KR20220052203A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The compound represented by chemical formula 1 described above can be used as a material for an organic layer of the organic light emitting device, and thus can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device. In particular, the compound represented by the chemical formula 1 can be used as a material for a light emitting layer.

Description

Novel compound and organic light emitting device comprising the same

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

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

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, 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.

Korean Patent Publication No. 10-2013-073537

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

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

[Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently N or CH, provided that at least two of them are N,

Y is O or S;

R' and R" are each independently substituted or unsubstituted C _1-60 alkyl or substituted or unsubstituted C _6-60 aryl;

R ₁ is each independently hydrogen or deuterium,

R ₂ and R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C containing one or more heteroatoms selected from the group consisting of N, O and S _2-60 heteroaryl;

a, b and c are each independently an integer from 0 to 8;

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of the present invention as described above.

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

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

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

(Explanation of terms)

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

and

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium (D); halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a 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 means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected to the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, in the ester group, 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 60. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 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 number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

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

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

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

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

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

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

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

(compound)

The present invention provides a compound represented by the formula (1). Formula 1 is a compound having a structure in which three substituents of carbazolyl (A), fluorenyl (B), and dibenzofuranyl (dibenzothiophenyl) (C) are directly bonded to a triazine-based core, and by linkers Compared to the compound to be connected, the electron donor unit and the core electron acceptor unit are adjacent to each other to form a stable structure that easily forms ICT (Intra charge transfer), and when applied as a host compound for the light emitting layer of an organic light emitting device, energy transfer to the dopant is advantageous.

In particular, among the three substituents, carbazolyl (A) does not include additional substituents other than hydrogen and deuterium. Compared to the compound of the structure in which the carbazolyl additionally includes an aryl group or a heteroaryl group, HOMO is higher It is effective in preventing excessive hole injection into the light emitting layer when applied to an organic light emitting device by preventing it from becoming too high, thereby maintaining an appropriate charge balance.

Accordingly, when the compound of Formula 1 is applied to an organic light emitting device, it can have high efficiency, high luminance, long lifespan, and the like. The specific structure of Formula 1 is as follows:

[Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently N or CH, provided that at least two of them are N,

Y is O or S;

R' and R" are each independently substituted or unsubstituted C _1-60 alkyl or substituted or unsubstituted C _6-60 aryl;

R ₁ is each independently hydrogen or deuterium,

R ₂ and R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C containing one or more heteroatoms selected from the group consisting of N, O and S _2-60 heteroaryl;

a, b and c are each independently an integer from 0 to 8;

Preferably, R' and R" are each independently methyl, ethyl, propyl, butyl, phenyl, biphenylyl or naphthyl. Most preferably, R' and R" are each independently, methyl or phenyl am.

Preferably, R ₂ and R ₃ are each independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carba zol-9-yl or 9-phenyl-9H-carbazolyl, the phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carbazole -9-yl and 9-phenyl-9H-carbazolyl are each independently unsubstituted or substituted with one or more deuterium. When substituted with deuterium, it is preferably substituted with at least two or more, or four or more deuterium.

Most preferably, R ₂ and R ₃ are each independently hydrogen, deuterium, phenyl, biphenylyl or naphthyl, said phenyl, biphenylyl and naphthyl being unsubstituted or substituted with one or more deuterium. When substituted with deuterium, it is preferably substituted with at least two or more, or four or more deuterium.

Preferably, b and c are each independently an integer from 0 to 2.

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

.

.

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

[Scheme 1]

In the above scheme, each X' is independently halogen, preferably bromo or chloro, and definitions for other substituents are the same as described above.

The reaction scheme is a Suzuki coupling reaction, and the reaction is preferably performed in the presence of a palladium catalyst and a base. In addition, the reactor, catalyst, solvent, etc. used for the reaction can be changed to suit the desired product. The preparation method of the compound of Formula 1 may be more specific in Preparation Examples to be described later.

(organic light emitting element)

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. 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 multi-layer 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, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. 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 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, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 The indicated compounds are included.

In addition, the organic layer may include an electron blocking layer, and the electron blocking layer includes the compound represented by Formula 1 above.

In addition, the organic layer may include a hole blocking layer, the hole blocking layer includes the compound represented by the formula (1).

In addition, the organic layer may include an electron transport layer, an electron injection layer, or a layer that transports and injects electrons at the same time, and the electron transport layer, the electron injection layer, or a layer that simultaneously transports and injects electrons is represented by the above formula The compound represented by 1 is included.

In addition, the organic layer includes a hole injection layer, a hole transport layer, an electron suppression layer, and a light emitting layer, and at least one selected from these includes the compound represented by Formula 1 above.

