WO2024049067A1 - 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 compounds and organic light-emitting devices containing them

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0111425 dated September 2, 2022 and Korean Patent Application No. 10-2023-0107078 dated August 16, 2023, and the relevant Korean patent applications All content disclosed in the literature is incorporated as part of this specification.

The present invention relates to novel compounds and organic light-emitting devices containing the same.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

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. 10-2000-0051826

The present invention relates to novel compounds and organic light-emitting devices containing them.

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

[Formula 1]

In Formula 1,

X is O or S,

R ₁ and R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _6-60 aryl,

L ₁ is a single bond,

L ₂ is a single bond, or substituted or unsubstituted C _6-60 arylene,

Ar ₁ is substituted or unsubstituted C _6-60 aryl,

Y ₁ to Y ₃ are each independently N, CH, or CD,

Y ₄ to Y ₆ are each independently N or CR ₃ ,

Y ₇ is CR ₃ ,

R ₃ is hydrogen, deuterium, or substituted or unsubstituted C _6-60 aryl,

At least one of Y ₁ to Y ₆ is N.

In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising 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 a compound represented by Formula 1. .

The compound represented by the above-mentioned formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device. In particular, the compound represented by the above-mentioned formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

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

Figure 2 shows 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 a cathode 4. An example of an organic light-emitting device is shown.

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

In this specification,

and

means a bond connected to another substituent, and “D” means deuterium.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with a substituent in which two or more of the above-exemplified substituents are connected. it means. For example, “a substituent group in which two or more substituents are connected” may be a biphenylyl group. That is, the biphenylyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected. For example, the term "substituted or unsubstituted" means "unsubstituted or selected from the group consisting of deuterium, halogen, cyano, C _1-10 alkyl, C _1-10 alkoxy and C _6-20 aryl. “substituted with one or more substituents”; or “unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano, methyl, ethyl, phenyl and naphthyl.” Additionally, in this specification, the term “substituted with one or more substituents” can be understood to mean “substituted with one to the maximum number of substitutable hydrogens.” Alternatively, the term “substituted with one or more substituents” as used herein may be understood to mean “substituted with 1 to 5 substituents,” or “substituted with 1 or 2 substituents.”

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, the substituent may have the structure shown below, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight-chain, branched-chain, or ring-chain alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a substituent of the following structural formula, but is not limited thereto.

In this specification, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, the substituent may have the following structure, but is not limited thereto.

As used herein, substituted or unsubstituted silyl group refers to -Si(Z ₁ )(Z ₂ )(Z ₃ ), where Z ₁ , Z ₂ and Z ₃ are each independently hydrogen, deuterium, substituted or unsubstituted. Substituted C _1-60 alkyl, substituted or unsubstituted C _1-60 haloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _2-60 haloalkenyl, or substituted or unsubstituted It may be a C _6-60 aryl group. According to one embodiment, Z ₁ , Z ₂ and Z ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, substituted or unsubstituted C _1-10 haloalkyl, substituted or unsubstituted It may be C _1-10 haloalkyl, or substituted or unsubstituted C _6-20 aryl. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. It is not limited.

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

In this specification, examples of halogen groups include fluoro, chloro, bromo, or iodo.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, 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-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1,1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5 -methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4,4-trimethyl-1-pentyl, 2,4,4- Trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, etc., but are not limited thereto.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another 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, etc., but are not limited thereto.

In the present specification, the alicyclic group refers to a monovalent substituent derived from a saturated or unsaturated hydrocarbon ring compound that contains only carbon as a ring-forming atom and has no aromaticity, and includes both monocyclic or condensed polycyclic compounds. It is understood to be inclusive. According to one embodiment, the carbon number of the aliphatic ring group is 3 to 60. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. Examples of such aliphatic groups include monocyclic groups such as cycloalkyl groups, bridged hydrocarbon groups, spiro hydrocarbon groups, substituents derived from hydrogenated derivatives of aromatic hydrocarbon compounds, etc. can be mentioned.

Specifically, examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- Examples include dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl, but are not limited thereto.

