstituted with two or more substituents of the above-exemplified substituents connected . 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 or 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 phenanthrenyl 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, heteroaryl is a heteroaryl 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 from 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, 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 ( phenanthroline), an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group is the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description regarding heteroaryl described above 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 heteroaryl described above 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 heterocycle is not a monovalent group, and the description of the above-described heteroaryl 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).

The compound represented by Formula 1 has a structure in which a fused ring of dibenzofuran and benzofuran is a core, has two or more amine substituents, and at least one or more fluorene derivatives are included in each amine substituent.

Due to such a structure, the compound of Formula 1 exhibits excellent solubility and can be suitably used in a solution process, and can be used as a dopant of an organic material layer of an organic light emitting device, preferably a light emitting layer, and in this case, it can exhibit improved lifespan and efficiency.

Preferably, the compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2 below:

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, Ar ₁ to Ar ₄ are as defined in Formula 1.

Preferably, Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted C _6-30 aryl; _{or C 2-30} heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

Preferably, Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

above,

X _{1 To} X ₅ are each independently, CR' ₁ or N,

R' ₁ are each independently hydrogen; halogen; C _1-10 alkyl; C _1-10 alkoxy; C _6-20 aryloxy; C _1-10 alkylamino; C _6-20 arylamino; C _1-10 alkylsilyl; C _6-20 arylsilyl; C _6-20 aryl; _{or C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S;

X ₆ is NR′ ₂ , C(R′ ₃ )(R′ ₄ ), O, or S;

R' _{2 To} R' ₄ are each independently hydrogen; C _1-10 alkyl; C _6-20 aryl; _{or C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S;

p is an integer from 0 to 7,

R' ₅ are each independently hydrogen; C _1-10 alkyl; C _6-20 aryl; _{or C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.

In the above, C _1-10 alkyl may be methyl or t-butyl.

In the above, C _6-20 aryloxy may be phenoxy.

In the above, C _1-10 alkylamino may be dimethylamino, and C _6-20 arylamino may be diphenylamino.

In the above, C _1-10 alkylsilyl may be trimethylsilyl, and C _6-20 arylsilyl may be triphenylsilyl.

In the above, C _6-20 aryl may be substituted or unsubstituted, for example, naphthyl or t-butylphenyl.

_{In the above, C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S may be substituted or unsubstituted, for example, carbazolyl or benzofuranyl.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenylnaphthyl, pyridinyl, benzofuranyl, benzothiophenyl, dimethylfluorenyl, diphenyl fluorenyl, dibenzofuranyl, dibenzothiophenyl, nylcarbazolyl, wherein Ar ₁ and Ar ₂ are each independently, unsubstituted, or methyl, isopropyl, sec-butyl, t-butyl, 1, one selected from the group consisting of 1,3,3-tetramethylbutyl, t-butylphenyl, naphthyl, triphenylsilyl, dimethylamino, diphenylamino, fluoro, phenoxy, carbazolyl, and benzofuranyl or two substituents.

Preferably, Ar ₁ and Ar ₂ may be the same as each other.

부분은 플루오렌 모이어티를 포함하며, B₁ 또는 B₂가 벤젠 이외의 아릴이거나 헤테로아릴일 경우,

부분은 플루오렌에 융합된 고리를 더 포함하는 구조이다.In Formulas 2 and 3, B ₁ and B ₂ each include a benzene ring fused to an adjacent pentagonal ring. That is, in Formula 2 and/or Formula 3

the moiety comprises a fluorene moiety, and when B ₁ or B ₂ is an aryl other than benzene or heteroaryl,

The moiety is a structure further comprising a ring fused to fluorene.

Preferably, B ₁ and B _{2 are each a C 6-30} aromatic ring fused with an adjacent pentacyclic ring; _{Or a C 2-30} heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

부분은 각각 독립적으로 하기로 이루어지는 군에서 선택되는 어느 하나일 수 있다:Preferably, B ₁ to B ₄ are each independently benzene fused to an adjacent pentacyclic ring; naphthalene; phenanthrene; or dibenzofuran. In this case, Formula 2 and/or Formula 3

Each moiety may be independently selected from the group consisting of:

Preferably, Ar ₃ and Ar ₄ may each independently be any one selected from the group consisting of:

In the above, R ₁ and R ₂ are as defined in Formula 2, and L is as defined in Formula 3.

