WO2022059923A1 - Novel compound and organic light-emitting device comprising same - Google Patents

Abstract

The present invention provides a novel compound and an organic light-emitting device comprising same.

Description

Novel compound and organic light emitting device using same

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0120806 on September 18, 2020 and Korean Patent Application No. 10-2021-0105511 on August 11, 2021, All content disclosed in the literature is incorporated as a part of this specification.

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

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

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

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

Prior art literature

Patent Literature

(Patent Document 0001) 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 , X ₂ and X ₃ are each independently O, S or CR, with the proviso that one of them is O or S, wherein each R is independently hydrogen, deuterium, substituted or unsubstituted C _{6 -60} aryl, a substituted or unsubstituted C _2-60 heteroaryl containing one or more hetero atoms selected from the group consisting of N, O and S, or a substituted or unsubstituted C ₆ - ₆₀ to form a condensed ring,

L is a single bond, substituted or unsubstituted C _6-60 arylene, or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S; ,

Ar is substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S;

R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- containing one or more heteroatoms selected from the group consisting of N, O and S ₆₀ heteroaryl;

n is 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 Chemical Formula 1 described above may be used as a material of 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 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light emitting layer 3, an electron injection and transport layer 8, and a cathode 4 An example of an organic light emitting device made of

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

(Explanation of terms)

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 atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . 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, 4-methylhexyl, 5-methylhexyl, and the like, but is 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.

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, "hetero-aromatic ring (heterocyclic ring)" is a heterocondensed monocyclic ring or heterocondensed polycyclic ring having aromaticity as a whole while including one or more heteroatoms among O, N, and S other than carbon as a ring forming atom. means ring. The number of carbon atoms of the hetero ring is 2 to 60, or 2 to 30, or 2 to 20, but is not limited thereto. In addition, the hetero ring may be a thiophene ring, a furan ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, etc., 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 above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied, except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

(compound)

The present invention provides a compound represented by the formula (1). The compound represented by Formula 1 includes a structure serving as an electron acceptor and a structure serving as an electron donor at the same time, and since two units having completely different properties are directly bonded, they exchange charges within a molecule and have a small band gap. This is advantageous for energy transfer to the red dopant, and thus is suitable for use as a host of the red light emitting layer in the organic light emitting device. In addition, in the parent nucleus structure serving as an electron donor, it contains a pentagonal condensed ring forming a heptagonal structure with benzocarbazole, and thus, the steric hindrance effect is reduced compared to other condensed ring structures (eg, hexagonal ring). less, indicating higher stability. Accordingly, when the compound represented by Formula 1 is applied to an organic light emitting device, high efficiency, low driving voltage, high luminance, long lifespan, and the like may be obtained. Looking at the structure of Formula 1, it is as follows:

[Formula 1]

In Formula 1,

X ₁ , X ₂ and X ₃ are each independently O, S or CR, with the proviso that one of them is O or S, wherein each R is independently hydrogen, deuterium, substituted or unsubstituted C _{6 -60} aryl, a substituted or unsubstituted C _2-60 heteroaryl containing one or more hetero atoms selected from the group consisting of N, O and S, or a substituted or unsubstituted C ₆ - ₆₀ to form a condensed ring,

L is a single bond, substituted or unsubstituted C _6-60 arylene, or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S; ,

Ar is substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S;

R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- containing one or more heteroatoms selected from the group consisting of N, O and S ₆₀ heteroaryl;

n is an integer from 0 to 8;

Preferably, Chemical Formula 1 is a compound represented by the following Chemical Formulas 1-1 to 1-6:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,

L, Ar, R ₁ and n are as defined in claim 1,

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

R ₂ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-30 aryl, or substituted or unsubstituted C _2- containing one or more heteroatoms selected from the group consisting of N, O and S ₃₀ heteroaryl;

m is an integer from 0 to 4.

Preferably, each R ₂ is independently hydrogen, deuterium, or phenyl.

Preferably, L is a single bond, or any one selected from the group consisting of:

In the group,

each R″ is independently hydrogen, deuterium or phenyl;

a is each independently an integer of 0 to 4,

b is each independently an integer of 0 to 6.

Preferably, Ar is any one selected from the group consisting of:

In the group,

X' ₁ , X' ₂ and X' ₃ are each independently N or CH, provided that at least two of them are N;

Y is each independently O or S,

Ar ₁ is each independently substituted or unsubstituted C _6-30 aryl, or substituted or unsubstituted C _2-30 heteroaryl including one or more heteroatoms selected from the group consisting of N, O and S .

