KR102252884B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light-emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

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

Korean Patent Publication No. 10-2013-073537

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

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

Compound represented by the following formula (1):

[Formula 1]

In Formula 1,

Y is a direct bond; O or S,

이고, 단, 이들 중 하나 이상이 나프탈렌 고리 또는

이고,A ₁ and A ₂ are each independently a benzene ring; Naphthalene ring; or

And, provided that at least one of these is a naphthalene ring or

ego,

Each X is independently CR ₁ R ₂ ; SiR ₃ R ₄ ; NR ₅ ; O; S; Or SO ₂ ,

R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl, or substituted or unsubstituted C _6-60 aryl; and,

L ₁ and L ₂ are each independently a direct bond; Substituted or unsubstituted C _6-60 arylene; _{Or a substituted or unsubstituted C 2-60} heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S,

B ₁ and B ₂ are each independently *-NR ₆ R ₇ ,

R ₆ and R ₇ are each independently substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 haloalkoxy; Tri(C _1-60 alkyl)silyl; Substituted or unsubstituted C _6-60 aryl; Tri(C _6-60 aryl)silyl; _{Substituted or unsubstituted C 2-60} heteroaryl including one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S; Or combined with an adjacent group to form a substituted or unsubstituted condensed ring,

R _'1 and R' ₂ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 haloalkoxy; Tri(C _1-60 alkyl)silyl; Or substituted or unsubstituted C _6-60 aryl,

m and n are each independently an integer of 0 to 3.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of the present invention.

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

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
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.

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

The present invention provides a compound represented by Chemical Formula 1.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

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

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

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

Can be, etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidine group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other and formed.

Preferably, the compound represented by Formula 1 is any one of the compounds represented by the following Formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the above formula,

_{A 1, A 2, B 1} , B 2, L 1, L 2, R '1, R' 2, m and n are as defined above.

Preferably, in Formula 1,

A ₁ is a benzene ring, A ₂ is a naphthalene ring;

A ₁ is a naphthalene ring, A ₂ is a benzene ring;

이거나; A ₁ is a benzene ring, A ₂ is

Or;

, A₂는 벤젠 고리이거나; A ₁ is

, A ₂ is a benzene ring;

이거나; A ₁ is a naphthalene ring, A ₂ is

Or;

, A₂는 나프탈렌 고리이거나; A ₁ is

, A ₂ is a naphthalene ring;

A ₁ is a naphthalene ring, A ₂ is a naphthalene ring; or

이고, A₂은

이고, 여기서, X는 앞서 정의한 바와 같다.A ₁ is

And A ₂ is

And, where X is as previously defined.

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

In the above formula,

X ₁ and X ₂ are each independently CR ₁ R ₂ ; SiR ₃ R ₄ ; NR ₅ ; O; S; Or SO ₂ ,

Y, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , B ₁ , B ₂ , R _1' , R _2' , m and n are as previously defined.

Preferably, each X is independently CR ₁ R ₂ , O, or S, wherein R ₁ and R ₂ are each independently methyl or ethyl.

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

Preferably, R ₆ and R ₇ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, cyclohexenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, Combined with benzonaphthofuranyl, benzonaphthothiophenyl, benzodimethylfluorenyl, or an adjacent substituent to form a substituted or unsubstituted condensed ring,

These are each independently deuterium, *-CD ₃ , C _1-4 alkyl, *-(C _1-4 alkyl) phenyl, C _3-10 cycloalkyl, phenyl, halogen, cyano, *-SiR ₁₁ R ₁₂ R ₁₃ substituted or unsubstituted,

R ₁₁ , R ₁₂ , and R ₁₃ are each independently methyl, ethyl, tertbutyl or phenyl.

Here, when R ₆ and R ₇ are bonded to adjacent substituents to form a substituted or unsubstituted condensed ring, they are structures formed including a nitrogen atom.

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

.

.

.

.

Preferably, R _'1 and R' ₂ are each independently, hydrogen or deuterium.

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

.

.

The compound represented by Formula 1 according to the present invention includes a core structure of fluorene substituted with ADAMANTANE, and thus has the bulkness and rigidity of the core structure, and has excellent sublimation and stability of the chemical structure, resulting in luminous efficiency. It rises and has excellent thermal stability. In particular, by including an amine substituent of a specific structure, it is possible to improve the efficiency and lifespan of the OLED device by simultaneously controlling the electrical and light-emitting characteristics, and thus, the conventional simple spiro-structured compound (for example, dimethylfluorene) can be used. Compared to the adopted organic light emitting device, it can have high efficiency, low driving voltage, high luminance, and long life.