Preferably, R ₁ and R ₂ are substituted or unsubstituted C _1-30 alkyl; substituted or unsubstituted C _6-30 aryl, or R ₁ and R ₂ are linked to each other to form a C _3-30 cycloalkane ring.

Preferably, R ₁ and R ₂ are each independently methyl; phenyl; methylphenyl; or t-butylphenyl, or R ₁ and R ₂ are connected to each other to form a cyclohexane ring.

Preferably, L is a single bond, O, or Si(CH ₃ ) ₂ .

Preferably, Ar ₃ and Ar ₄ may be the same as each other.

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

On the other hand, the present invention provides a method for preparing the compound represented by the above formula (1). For example, the compound of Formula 1 may be prepared by a preparation method as shown in Scheme 1:

[Scheme 1]

In Scheme 1, definitions other than X' are the same as defined above, and X' is halogen, preferably chloro or bromo.

Scheme 1 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art.

The manufacturing method may be more specific in Preparation Examples to be described later.

(Coating composition)

On the other hand, the compound according to the present invention can form an organic material layer, particularly, a light emitting layer of an organic light emitting device by a solution process. Specifically, the compound may be used as a dopant material of the emission layer. 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-phenoxytoluene. In addition, the above-mentioned solvents may be used alone or as a mixture of two or more solvents. Preferably, toluene may be used as the solvent.

In addition, the coating composition may further include a compound used as a host material, and a description of the compound used for the host material will be described later.

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 concentration of the compound according to the present invention in the coating composition is preferably 0.1 wt/v% to 20 wt/v%.

In addition, the present invention provides a method of forming a light emitting layer using the above-described coating composition. Specifically, coating the light emitting layer according to the present invention on the anode or on the hole transport layer formed on the anode 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.

(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 an emission layer provided between the first electrode and the second electrode, wherein the emission layer includes the compound represented by Formula 1 above.

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

2 shows 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, an electron injection layer 9 and a cathode 4 An example of an organic light emitting device is shown. In such a structure, the compound represented by Formula 1 may be included in 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 that the light emitting layer includes the compound according to the present invention and is manufactured as described above.

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 preferred so that holes can be smoothly injected 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. As the dopant material, the compound represented by the above-described Chemical Formula 1 may be used. In addition, as a host material, a condensed aromatic ring derivative, a heterocyclic ring containing compound, etc. can be used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the electron control layer. As the electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or LiF, NaF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, pre Orenylidene methane, anthrone, etc. derivatives thereof, metal complex compounds, or nitrogen-containing 5-membered ring derivatives may be used, but the present invention is 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.

[Synthesis Example]

Synthesis Example 1: Preparation of compound BD1

Synthesis Example 1-1) Preparation of Intermediate 1

3,7-dibromobenzene [b, d] furan-2,8-diol (14.3 g, 40 mmol), (4-chloro-2-fluorophenyl) boronic acid in a 500 mL round-bottom flask under nitrogen atmosphere (16.5 g, 48 mmol), tetrakis (triphenylphosphine) palladium (2.3 g, 2 mmol), potassium carbonate (16.6 g, 60 mmol) were added, and tetrahydrofuran 300 mL and water 60 mL were added. The temperature of the reactor ^{was raised to 80 o} C and stirred for 12 hours. When the reaction was completed, the temperature was lowered to room temperature and the organic layer was extracted. After the obtained organic layer was concentrated, intermediate 1 (15.3 g, yield 84%) was obtained by hexane/ethyl acetate chromatography separation method.

Synthesis Example 1-2) Preparation of Intermediate 2

Intermediate 1 (15.3 g, 33.6 mmol) and potassium carbonate (10.2 g, 74 mmol) were placed in a 500 mL round-bottom flask in a nitrogen atmosphere, and 180 mL of N-methyl-2-pyrrolidone was added. The temperature of the reactor ^{was raised to 120 °} C and stirred for 4 hours. After completion of the reaction, the temperature was lowered to room temperature, water was added to precipitate a solid, filtered, washed with ethanol and tetrahydrofuran to remove impurities, and Intermediate 2 (9.3 g, yield 66%) was obtained.