In addition, examples of the bridged hydrocarbon group include bicyclo[1.1.0]butyl, bicyclo[2.2.1]heptyl, bicyclo[4.2.0]octa-1,3,5-trienyl, adamantyl, Decalinil, etc., but is not limited thereto.

Additionally, examples of the spiro ring hydrocarbon group include spiro[3.4]octyl and spiro[5.5]undecanyl, but are not limited thereto.

In addition, the substituent derived from the hydrogenated derivative of the aromatic hydrocarbon compound refers to a substituent derived from a compound in which hydrogen is added to a portion of the unsaturated bond of a monocyclic or polycyclic aromatic hydrocarbon compound. An example of such a substituent is 1 H -indenyl. , 2 H -indenyl, 4 H -indenyl, 2,3-dihydro-1 H -indenyl , 1,4-dihydronaphthalenyl, 1,2,3,4-tetrahydronaphthalenyl, 6,7,8,9-tetrahydro-5 H -benzo [7] annulenyl (6,7,8,9-tetrahydro-5 H -benzo [7] annulenyl), 6,7-dihydro-5 H -Benzocycloheptenyl, etc., but is not limited thereto.

In the present specification, an aryl group is understood to mean a substituent derived from a monocyclic or condensed polycyclic compound containing only carbon as a ring-forming atom and having aromaticity. The number of carbon atoms is not particularly limited, but is preferably 6 to 60 carbon atoms. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenylyl group, or a terphenylyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be etc. However, it is not limited to this.

As used herein, heterocyclic group refers to a monovalent substituent derived from a monocyclic or condensed polycyclic compound that further contains one or more heteroatoms selected from O, N, Si, and S in addition to carbon as a ring-forming atom. This is understood to encompass both substituents with aromaticity and substituents without aromaticity. According to one embodiment, the carbon number of the heterocyclic group is 2 to 60 carbon atoms. According to another embodiment, the heterocyclic group has 2 to 30 carbon atoms. According to another embodiment, the heterocyclic group has 2 to 20 carbon atoms. Examples of such heterocyclic groups include heteroaryl groups and substituents derived from hydrogenated derivatives of heteroaromatic compounds.

Specifically, the heteroaryl group refers to a substituent derived from a monocyclic or condensed polycyclic compound further containing one or more heteroatoms selected from N, O, and S in addition to carbon as a ring forming atom, and refers to a substituent having aromaticity. do. According to one embodiment, the carbon number of the heteroaryl group is 2 to 60 carbon atoms. According to another embodiment, the heteroaryl group has 2 to 30 carbon atoms. According to another embodiment, the heteroaryl group has 2 to 20 carbon atoms. Examples of the heteroaryl group include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, bipyridinyl group, pyrimidinyl group, and triazinyl group. group, acridinyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, isoquinolinyl group, indole Diary group, carbazolyl group, benzoxazolyl group, benzoimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, dibenzofuranyl group, phenanthrolinyl group, isoxa These include, but are not limited to, azolyl group, thiadiazolyl group, and phenothiazinyl group.

In addition, the substituent derived from the hydrogenated derivative of the heteroaromatic compound refers to a substituent derived from a compound in which hydrogen is added to a portion of the unsaturated bond of a monocyclic or polycyclic heteroaromatic compound. An example of such a substituent is 1,3-di. Hydroisobenzofuranyl (1,3-dihydroisobenzofuranyl), 2,3-dihydrobenzofuranyl (2,3-dihydrobenzofuranyl), 1,3-dihydrobenzo [ c ] thiophenyl (1,3-dihydrobenzo [ c ]thiophenyl), 2,3-dihydro[ b ]thiophenyl (2,3-dihydro[ b ]thiophenyl), etc., but are not limited thereto.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above. In this specification, the aralkyl group, alkylaryl group, and alkylamine group are the same as the examples of the alkyl group described above. In the present specification, the description regarding heteroaryl described above may be applied to heteroaryl among heteroarylamines. In this specification, the alkenyl group among the aralkenyl groups is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above can be applied, except that arylene is a divalent group. In the present specification, the description of heteroaryl described above can be applied, except that heteroarylene is a divalent group. In the present specification, the description of the aryl group or cycloalkyl group described above can be applied, except that the hydrocarbon ring is not monovalent and is formed by combining two substituents. In the present specification, the description of heteroaryl described above can be applied, except that the heterocycle is not monovalent and is formed by combining two substituents.