The compound represented by Formula 1 can be prepared by a method according to the multi-step reaction of Scheme 1 below. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In the formula, the other variables excluding X'are as defined above, and each of X'is independently halogen, preferably chloro or bromo, more preferably bromo.

In Reaction Scheme 1, the reactants, catalysts, solvents, and the like to be used can be changed to suit the desired product.

The STEP 2 reaction is a Suzuki coupling reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art.

On the other hand, _{the synthesis of an asymmetric compound of an amine substituent (*-L 1} -B ₁ /*-L ₂ -B ₂ ) in the final product was performed by two Suzuki coupling reactions for intermediate compounds of different structures in STEP 2. I can. The preparation method of the compound may be more specific in Preparation Examples to be described later.

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 injects and transports electrons includes the compound represented by Formula 1 above. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, a high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic material layer capable of simultaneously injecting electrons and transporting electrons, an n-type dopant used in the art may be mixed and used.

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.

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.

The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, when the organic light-emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

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

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SNO _{2 :Sb;} Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

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

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

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the 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.

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 receiving electrons from the cathode and transferring them to the emission layer 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, perylenetetracarboxylic 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.

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

Preparation Example 1: Synthesis of Compound 1

(1) Preparation Example 1-1: Synthesis of Intermediate Compound C

Compound A (30 g, 90.0 mmol) was added to tetrahydrofuran (900 mL). After adding 2.5M nBuLi (36 mL) at 0° C., the mixture was stirred for 5 hours under nitrogen conditions. After raising the temperature to room temperature, the compound B (13.5 g, 90.0 mmol) was added and stirred for 12 hours. After the reaction, 3M NH ₄ Cl (300 mL) was added, and the organic layer was extracted and recrystallized with ethanol to prepare the compound C (32.0 g, yield 88%, MS:[M+H]+=405).

(2) Preparation Example 1-2: Synthesis of Intermediate Compound D

After the compound C (32 g, 79.10 mmol) and CH ₃ SO ₂ OH (64 mL) were added, the mixture was stirred for 5 hours. After cooling to room temperature, the reactant was poured into water, and the resulting solid was filtered, and the resulting solid was recrystallized with chloroform and ethanol to prepare Compound D (23.3 g, yield 76%, MS:[M+H]+= 387). .

(3) Preparation Example 1-3: Synthesis of Intermediate Compound E

Compound D (23.3 g, 60.3 mmol) was added to chloroform (400 mL). Br ₂ (19.3 g) was slowly added dropwise, followed by stirring for 5 hours. After the reaction was completed, the solid produced by filtration was recrystallized with tetrahydrofuran and ethanol to prepare Compound E (17.4 g, yield 53%, MS:[M+H]+=545).

(4) Preparation Example 1-4: Synthesis of Compound 1

The compound E (17.4 g, 32.0 mmol) and the compound F (20.2 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 1 (16.2 g, yield 50%, MS:[M+H]+= 1014).

Preparation Example 2: Synthesis of Compound 2

(1) Preparation Example 2-1: Synthesis of Intermediate Compound H

The compound G (30 g, 106 mmol) was added to tetrahydrofuran (900 mL). After adding 2.5M nBuLi (42.4 mL) at 0°C, the mixture was stirred for 5 hours under nitrogen conditions. After raising the temperature to room temperature, the compound B (15.9 g, 106 mmol) was added and stirred for 12 hours. After the reaction, 3M NH ₄ Cl (300 mL) was added, and the organic layer was extracted and recrystallized with ethanol to prepare the compound H (31.9 g, yield 85%, MS: [M+H]+= 355).

(2) Preparation Example 2-2: Synthesis of Intermediate Compound I

After the compound H (31.9 g, 90.1 mmol) and CH ₃ SO ₂ OH (73 mL) were added, the mixture was stirred for 5 hours. After cooling to room temperature, the reactant was poured into water, and the resulting solid was filtered and the resulting solid was recrystallized with chloroform and ethanol to prepare the compound I (21.2 g, yield 70%, MS:[M+H]+= 337). .