Synthesis Example 1-3) Preparation of compound BD 1

Intermediate 2 (1.2 g, 3.7 mmol), N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine (2.8 g, 8.1 mmol), in a 250 mL flask under nitrogen atmosphere, Bis(tri-tert-butylphosphine)palladium(0) (0.23 g, 0.4 mmol), sodium tert-butoxide (0.8 g, 8.1 mmol) and 100 mL of toluene were added and stirred at 105° C. for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and then a precipitate was formed with hexane. After filtering the precipitate, it was washed with methanol and toluene to obtain an organic material. The resulting organic material was dissolved in dichloromethane, passed through an acid alumina filter and a 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 71%). MS[M+H] ⁺ = 999.44

Synthesis Example 2: Preparation of compound BD 2

In Synthesis Example 1-3, 9,9-dimethyl-N-(2-naphthyl)-fluorene- instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine Compound BD 2 (2.3 g, yield 67%) was obtained in the same manner as in the preparation of Compound BD 1, except that 2-amine was used. MS[M+H] ⁺ = 1015.38

Synthesis Example 3: Preparation of compound BD 3

Except for using bis(9,9-dimethylfluorene)-2-amine instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine in Synthesis Example 1-3 Then, compound BD 3 (2.7 g, yield 60%) was obtained in the same manner as in the preparation method of compound BD 1. MS[M+H] ⁺ = 1119.44

Synthesis Example 4: Preparation of compound BD 5

In Synthesis Example 1-3, N-(4-(benzofuran-2-)phenyl)-9,9 instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine - Compound BD 4 (2. g, yield 61%) was obtained in the same manner as in the preparation of Compound BD 1, except that dimethylfluoren-2-amine was used. MS[M+H] ⁺ = 1147.40

Synthesis Example 5) Preparation of compound BD 5

In Synthesis Example 1-3, N-(3-(carbazole-9-)phenyl)-9,9 instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine -Compound BD 5 (1.9 g, yield 56%) was obtained in the same manner as in the preparation of Compound BD 1, except that dimethylfluoren-2-amine was used. MS[M+H] ⁺ = 1245.47

Synthesis Example 6) Preparation of compound BD 6

In Synthesis Example 1-3, N-(6-(benzofuran-2-)naphthalene-2)-9 instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine Compound BD 6 (3.1 g, yield 63%) was obtained in the same manner as in the preparation method of Compound BD 1, except that ,9-diphenylfluoren-2-amine was used. MS[M+H] ⁺ = 1495.50

Synthesis Example 7) Preparation of compound BD 7

In Synthesis Example 1-3, 11,11-dimethyl-N-(naphthalene-2)-benzofluorene- instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine Compound BD 7 (1.8 g, yield 63%) was obtained in the same manner as in the preparation of Compound BD 1, except that 2-amine was used. MS[M+H] ⁺ = 963.28

Synthesis Example 8) Preparation of compound BD 8

In Synthesis Example 1-3, N-(4'-isopropyl-[1,1'-biphenyl] instead of N-(4-(tert-butyl)phenyl)-9,9-dimethyl-fluoren-2-amine Compound BD 8 (2.5 g, yield 65%) was obtained in the same manner as in the preparation of Compound BD 1, except that -4)-9,9-dimethylfluoren-3-amine was used. MS[M+H] ⁺ = 1115.41

[Example]

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 then washed with ultrasonic waves for 30 minutes. Thereafter, 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 thus prepared ITO transparent electrode 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 obtained by dissolving the following compound B and the previously prepared compound BD 1 in toluene at 0.6 wt % (compound B: weight ratio of compound BD 1 = 98: 2) was spin-coated to form a light emitting layer with a thickness of 200 Å The coating composition was cured at 120° C. and 10 minutes on a hot plate under a nitrogen atmosphere. Thereafter, the following compound G (electron transport layer, 200 Å), LiF (electron injection layer, 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.