In addition, the organic layer may include an emission layer, and the emission layer includes the compound represented by Formula 1 above. In the light emitting layer, the compound represented by Formula 1 is used as a host material.

Preferably, the light emitting layer including the compound represented by Formula 1 may further include the compound represented by Formula 2, and when the two compounds are used in combination as a host material in the light emitting layer, an exciplex is formed. This is advantageous, and accordingly, when applied to an organic light emitting device, the characteristic effects of low voltage, high efficiency and long life can be further improved.

The specific structure of the compound of formula 2 is as follows:

[Formula 2]

In Formula 2,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl or C _5-60 heteroaryl that is unsubstituted or substituted for a hetero atom selected from the group consisting of N, O and S,

R ₄ and R ₅ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S ego,

p and q are each independently an integer of 0 to 7.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl or dimethylfluorenyl.

Preferably, the compound represented by Formula 2 is any one selected from the group consisting of:

.

.

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

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

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, 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 diode 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, 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, after forming an organic 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 into 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 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 polymers 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 multi-layered 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 on 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. It is preferable that 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, and conductive polymers of polyaniline and polythiophene series, 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. As a hole transport material, a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and transferring them to the light emitting layer. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The electron blocking layer (or electron blocking layer) is a layer interposed between the hole transport layer and the emission layer in order to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the emission layer. A material having an electron affinity lower than that of the electron transport layer is preferable for the electron suppressing layer.

The light emitting material of the light emitting layer is a material capable of emitting light in the visible ray region by receiving 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 include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The light emitting layer includes a host material and a dopant material, and the compound represented by Formula 1 of the present application is used as a host material and a red host material, and preferably a compound represented by Formula 2 is combined and used as a cohost material.

In addition, a host material may be further used, for example, a condensed aromatic ring derivative or a heterocyclic compound containing compound may be further included. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

The hole-blocking layer (or hole-blocking layer) is formed on the light-emitting layer, preferably provided in contact with the light-emitting layer, to control electron mobility and prevent excessive movement of holes, thereby increasing the probability of hole-electron bonding. It refers to a layer that plays a role in improving device efficiency. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but the present invention is not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the hole blocking 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. Specific examples of the electron injection and transport material 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 fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

The electron injection and transport layer may be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and the electron injection material included in the electron injection layer is LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc. can be used.

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

The 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 intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1: Synthesis of Intermediate 1-a

Step 1) Synthesis of Intermediate 1-a

In a nitrogen atmosphere, 2,4,6-trichloro-1,3,5-triazine (15.0 g, 81.3 mmol) and 9H-carbazole (15.0 g, 89.5 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, sodium tert-butoxide (11.7g, 122mmol) and bis(tri-tert-butylphosphine)palladium(0) (1.2g, 2.4mmol) were added. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 20.5 g of Intermediate 1-a was prepared through sublimation purification. (yield 80%, MS: [M+H] ⁺ = 316)

Step 2) Synthesis of Intermediate 1-b

Intermediate 1-a (15.0 g, 47.6 mmol) and 2-(dibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (15.4) in nitrogen atmosphere g, 52.4 mmol) was added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (26.3g, 190.4mmol) was dissolved in 79ml of water, and after sufficient stirring, potassium carbonate (0.2g, 1.4mmol) was added. After the reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of Intermediate 1-b. (Yield 63%, MS: [M+H] ⁺ = 448)

Step 3) Synthesis of compound 1

Intermediate 1-b (15.0 g, 33.6 mmol) and 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in nitrogen atmosphere (10.9 g, 36.9 mmol) was added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (18.6g, 134.3mmol) was dissolved in 56ml of water, and after sufficient stirring, potassium carbonate (0.1g, 1mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 6.1 g of compound 1 was prepared through sublimation purification. (Yield 30%, MS: [M+H] ⁺ = 606)

Synthesis Example 2: Synthesis of compound 2

In Synthesis Example 1, 9H-carbazole was changed to 9H-carbazole-1,3,4,5,6,8-d6 and compound 2 was prepared in the same manner as in the preparation method of compound 1, except that it was used. . (MS: [M+H] ⁺ = 612)

Synthesis Example 3: Synthesis of compound 3

In Synthesis Example 1, 2-(dibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 4,4,5,5-tetramethyl-2 As -(9-phenyldibenzo[b,d]furan-3-yl)-1,3,2-dioxaborolane, 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5, 5-tetramethyl-1,3,2-dioxaborolane was replaced with 2-(9,9-dimethyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Except for the use, compound 3 was prepared in the same manner as that of compound 1. (MS: [M+H] ⁺ = 682)