(3) Preparation Example 2-3: Synthesis of Intermediate Compound J

The compound I (21.2 g, 63.1 mmol) was added to chloroform (400 mL). Br ₂ (20.2 g) was slowly added dropwise, followed by stirring for 5 hours. After the reaction was completed, the resulting solid was filtered and recrystallized with tetrahydrofuran and ethanol to prepare Compound J (15.0 g, yield 48%, MS: [M+H]+=495).

(3) Preparation Example 2-4: Synthesis of Compound 2

The compound J (15.0 g, 30.3 mmol) and the compound K (15.7 g, 60.6 mmol) were added to xylene (400 mL). After adding NatBuO (17.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 2 (10.1 g, yield 39%, MS:[M+H]+=852).

Preparation Example 3: Synthesis of Compound 3

Compound 3-1 (20.0 g, 32.0 mmol) and compound 3-2 (17.63 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 3 (23.02 g, yield 71%, MS:[M+H]+= 1014).

Preparation Example 4: Synthesis of Compound 4

Compound 4-1 (20.0 g, 32.0 mmol) and compound 4-2 (16.22 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 4 (20.16 g, yield 65%, MS:[M+H]+= 970).

Preparation Example 5: Synthesis of Compound 5

Compound 5-1 (21.0 g, 32.0 mmol) and compound 5-2 (19.80 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 5 (28.86 g, yield 81%, MS:[M+H]+= 1114).

Preparation Example 6: Synthesis of Compound 6

Compound 6-1 (17.1 g, 32.0 mmol) and compound 6-2 (19.16 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 6 (23.93 g, yield 77%, MS:[M+H]+= 972).

Preparation Example 7: Synthesis of Compound 7

Compound 7-1 (20.5 g, 32.0 mmol) and compound 7-2 (15.70 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 7 (24.19 g, yield 78%, MS:[M+H]+= 970).

Preparation Example 8: Synthesis of Compound 8

Compound 8-1 (19.2 g, 32.0 mmol) and compound 8-2 (18.01 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 8 (22.11 g, yield 69%, MS:[M+H]+= 765).

Preparation Example 9: Synthesis of Compound 9

Compound 9-1 (17.4 g, 32.0 mmol) and compound 9-2 (19.04 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 9 (20.65 g, yield 66%, MS:[M+H]+=978).

Preparation Example 10: Synthesis of Compound 10

Compound 10-1 (19.5 g, 32.0 mmol) and compound 10-2 (26.99 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 10 (33.49 g, yield 81%, MS:[M+H]+= 1292).

Preparation Example 11: Synthesis of Compound 11

Compound 11-1 (19.5 g, 32.0 mmol) and compound 11-2 (13.01 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 11 (19.16 g, yield 70%, MS:[M+H]+= 856).

Preparation Example 12: Synthesis of Compound 12

Compound 12-1 (20.5 g, 32.0 mmol) and compound 12-2 (10.83 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 12 (19.87 g, yield 76%, MS:[M+H]+=818).

Preparation Example 13: Synthesis of Compound 13

Compound 13-1 (20.5 g, 32.0 mmol) and compound 13-2 (14.42 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 13 (19.92 g, yield 67%, MS:[M+H]+= 930).

Preparation Example 14: Synthesis of Compound 14

Compound 14-1 (16.3 g, 32.0 mmol) and compound 14-2 (13.3 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 14 (14.9 g, yield 61%, MS:[M+H]+= 765).

Preparation Example 15: Synthesis of Compound 15

Compound 15-1 (18.4 g, 32.0 mmol) and compound 15-2 (10.8 g, 64.0 mmol) were added to xylene (400 mL). After adding NatBuO (18.5 g) and BTP (0.2 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized with ethyl acetate 3 times to prepare compound 15 (18.8 g, yield 78%, MS:[M+H]+= 754).

Example 1: Fabrication of an organic light emitting device

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was placed in distilled water dissolved in a dispersant and washed with ultrasonic waves. The detergent was manufactured by Fischer Co., and the distilled water was Millipore Co. Distilled water filtered secondarily with the product filter 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, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

On the prepared ITO transparent electrode, the following HAT was thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer. On it, 1000 Å of HT-A below was vacuum-deposited as a hole transport layer, and 100 Å of HT-B below was deposited. Compound 3 of Preparation Example 3 was doped with 4wt% of H-A as a host as a light emitting layer as a dopant and vacuum-deposited to a thickness of 200Å. Then, 300Å of the following ET-A and the following Liq were deposited at a 1:1 ratio, and magnesium (Mg) doped with 10wt% of silver (Ag) having a thickness of 150Å and aluminum having a thickness of 1,000Å were sequentially deposited thereon. By forming a cathode, an organic light emitting device was manufactured.