Examples 2 to 8

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

Comparative Examples 1 to 3

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

Experimental example

For the organic light-emitting devices prepared in Examples and Comparative Examples, the driving voltage, the maximum emission wavelength, the current efficiency, and the 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) drive voltage
(V) current efficiency
(cd/A) quantum efficiency
(%) Example 1 compound BD 1 456 4.67 7.8 7.61 Example 2 compound BD 2 455 4.68 6.7 7.83 Example 3 compound BD 3 456 4.63 6.8 7.68 Example 4 compound BD 4 457 4.71 6.9 7.51 Example 5 compound BD 5 460 4.66 7.6 8.01 Example 6 compound BD 6 459 4.66 6.9 7.71 Example 7 compound BD 7 456 4.59 7.5 7.69 Example 8 Compound BD 8 458 4.69 7.1 7.9 Comparative Example 1 compound C 441 4.76 3.6 5.8 Comparative Example 2 compound D 442 4.76 4.5 6.1 Comparative Example 3 compound E 450 4.71 5.1 5.3

As shown in Table 1, it was confirmed that the organic light emitting device using the compound of the present invention as a dopant of the light emitting layer exhibited remarkable effects in terms of driving voltage, current efficiency, or quantum efficiency.

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

Claims (11)

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

In Formula 1,
A ₁ and A ₂ are each a benzene ring fused with two adjacent pentagonal rings,
Ar ₁ and Ar ₂ are each independently, 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,
Ar ₃ and Ar ₄ are each independently represented by Formula 2 or Formula 3,
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
B ₁ and B ₂ are each independently a C _6-60 aromatic ring fused to an adjacent pentacyclic ring; _{Or a C 2-60} heteroaromatic ring containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, provided that B ₁ and B ₂ are each fused with an adjacent pentacyclic ring a benzene ring;
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C _6-60 alkyl; or substituted or unsubstituted C _6-60 aryl, or R ₁ and R ₂ are linked to each other to form a C _3-60 cycloalkane ring,
L is a single bond; O; or Si(R ₃ )(R ₄ ),
R ₃ to R ₄ are each independently hydrogen; heavy hydrogen; or C _1-10 alkyl.
According to claim 1,
Formula 1 is represented by the following Formula 1-1 or Formula 1-2,
compound:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, Ar ₁ to Ar ₄ are as defined in claim 1.
According to claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of
compound:

above,
X _{1 To} X ₅ are each independently, CR' ₁ or N,
R' ₁ are each independently hydrogen; halogen; C _1-10 alkyl; C _1-10 alkoxy; C _6-20 aryloxy; C _1-10 alkylamino; C _6-20 arylamino; C _1-10 alkylsilyl; C _6-20 arylsilyl; C _6-20 aryl; _{or C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S;
X ₆ is NR′ ₂ , C(R′ ₃ )(R′ ₄ ), O, or S;
R' _{2 To} R' ₄ are each independently hydrogen; C _1-10 alkyl; C _6-20 aryl; _{or C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S;
p is an integer from 0 to 7,
R' ₅ are each independently hydrogen; C _1-10 alkyl; C _6-20 aryl; _{or C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.
According to claim 1,
B ₁ and B ₂ are each independently benzene fused to an adjacent pentacyclic ring; naphthalene; phenanthrene; or dibenzofuran,
compound.
According to claim 1,
Formula 2 and/or Formula 3

Each part is independently any one selected from the group consisting of
compound:

According to claim 1,
Ar ₃ and Ar ₄ are each independently any one selected from the group consisting of:

In the above, R ₁ , R ₂ , and L are as defined in claim 1
According to claim 1,
R ₁ and R ₂ are each independently, substituted or unsubstituted C _1-30 alkyl; substituted or unsubstituted C _6-30 aryl, or R ₁ and R ₂ are linked to each other to form a _{C 3-30 cycloalkane ring,}
compound.
According to claim 1,
R ₁ and R ₂ are each independently methyl; phenyl; methylphenyl; or t-butylphenyl, or R ₁ and R ₂ are linked to each other to form a cyclohexane ring,
compound.
According to claim 1,
L is a single bond, O, or Si(CH ₃ ) ₂ ;
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

a first electrode; a second electrode provided to face the first electrode; and a light emitting layer provided between the first electrode and the second electrode, wherein the light emitting layer comprises the compound according to any one of claims 1 to 10. .

Images