Synthesis Example 4: Synthesis of compound 4

In Synthesis Example 1, 2- (dibenzo [b, d] furan-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2- (dibenzo [b, d] furan- 1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used, except that compound 4 was prepared in the same manner as in the preparation method of compound 1. (MS: [M+H] ⁺ = 606)

Synthesis Example 5: Synthesis of compound 5

In Synthesis Example 1, 2- (dibenzo [b, d] furan-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2- (dibenzo [b, d] furan- 1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, as 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5- tetramethyl-1,3,2-dioxaborolane to 2-(9,9-dimethyl-2-phenyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Except for the changes used, compound 5 was prepared in the same manner as in the preparation method of compound 1. (MS: [M+H] ⁺ = 682)

Synthesis Example 6: Synthesis of compound 6

In Synthesis Example 1, 2-(dibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 4,4,5,5-tetramethyl-2 -(7-phenyldibenzo[b,d]furan-1-yl)-1,3,2-dioxaborolane, 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5, 5-tetramethyl-1,3,2-dioxaborolane was replaced with 2-(9,9-dimethyl-9H-fluoren-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Except for the use, compound 6 was prepared in the same manner as in the preparation method of compound 1. (MS: [M+H] ⁺ = 682)

Synthesis Example 7: Synthesis of compound 7

In Synthesis Example 1, 2-(dibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with dibenzo[b,d]thiophen-4-ylboronic Compound 7 was prepared in the same manner as in the preparation method of compound 1, except that it was changed to acid. (MS: [M+H] ⁺ = 622)

Synthesis Example 8: Synthesis of compound 8

In Synthesis Example 1, 9H-carbazole to 9H-carbazole-1,3,4,5,6,8-d6, 2-(dibenzo[b,d]furan-3-yl)-4,4,5, 5-tetramethyl-1,3,2-dioxaborolane to dibenzo[b,d]thiophen-4-ylboronic acid, 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5, 5-tetramethyl-1,3,2-dioxaborolane was replaced with 2-(9,9-dimethyl-9H-fluoren-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Except for the use, compound 8 was prepared in the same manner as in the preparation method of compound 1. (MS: [M+H] ⁺ = 630)

[Examples and Comparative Examples]

Example 1

A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. 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 with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HT-A and 5% by weight of PD were thermally vacuum deposited to a thickness of 100 Å to form a hole injection layer. Then, only the HT-A material was deposited to a thickness of 1150 Å to form a hole transport layer. The following HT-B was thermally vacuum-deposited to a thickness of 450 Å as an electron blocking layer thereon. Then, compound 1 was vacuum-deposited as a host to a thickness of 400 Å using GD of 15 wt% of the host as a dopant. Then, as a hole blocking layer, the following ET-A was vacuum-deposited to a thickness of 50 Å. Then, as the electron transport and injection layer, the following ET-B and Liq were thermally vacuum-deposited at a ratio of 2:1 to a thickness of 250 Å, and then LiF and magnesium were vacuum-deposited to a thickness of 30 Å at a ratio of 1:1. On the electron transport and injection layer, magnesium and silver were deposited in a ratio of 1:4 to a thickness of 160 Å to form a cathode, thereby manufacturing an organic light emitting diode.

Examples 2 to 21 and Comparative Examples 1 to 11

Organic light emitting devices of Examples 2 to 21 and Comparative Examples 1 to 11 were respectively prepared in the same manner as in Example 1, except that the host material was changed as shown in Table 1 below. In this case, when a mixture of two types of compounds is used as the host, the weight ratio between the host compounds is indicated in parentheses. The compounds used in Comparative Examples are as follows.

[Experimental example]

The organic light emitting diodes manufactured in Examples 1 to 21 and Comparative Examples 1 to 11 were heat-treated in an oven at 100° C. for 30 minutes, then taken out, and voltage, efficiency, and lifespan (T95) were measured by applying a current, and the results are shown in the table below 1 is shown. At this time, the voltage and the efficiency were measured by applying a current density of 10mA/cm ² , and T95 is the time until the initial luminance decreases to 95% at the current density of 20mA/cm ² .