As used herein, “deuterated or substituted with deuterium” means that at least one of the replaceable hydrogens in a compound, a divalent linking group, or a monovalent substituent is replaced with deuterium.

In addition, “unsubstituted or substituted with deuterium” or “substituted or unsubstituted with deuterium” means “one to the maximum number of unsubstituted or replaceable hydrogens is substituted with deuterium.” For example, the term “phenanthryl unsubstituted or substituted with deuterium” means “unsubstituted or substituted with 1 to 9 deuteriums,” considering that the maximum number of hydrogens that can be substituted with deuterium in the phenanthryl structure is 9. It can be understood to mean “substituted phenanthryl.”

In addition, the meaning of “deuterated structure” refers to compounds of all structures in which at least one hydrogen is replaced with deuterium, a divalent linking group, or a monovalent substituent. For example, the deuterated structure of phenyl can be understood to refer to monovalent substituents of all structures in which at least one replaceable hydrogen in the phenyl group is replaced with deuterium, as follows.

Additionally, the “deuterium substitution rate” or “deuteration degree” of a compound is the number of substituted deuteriums relative to the total number of hydrogens that can be present in the compound (the total sum of the number of hydrogens that can be replaced by deuterium and the number of substituted deuteriums in the compound). It means calculating the ratio as a percentage. Therefore, when the “deuterium substitution rate” or “deuteration degree” of a compound is “K%”, it means that K% of the hydrogen replaceable by deuterium in the compound has been replaced with deuterium.

At this time, the “deuterium substitution rate” or “deuteration degree” is measured using MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer), nuclear magnetic resonance spectroscopy ( ^1H NMR), and TLC/MS (Thin -It can be measured according to commonly known methods using Layer Chromatography/Mass Spectrometry) or GC/MS (Gas Chromatography/Mass Spectrometry). More specifically, when using MALDI-TOF MS, the “deuterium substitution rate” or “deuteration degree” is calculated by calculating the number of deuterium substituted in the compound through MALDI-TOF MS analysis, and then comparing the total number of hydrogens that may exist in the compound. The ratio of the number of deuteriums formed can be calculated as a percentage.

(compound)

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

Preferably, R ₁ is each independently hydrogen or deuterium.

Preferably, R ₂ is hydrogen, deuterium, phenyl, or naphthyl; The phenyl and naphthyl are unsubstituted or substituted with one or more hydrogen atoms.

Preferably, L ₂ is a single bond.

Preferably, Ar ₁ is phenyl, biphenylyl, naphthyl, naphthyl-phenyl, or phenyl-naphthyl; Ar ₁ is unsubstituted or substituted with one or more deuterium. For example, Ar ₁ is phenyl, biphenylyl, naphthyl, naphthyl-phenyl, or phenyl-naphthyl, and when Ar ₁ is phenyl, it is unsubstituted, or 1, 2, 3, 4, Alternatively, it may be substituted with 5 deuterium atoms.

Preferably, R ₃ is hydrogen, deuterium, or phenyl, wherein the phenyl is unsubstituted or substituted with one or more deuterium.

Preferably, any one of Y ₁ to Y ₆ is N.

Specifically, Y ₁ is N, Y ₂ to Y ₄ are each independently CH or CD, Y ₅ and Y ₆ are each independently CH, CD, or C (unsubstituted or substituted with one or more deuterium) phenyl) or;

Y ₂ is N, Y ₁ , Y ₃ and Y ₄ are each independently CH or CD, Y ₅ and Y ₆ are each independently CH, CD, or C (unsubstituted or substituted with one or more deuterium phenyl) or;

Y ₃ is N, Y ₁ , Y ₂ , Y ₄ are each independently CH or CD, Y ₅ and Y ₆ are each independently CH, CD, or C (unsubstituted or substituted with one or more deuterium) phenyl) or;

Y ₄ is N, Y ₁ to Y ₃ are each independently CH or CD, Y ₅ and Y ₆ are each independently CH, CD, or C (unsubstituted or phenyl substituted with one or more deuterium) ;

Y ₅ is N, Y ₁ to Y ₄ are each independently CH or CD, and Y ₆ is CH, CD, or C (unsubstituted or phenyl substituted with one or more deuterium);

Y ₆ is N, Y ₁ to Y ₄ are each independently CH or CD, and Y ₅ may be CH, CD, or C (unsubstituted or phenyl substituted with one or more deuterium).