In the above process, the deposition rate of the organic material was maintained at 1 Å/sec, the deposition rate for LiF was 0.2 Å/sec, and the deposition rate for aluminum was 3 Å/sec to 7 Å/sec.

Examples 2 to 39 and Comparative Examples 1 to 12: Fabrication of an organic light emitting device

In the manufacture of the organic light-emitting device of Example 1, the compounds of Tables 1 to 3 were used instead of HA as the light emitting layer host, and the compounds of Tables 1 to 3 were used instead of the compound 3 of Preparation Example 3 as the light emitting layer dopant. Except for, an organic light emitting device was manufactured in the same manner as in Example 1.

Experimental example

The driving voltage and luminous efficiency of the organic light emitting devices of Examples 1 to 39 and Comparative Examples 1 to 12 were measured at a current density of ^{10 mA/cm 2} , and 95% of the initial luminance at a current density of ^{20 mA/cm 2} The time to become (LT95) was measured. The results are shown in Tables 1 to 3 below.

division Host Dopant @ 10 mA / cm ² LT95 Voltage(V) Efficiency (cd/A) color Life (hr) Example 1 H-A Compound 3 4.21 6.28 blue 100 Example 2 H-A Compound 4 4.22 5.84 blue 110 Example 3 H-A Compound 5 4.25 6.81 blue 120 Example 4 H-A Compound 6 4.26 6.50 blue 120 Example 5 H-A Compound 7 4.31 6.70 blue 115 Example 6 H-A Compound 8 4.19 6.68 blue 120 Example 7 H-A Compound 9 4.21 6.98 blue 130 Example 8 H-A Compound 10 4.18 6.28 blue 125 Example 9 H-A Compound 11 4.23 6.29 blue 110 Example 10 H-A Compound 12 4.10 6.27 blue 115 Example 11 H-A Compound 13 4.00 6.78 blue 110 Example 12 H-A Compound 14 4.10 6.28 blue 120 Example 13 H-A Compound 15 4.20 6.10 blue 140 Comparative Example 1 H-A D-1 4.39 5.31 blue 75 Comparative Example 2 H-A D-2 4.42 3.50 blue 50 Comparative Example 3 H-A D-3 4.40 4.88 blue 85 Comparative Example 4 H-A D-4 4.54 5.12 blue 55

Host Dopant @ 10 mA / cm ² LT95 Voltage(V) Efficiency (cd/A) color Life (hr) Example 14 H-B Compound 3 4.32 7.12 blue 120 Example 15 H-B Compound 4 4.31 6.77 blue 120 Example 16 H-B Compound 5 4.40 6.98 blue 130 Example 17 H-B Compound 6 4.46 6.45 blue 125 Example 18 H-B Compound 7 4.41 6.44 blue 115 Example 19 H-B Compound 8 4.29 6.97 blue 120 Example 20 H-B Compound 9 4.30 6.28 blue 130 Example 21 H-B Compound 10 4.30 6.57 blue 125 Example 22 H-B Compound 11 4.25 6.48 blue 115 Example 23 H-B Compound 12 4.25 6.53 blue 125 Example 24 H-B Compound 13 4.27 6.08 blue 125 Example 25 H-B Compound 14 4.29 6.65 blue 115 Example 26 H-B Compound 15 4.28 6.10 blue 140 Comparative Example 5 H-B D-1 4.56 5.12 blue 80 Comparative Example 6 H-B D-2 4.54 4.50 blue 60 Comparative Example 7 H-B D-3 4.55 5.32 blue 95 Comparative Example 8 H-B D-4 4.60 4.80 blue 70