Preferably, Ar ₁ is each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl , dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, which is unsubstituted or substituted with one or more deuterium (D).

Most preferably, each Ar ₁ is independently phenyl, biphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl , or 9-phenyl-9H-carbazolyl, which is unsubstituted or substituted with one or more deuterium (D).

Preferably, each R ₁ is independently hydrogen, deuterium, or phenyl.

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.

Specifically, the compound represented by Formula 1 is prepared by combining starting materials SM1 and SM2 through an amine substitution reaction. This amine substitution reaction is preferably performed in the presence of a palladium catalyst and a base. In addition, the reactive group for the amine substitution reaction may be appropriately changed, and the method for preparing the compound represented by Chemical Formula 1 may be more specific in Synthesis 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. Preferably, the compound represented by Formula 1 is used as the host compound of the light emitting layer.

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. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. A material with high hole mobility. 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.

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, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. 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 A: Synthesis of Intermediate A

Step 1) Synthesis of Intermediate A-1

In a nitrogen atmosphere, 1,8-dibromonaphthalene (15.0 g, 52.5 mmol) and (2-nitrophenyl) boronic acid (9.6 g, 57.7 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, sodium hydroxide (8.4g, 209.8mmol) was dissolved in 25ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (1.8g, 1.6mmol) was added.

After 10 hours of reaction, the mixture 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 12.0 g of Intermediate A-1.

(Yield 70%, MS: [M+H] ⁺ = 329)

Step 2) Synthesis of Intermediate A-2

Intermediate A-1 (15.0 g, 45.7 mmol) and 2-(2-chlorobenzofuran-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (14.0 g, 50.3 mmol) in nitrogen atmosphere ) was added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.3g, 182.8mmol) was dissolved in 76ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (1.6g, 1.4mmol) was added. After the reaction for 12 hours, the mixture 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 11.9 g of Intermediate A-2.

(Yield 65%, MS: [M+H] ⁺ = 401)

Step 3) Synthesis of Intermediate A-3

Intermediate A-2 (15.0 g, 37.5 mmol) was refluxed in 300 ml of 1,4-dioxane in a nitrogen atmosphere and stirred. After that, potassium phosphate (9.6g, 45mmol) was dissolved in 29ml of water, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.3mmol) were added. After reacting for 5 hours, cooling to room temperature, and separating the organic layer using chloroform and water, 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 9.4 g of Intermediate A-3.

(yield 69%, MS: [M+H] ⁺ = 364)

Step 3) Synthesis of Intermediate A

Intermediate A-3 (20.0g, 55mmol) and triethyl phosphite (13.7ml, 82.6mmol) were refluxed in 200ml of o-dichlorobenzene and stirred in a nitrogen atmosphere. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, 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 10.4 g of Intermediate A.

(Yield 57%, MS: [M+H] ⁺ = 332)

Synthesis Example B: Synthesis of Intermediate B

In Synthesis Example A, 2-(2-chlorobenzofuran-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 2-(3-chlorobenzofuran-2-yl)-4,4 ,5,5-tetramethyl-1,3,2-dioxaborolane Intermediate B was prepared in the same manner as in the preparation method of Intermediate A, except that it was used.

(MS: [M+H] ⁺ = 332)

Synthesis Example C: Synthesis of Intermediate C

In Synthesis Example A, 2-(2-chlorobenzofuran-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 2-(2-chlorobenzo[b]thiophen-3-yl) Except for using -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, Intermediate C was prepared in the same manner as that of Intermediate A.

(MS: [M+H] ⁺ = 348)

Synthesis Example D: Synthesis of Intermediate D

In Synthesis Example A, 2-(2-chlorobenzofuran-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 2-(3-chlorobenzo[b]thiophen-2-yl) Except for using -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, Intermediate D was prepared in the same manner as in the preparation of Intermediate A.

(MS: [M+H] ⁺ = 348)

Synthesis Example E: Synthesis of Intermediate E

In Synthesis Example A, 2-(2-chlorobenzofuran-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 2-(4-chlorofuran-3-yl)-4,4 ,5,5-tetramethyl-1,3,2-dioxaborolane Intermediate E was prepared in the same manner as in the preparation method of Intermediate A, except that it was used.

(MS: [M+H] ⁺ = 282)

Synthesis Example F: Synthesis of Intermediate F

In Synthesis Example A, 2-(2-chlorobenzofuran-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was mixed with 2-(4-chlorothiophen-3-yl)-4,4 ,5,5-tetramethyl-1,3,2-dioxaborolane Intermediate F was prepared in the same manner as in the preparation method of Intermediate A, except that it was used.