Additionally, Y ₇ may be CH or CD.

Preferably, the substituent

may be a substituent represented by any of the following formulas (a) to (d):

In the above formulas (a) to (d),

X is as defined above.

Representative examples of compounds represented by Formula 1 are as follows:

.

Additionally, the present invention provides a method for producing a compound represented by Chemical Formula 1, as shown in Scheme 1 below:

[Scheme 1]

In Scheme 1, all elements except Z are as defined above, and Z is halogen, preferably bromo or chloro.

The reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the reaction can be changed according to what is known in the art. The manufacturing method may be further detailed in the manufacturing examples described later.

(Organic light emitting device)

Additionally, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a compound represented by Formula 1. .

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or 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, 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 to this and may include fewer organic layers.

Additionally, the organic layer may include a light-emitting layer, and in this case, the organic layer containing the compound represented by Formula 1 may be a light-emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron injection and transport layer, and in this case, the organic material layer containing the compound may be a light emitting layer.

Additionally, 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. Additionally, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In this structure, the compound represented by Formula 1 may be included in the light-emitting layer.

Figure 2 shows 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 a cathode 4. An example of an organic light-emitting device is shown. In this structure, the compound represented by Formula 1 may be included in the light-emitting layer.

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

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

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

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

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

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

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

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The electron blocking layer is formed on the hole transport layer, preferably in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. This refers to the layer that plays a role in improving. The electron blocking layer includes an electron blocking material, and examples of the electron blocking material include arylamine-based organic materials, but are not limited thereto.

The light-emitting material is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

The light emitting layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The hole blocking layer is formed on the light-emitting layer, preferably in contact with the light-emitting layer, to improve the efficiency of the organic light-emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling. It refers to the layer that plays a role. The hole blocking layer includes a hole blocking material. Examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; Oxadiazole derivatives; phenanthroline derivatives; Compounds into which electron-withdrawing groups are introduced, such as phosphine oxide derivatives, may be used, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously performs the roles of an electron transport layer and an electron injection layer, injecting electrons from an electrode and transporting the received electrons to the light-emitting layer, and is formed on the light-emitting layer or the hole blocking layer. As such an electron injection and transport material, a material that can easily inject electrons from the cathode and transfer them to the light emitting layer, and a material with high mobility for electrons, is suitable. Examples of electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complex; Triazine derivatives, etc., but are not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds. , or a nitrogen-containing 5-membered ring derivative, etc., but is not limited thereto.

The electron injection and transport layer may also be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting 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, an electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include 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 and nitrogen-containing five-membered ring derivatives can be used.

Examples of the metal complex compounds 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-hydroxyquinolinato)chlorogallium, bis(2-methyl-8-hydroxyquinolinato) Nolinato) (o-cresolato) gallium, bis (2-methyl-8-hydroxyquinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-hydroxyquinolinato) (2- Naphtolato) gallium, etc., but is not limited thereto.

The organic light-emitting device according to the present invention may be a bottom-emitting device, a top-emitting device, or a double-sided light-emitting device. In particular, it may be a bottom-emitting device that requires relatively high luminous efficiency.

Additionally, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to an organic light-emitting device.

Hereinafter, the present invention will be described in more detail to aid understanding. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

[Manufacturing example]

Preparation Example 1: Preparation of Intermediate 1-2

Step 1) Preparation of Compound 1-1

1-bromodibenzo[b,d]furan (20.0 g, 81.3 mmol), PtO ₂ (4.6 g, 20.3 mmol), and D ₂ O (293 ml) were added to the shaker tube, then the tube was sealed and incubated at 250°C and 600°C. Heated at psi for 9 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried and concentrated with anhydrous magnesium sulfate, and the sample was purified by silica gel column chromatography to prepare Intermediate 1-1 (14.6 g, 72%).