division host
matter @ 10mA/cm ² @ 20mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 1 compound 1 4.64 52.3 84 Example 2 compound 2 4.64 52.2 96 Example 3 compound 3 4.71 54.6 80 Example 4 compound 4 4.73 51.4 78 Example 5 compound 5 4.79 51.0 77 Example 6 compound 6 4.74 51.5 81 Example 7 compound 7 4.61 53.6 69 Example 8 compound 8 4.67 54.2 93 Example 9 PGH-1:Compound 1 (60:40) 4.10 61.5 131 Example 10 PGH-1:Compound 3 (60:40) 4.24 63.9 128 Example 11 PGH-1:Compound 5 (60:40) 4.31 60.8 119 Example 12 PGH-1: Compound 7 (60:40) 4.13 62.2 115 Example 13 PGH-2:Compound 2 (60:40) 4.16 61.4 139 Example 14 PGH-2:Compound 4 (60:40) 4.21 60.3 120 Example 15 PGH-2:Compound 6 (60:40) 4.33 60.4 123 Example 16 PGH-2: Compound 8 (60:40) 4.19 63.3 140 Comparative Example 1 GH-A 4.50 38.6 34 Comparative Example 2 GH-B 4.52 40.1 31 Comparative Example 3 GH-C 4.82 41.4 42 Comparative Example 4 GH-D 5.09 30.9 25 Comparative Example 5 PGH-1:GH-A (60:40) 4.48 47.9 51 Comparative Example 6 PGH-2:GH-D (60:40) 4.81 32.4 31

The compound represented by Formula 1 is a compound having a structure in which three substituents of carbazolyl (A), fluorenyl (B), and dibenzofuranyl (dibenzothiophenyl) (C) are directly bonded to the triazine-based core. For example, the triazine-based core located at the center has an electron-attracting property, and the three substituents bonded thereto have an electron-donating property, among which carbazolyl (A), fluorenyl (B), and dibenzofurani ( In the order of dibenzothiophenyl (C), carbazole has the greatest effect, and through this structure, both holes and electrons can be transported, so it is suitable as a host for the light emitting layer.

As can be seen in Table 1, the examples of the present application exhibit high efficiency, high luminance, and long lifespan. In contrast to this, by including additional substituents on carbazolyl from GH-A and GH-B of Comparative Examples 1 and 2, the HOMO level is increased, which is advantageous for hole injection, and the voltage is lowered, but the holes in the light emitting layer It can be seen that the excessive charge breaks the charge balance and reduces the efficiency and lifetime.

On the other hand, in the case of GH-C that does not include a fluorenyl substituent, the hole injection ability is too low, the voltage rises, and the balance of charges is disturbed. In addition, in the case of GH-C in which each substituent is connected to the core through a linker, the distance between the electron donor and the electron acceptor becomes too great, so that efficient charge transfer is not achieved.

In addition, in Examples 9 to 16, when the compound of Formula 1 is mixed with the compound of Formula 2 and used, an exciplex is formed, and the properties of low voltage, high efficiency, and long life are further improved. In particular, as can be seen from the comparison with Comparative Examples 5 and 6, when the compound of Formula 1 is mixed, the stability of the exciplex formed with Formula 2 is greatly improved, and it can be confirmed that superior properties are exhibited.

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

Claims (11)

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

In Formula 1,
X ₁ to X ₃ are each independently N or CH, provided that at least two of them are N,
Y is O or S;
R' and R" are each independently substituted or unsubstituted C _1-60 alkyl or substituted or unsubstituted C _6-60 aryl;
R ₁ is each independently hydrogen or deuterium,
R ₂ and R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C containing one or more heteroatoms selected from the group consisting of N, O and S _2-60 heteroaryl;
a, b and c are each independently an integer from 0 to 8;
The method of claim 1,
R' and R" are each independently methyl, ethyl, propyl, butyl, phenyl, biphenylyl or naphthyl;
compound.
The method of claim 1,
R ₂ and R ₃ are each independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carbazole-9- yl or 9-phenyl-9H-carbazolyl;
The phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl and 9-phenyl-9H-carbazolyl are each independently To be unsubstituted or substituted with one or more deuterium,
compound.
The method of claim 1,
R ₂ and R ₃ are each independently hydrogen, deuterium, phenyl, biphenylyl or naphthyl;
The phenyl, biphenylyl and naphthyl are each independently substituted or unsubstituted with one or more deuterium,
compound.
The method of claim 1,
b and c are each independently an integer from 0 to 2,
compound.
The method of 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer includes the compound according to any one of claims 1 to 6 which is an organic light emitting device.
8. The method of claim 7,
The organic material layer containing the compound is a light emitting layer,
organic light emitting device.
9. The method of claim 8,
The light emitting layer further comprises a compound represented by the following formula (2),
Organic light emitting device:
[Formula 2]

In Formula 2,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl or C _5-60 heteroaryl that is unsubstituted or substituted for a hetero atom selected from the group consisting of N, O and S,
R ₄ and R ₅ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S ego,
p and q are each independently an integer of 0 to 7.
10. The method of claim 9,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl or dimethylfluorenyl;
organic light emitting device.
10. The method of claim 9,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

.

Images