(MS: [M+H] ⁺ = 298)

Synthesis Example 1: Synthesis of compound 1

In a nitrogen atmosphere, Intermediate A (15.0 g, 45.3 mmol) and Intermediate a (12.0 g, 49.8 mmol) were added to 300 ml of xylene, stirred and refluxed. Then, sodium tert-butoxide (6.5g, 67.9mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.7g, 1.4mmol) were added. After 8 hours of reaction, the mixture 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, 8.7 g of compound 1 was prepared through sublimation purification.

(Yield 36%, MS: [M+H] ⁺ = 537)

Synthesis Example 2: Synthesis of compound 2

In Synthesis Example 1, compound 2 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate a was changed to the intermediate b and used.

(MS: [M+H] ⁺ = 716)

Synthesis Example 3: Synthesis of compound 3

In Synthesis Example 1, compound 3 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate A was changed to the intermediate B and the intermediate a was changed to the intermediate c.

(MS: [M+H] ⁺ = 587)

Synthesis Example 4: Synthesis of compound 4

In Synthesis Example 1, compound 4 was prepared by the same preparation method as that of compound 1, except that Intermediate A was changed to Intermediate B and Intermediate a was changed to Intermediate d.

(MS: [M+H] ⁺ = 627)

Synthesis Example 5: Synthesis of compound 5

In Synthesis Example 1, compound 5 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate A was changed to the intermediate C and the intermediate a was changed to the intermediate e.

(MS: [M+H] ⁺ = 706)

Synthesis Example 6: Synthesis of compound 6

In Synthesis Example 1, compound 6 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate A was changed to the intermediate D and the intermediate a was changed to the intermediate f.

(MS: [M+H] ⁺ = 774)

Synthesis Example 7: Synthesis of compound 7

In Synthesis Example 1, compound 7 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate A was changed to the intermediate D and the intermediate a was changed to the intermediate g.

(MS: [M+H] ⁺ = 603)

Synthesis Example 8: Synthesis of compound 8

In Synthesis Example 1, compound 8 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate A was changed to the intermediate E and the intermediate a was changed to the intermediate h.

(MS: [M+H] ⁺ = 640)

Synthesis Example 9: Synthesis of compound 9

In Synthesis Example 1, compound 9 was prepared in the same manner as in the preparation method of compound 1, except that the intermediate A was changed to the intermediate F and the intermediate a was changed to the intermediate i.

(MS: [M+H] ⁺ = 706)

[Examples and Comparative Examples]

Comparative 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 HI-A and hexanitrile hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. Thereafter, HT-A as a hole transport layer was vacuum deposited to a thickness of 800 Å, and then EB-A to a thickness of 600 Å as an electron suppression layer was vacuum-deposited. Subsequently, the following host RH-A and a 2wt% dopant RD were vacuum-deposited to a thickness of 400 Å as a light emitting layer. Then, as an electron transport and injection layer, the following ET-A and Liq were thermally vacuum-deposited at a ratio of 1:1 to a thickness of 360 Å, followed by vacuum deposition of Liq to a thickness of 5 Å.

On the electron injection layer, magnesium and silver were sequentially deposited at a ratio of 10:1 to a thickness of 220 Å and aluminum to a thickness of 1000 Å to form a cathode, thereby manufacturing an organic light emitting diode.

Examples 1 to 9 and Comparative Examples 2 to 5

Organic light emitting devices of Examples 1 to 9 and Comparative Examples 2 to 3 using the same method as in Comparative Example 1, except that the compound listed in Table 1 was used instead of RH-A as the light emitting layer host compound in Comparative Example 1 were produced respectively.

[Experimental example]

Experimental Examples 1 to 9 and Comparative Experimental Examples 1 to 5

By applying a current to the organic light emitting diodes manufactured in Examples 1 to 9 and Comparative Examples 1 to 5, voltage, efficiency, and lifetime were measured, and the results are shown in Table 1 below.