MS: [M+H] ⁺ = 251

Step 2) Preparation of Compound 1-2

Intermediate 1-1 (14.6 g, 58.1 mmol) and bis(pinacolato)diboron (17.7 g, 69.8 mmol) were added to Dioxane (292 ml) in a nitrogen atmosphere, stirred and refluxed. Afterwards, potassium acetate (16.8 g, 174.4 mmol) was added, stirred sufficiently, and then bis(dibenzylideneacetone)palladium (1 g, 1.7 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. After reacting for 7 hours, the mixture was cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in 520 mL of 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 recrystallized with chloroform and ethanol to prepare solid compound Intermediate 1-2 (14.9 g, 86%).

MS: [M+H] ⁺ = 299.2

Preparation Example 2: Preparation of Intermediate 2-1

Intermediate 2-1 (11.5 g, yield 86%) was prepared in the same manner as the preparation method of Intermediate 1-2 in Preparation Example 1, except that 1-chloro-7-phenyldibenzo[b,d]furan was used instead of Intermediate 1-1. ) was prepared.

MS: [M+H] ⁺ = 371

Preparation Example 3: Preparation of Intermediate 3-1

7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline (5 g, 15.1 mmol) and 2,4-dichloro-6-( naphthalen-2-yl)-1,3,5-triazine (4.2 g, 15.1 mmol) was added to 100 ml of toluene, stirred, and refluxed. Afterwards, sodium carbonate (4.8 g, 45.3 mmol) was dissolved in 5 ml of water, stirred sufficiently, and tetrakistriphenyl-phosphinopalladium (0.5 g, 0.5 mmol) was added. After 9 hours of reaction, the reaction mixture was cooled to room temperature and the resulting solid was filtered. The solid was dissolved in 302 mL of 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 recrystallized with chloroform and ethanol to prepare solid compound Intermediate 3-1 (5.7 g, 85%).

MS: [M+H] ⁺ = 445.1

Preparation Example 4: Preparation of Intermediate 3-2

Instead of 7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline, use 7-phenyl-3-(4,4,5,5-tetramethyl-1, Intermediate 3-2 (5.4 g, yield 80%) was prepared in the same manner as the preparation of Intermediate 3-1 in Preparation Example 3, except that 3,2-dioxaborolan-2-yl)quinoline was used.

MS: [M+H] ⁺ = 445

Preparation Example 5: Preparation of Intermediate 3-3

Instead of 7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline, use 7-phenyl-6-(4,4,5,5-tetramethyl-1, Intermediate 3-3 (4.0 g, yield 60%) was prepared in the same manner as the preparation of Intermediate 3-1 in Preparation Example 3, except that 3,2-dioxaborolan-2-yl)isoquinoline was used.

MS: [M+H] ⁺ = 445

Preparation Example 6: Preparation of Intermediate 3-4

7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline and 2,4-dichloro-6-(naphthalen-2-yl)-1,3 , 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline and 2,4-dichloro-6-(4-(naphthalen-2-yl) instead of 5-triazine Intermediate 3-4 (6.8 g, yield 78%) was prepared in the same manner as the preparation of Intermediate 3-1 in Preparation Example 3, except that phenyl)-1,3,5-triazine was used.

MS: [M+H] ⁺ = 445

Preparation Example 7: Preparation of Intermediate 3-5

7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline and 2,4-dichloro-6-(naphthalen-2-yl)-1,3 , Instead of 5-triazine, use 3-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline and 2-([1,1'-biphenyl]-4- Intermediate 3-5 (4.2 g, yield 59%) was prepared in the same manner as the preparation of Intermediate 3-1 in Preparation Example 3, except that yl)-4,6-dichloro-1,3,5-triazine was used. .