division Host Dopant @ 10 mA / cm ² LT95 Voltage(V) Efficiency (cd/A) color Life (hr) Example 27 H-C Compound 3 4.00 7.10 blue 120 Example 28 H-C Compound 4 4.10 6.64 blue 110 Example 29 H-C Compound 5 4.11 6.91 blue 120 Example 30 H-C Compound 6 4.01 6.28 blue 130 Example 31 H-C Compound 7 4.05 6.31 blue 115 Example 32 H-C Compound 8 4.09 6.22 blue 120 Example 33 H-C Compound 9 4.11 6.90 blue 125 Example 34 H-C Compound 10 4.12 6.24 blue 125 Example 35 H-C Compound 11 4.07 6.24 blue 110 Example 36 H-C Compound 12 4.01 6.22 blue 130 Example 37 H-C Compound 13 4.07 6.61 blue 120 Example 38 H-C Compound 14 4.05 6.25 blue 100 Example 39 H-C Compound 15 4.10 6.22 blue 120 Comparative Example 9 H-C D-1 4.32 5.10 blue 70 Comparative Example 10 H-C D-2 4.33 4.50 blue 50 Comparative Example 11 H-C D-5 4.40 4.78 blue 75 Comparative Example 12 H-C D-6 4.44 4.01 blue 55

From Tables 1 to 3, it can be seen that in Examples 1 to 36 of the present application, the driving voltage of the device is lower than that of Comparative Examples 1 to 12, and efficiency and lifetime characteristics are very excellent.

Specifically, in Comparative Examples 1, 3 to 5, 7 to 9, 11 and 12, pyrene, naphthobenzofuran, fluorene, dibenzofluorene, or dinaphthofuran is bonded between two amine groups, respectively. Compound D-1, Compound D-3, Compound D-4, Compound D-5, or Compound D-6 is used as a dopant for the light emitting layer, but these structures do not contain adamantane, and are more It can be seen that the performance is significantly lowered.

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 (11)

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

In Formula 1,
Y is a direct bond; O or S,
A ₁ and A ₂ are each independently a benzene ring; Naphthalene ring; or

And, provided that at least one of these is a naphthalene ring or

ego,
Each X is independently CR ₁ R ₂ , O, or S,
R ₁ and R ₂ are each independently methyl or ethyl,
L ₁ and L ₂ are each independently a direct bond or phenylene,
B ₁ and B ₂ are each independently *-NR ₆ R ₇ ,
R ₆ and R ₇ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, cyclohexenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, benzonaphthofuranyl , Benzonaphthothiophenyl, benzodimethylfluorenyl, or an adjacent substituent to form a condensed ring, which are each independently deuterium, *-CD ₃ , C _1-4 alkyl, *-(C _1-4 Alkyl) phenyl, C _3-10 cycloalkyl, phenyl, halogen, cyano and *-SiR ₁₁ R ₁₂ R ₁₃ substituted or unsubstituted with one or more substituents selected from the group consisting of,
R ₁₁ , R ₁₂ , R ₁₃ are each independently methyl, ethyl, tertbutyl or phenyl,
R _'1 and R' ₂ are, each independently, is hydrogen,
m and n are each independently an integer of 0 to 3.
The method of claim 1,
The compound represented by Formula 1 is any one of the compounds represented by Formulas 1-1 to 1-3 below:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the above formula,
_{A 1, A 2, B 1} , B 2, L 1, L 2, R '1, R' 2, m and n are as defined in claim 1.
The method of claim 1,
A ₁ is a benzene ring, A ₂ is a naphthalene ring;
A ₁ is a naphthalene ring, A ₂ is a benzene ring;
A ₁ is a benzene ring, A ₂ is

Or;
A ₁ is

, A ₂ is a benzene ring;
A ₁ is a naphthalene ring, A ₂ is

Or;
A ₁ is

, A ₂ is a naphthalene ring;
A ₁ is a naphthalene ring, A ₂ is a naphthalene ring; or
A ₁ is

And A ₂ is

Phosphorus, compound:
In the above formula,
X is as defined in claim 1.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

In the above formula,
X ₁ and X ₂ are each independently CR ₁ R ₂ ; SiR ₃ R ₄ ; NR ₅ ; O; S; Or SO ₂ ,
Y, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , B ₁ , B ₂ , R _1' , R _2' , m and n are as defined in claim 1.
delete delete delete The method of claim 1,
B ₁ and B ₂ are each independently any one selected from the group consisting of, a compound:

.
delete The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 4, 8, and 10. One comprising the compound according to claim one, an organic light-emitting device.

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