At this time, the voltage and efficiency were measured by applying a current density of 10mA/cm ² , the lifetime characteristic LT97 was measured at a current density of 20mA/cm ² , and LT97 means the time until the initial luminance decreases to 97% .

division	light emitting layer host	@10mA/cm 2		@20mA/cm 2
		V	cd/A	LT97(hr)
Experimental Example 1	compound 1	4.61	23.3	121
Experimental Example 2	compound 2	4.53	23.1	127
Experimental Example 3	compound 3	4.66	23.2	119
Experimental Example 4	compound 4	4.42	23.5	108
Experimental Example 5	compound 5	4.60	23.7	112
Experimental Example 6	compound 6	4.67	22.9	103
Experimental Example 7	compound 7	4.65	23.6	102
Experimental Example 8	compound 8	4.52	24.0	94
Experimental Example 9	compound 9	4.58	24.9	93
Comparative Experimental Example 1	RH-A	5.10	18.3	65
Comparative Experimental Example 2	RH-B	4.92	20.9	86
Comparative Experimental Example 3	RH-C	5.37	12.3	45
Comparative Experimental Example 4	RH-D	5.06	18.8	38
Comparative Experimental Example 5	RH-E	4.96	19.8	51

The compound of Formula 1 herein has a unique core structure, and includes a structure serving as an electron acceptor and a structure serving as an electron donor at the same time. The compound has a small band gap by exchanging charges inside the molecule because two units having completely different properties are directly bonded. This is advantageous for energy transfer to the red dopant, and thus is suitable for use as a host of the red light emitting layer in the organic light emitting device.

As can be seen from the data in Table 1, when the compound of Formula 1 is used, it can be confirmed that the driving voltage is low, the efficiency is high, and the long life characteristics are realized. In particular, the compound of Formula 1 herein forms a heptagonal structure condensed with benzocarbazole and a pentagonal ring, and thus an organic light emitting device using a RH-A compound that does not contain a condensed heptagonal structure inside the core, or a heptagonal structure An organic light emitting device using RH-B or RH-C containing a benzene ring that does not contain a hetero atom as a condensed ring, or an organic light emitting device using RH-D or RH-E that is not condensed with a pentagonal ring and In contrast, it was confirmed that low driving voltage and high efficiency and long life were exhibited.

Explanation of symbols

1: Substrate 2: Anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron suppression layer 8: electron injection and transport layer

Claims (9)

1. A compound represented by the following formula (1):

   [Formula 1]

   

   In Formula 1,

   X ₁ , X ₂ and X ₃ are each independently O, S or CR, with the proviso that one of them is O or S, wherein each R is independently hydrogen, deuterium, substituted or unsubstituted C _{6 -60} aryl, a substituted or unsubstituted C _2-60 heteroaryl containing one or more hetero atoms selected from the group consisting of N, O and S, or a substituted or unsubstituted C ₆ - ₆₀ to form a condensed ring,

   L is a single bond, substituted or unsubstituted C _6-60 arylene, or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of N, O and S; ,

   Ar is substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S;

   R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- containing one or more heteroatoms selected from the group consisting of N, O and S ₆₀ heteroaryl;

   n is an integer from 0 to 8;
2. The method of claim 1,

   The compound represented by Formula 1 is represented by the following Formulas 1-1 to 1-6,

   compound:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   [Formula 1-4]

   

   [Formula 1-5]

   

   [Formula 1-6]

   

   In Formulas 1-1 to 1-6,

   L, Ar, R ₁ and n are as defined in claim 1,

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

   R ₂ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-30 aryl, or substituted or unsubstituted C _2- containing one or more heteroatoms selected from the group consisting of N, O and S ₃₀ heteroaryl;

   m is an integer from 0 to 4.
3. The method of claim 1,

   L is a single bond, or any one selected from the group consisting of

   compound:

   

   In the group,

   each R″ is independently hydrogen, deuterium or phenyl;

   a is each independently an integer of 0 to 4,

   b is each independently an integer of 0-6.
4. The method of claim 1,

   Ar is any one selected from the group consisting of

   compound:

   

   In the group,

   X' ₁ , X' ₂ and X' ₃ are each independently N or CH, provided that at least two of them are N;

   Y is each independently O or S,

   Ar ₁ is each independently substituted or unsubstituted C _6-30 aryl, or substituted or unsubstituted C _2-30 heteroaryl including one or more heteroatoms selected from the group consisting of N, O and S .
5. 5. The method of claim 4,

   Ar ₁ is each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, dimethyl fluorenyl, diphenylfluorenyl, dibenzofu ranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl;

   which are unsubstituted or substituted with one or more deuterium;

   compound.
6. The method of claim 1,

   R ₁ is each independently hydrogen, deuterium, or phenyl;

   compound.
7. The method of claim 1,

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

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
8. 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 7 which is an organic light emitting device.
9. 9. The method of claim 8,

   The organic material layer containing the compound is a light emitting layer,

   organic light emitting device.

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