MS: [M+H] ⁺ = 471

Preparation Example 8: Preparation of Intermediate 3-6

7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline and 2,4-dichloro-6-(naphthalen-2-yl)-1,3 , Instead of 5-triazine, use 6-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline and 2,4-dichloro-6-(naphthalen-1-yl ) Intermediate 3-6 (4.5 g, yield 67%) was prepared in the same manner as the preparation of Intermediate 3-1 in Preparation Example 3, except that -1,3,5-triazine was used.

MS: [M+H] ⁺ = 445

Preparation Example 9: Preparation of Intermediate 3-7

Instead of 7-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline, use 2-(4,4,5,5-tetramethyl-1,3,2- Intermediate 3-7 (6.4 g, yield 89%) was prepared in the same manner as the preparation of Intermediate 3-1 in Preparation Example 3, except that dioxaborolan-2-yl)quinoline was used.

MS: [M+H] ⁺ = 369

[Synthesis example]

Synthesis Example 1: Preparation of Compound 1

In a nitrogen atmosphere, Intermediate 1-3 (5 g, 11.3 mmol) and dibenzo[b,d]furan-1-ylboronic acid (2.4 g, 11.3 mmol) were added to 100 ml of toluene, stirred, and refluxed. Afterwards, potassium carbonate (4.7 g, 33.8 mmol) was dissolved in 5 ml of water, stirred sufficiently, and then bis(tri-butylphosphine)palladium (0.1 g, 0.1 mmol) was added. After reaction for 1 hour, the reaction mixture was cooled to room temperature and the resulting solid was filtered. The solid was dissolved in 292 mL of dichlorobenzene, 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 solid compound Compound 1 (4.7 g, 73%) was prepared through recrystallization of the concentrated compound with dichlorobenzene and tetrahydrofuran.

MS: [M+H] ⁺ = 577

Synthesis Example 2: Preparation of Compound 2

Compound 2 was prepared in the same manner as the preparation of Compound 1 in Synthesis Example 1, except that Intermediate 3-2 and Intermediate 1-2 were used instead of Intermediate 1-3 and dibenzo[b,d]furan-1-ylboronic acid ( 4.2 g, yield 65%).

MS: [M+H] ⁺ = 581

Synthesis Example 3: Preparation of Compound 3

Compound 3 was prepared in the same manner as the preparation of Compound 1 in Synthesis Example 1, except that Intermediate 3-3 was used instead of Intermediate 1-3 (5.1 g, yield 78%).

MS: [M+H] ⁺ = 577

Synthesis Example 4: Preparation of Compound 4

Compound 4 was prepared in the same manner as the preparation of Compound 1 in Synthesis Example 1, except that Intermediate 3-4 was used instead of Intermediate 1-3 (5.4 g, yield 84%).

MS: [M+H] ⁺ = 577

Synthesis Example 5: Preparation of Compound 5

Compound 5 was prepared in the same manner as the preparation of Compound 1 in Synthesis Example 1, except that Intermediate 3-5 was used instead of Intermediate 1-3 (5.6 g, yield 87%).

MS: [M+H] ⁺ = 603

Synthesis Example 6: Preparation of Compound 6

Compound 6 was prepared in the same manner as the preparation of Compound 1 in Synthesis Example 1, except that Intermediate 3-6 was used instead of Intermediate 1-3 (5.1 g, yield 79%).

MS: [M+H] ⁺ = 577

Synthesis Example 7: Preparation of Compound 7

Compound 7 was prepared in the same manner as the preparation of compound 1 in Synthesis Example 1, except that intermediate 3-7 and intermediate 2-1 were used instead of intermediate 1-3 and dibenzo[b,d]furan-1-ylboronic acid ( 4.9 g, yield 75%).

MS: [M+H] ⁺ = 577

[Example]

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1,000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent manufactured by Fischer Co. was used, and distilled water filtered secondarily using a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, the following HI-1 compound was formed as a hole injection layer to a thickness of 1150 Å, and the following HAT compound was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer with a film thickness of 800 Å. Subsequently, the following EB-1 compound was vacuum deposited on the hole transport layer to a film thickness of 150 Å to form an electron blocking layer.

Next, Compound 1 prepared in Synthesis Example 1 and the following RD compound were vacuum deposited on the EB-1 deposition film at a weight ratio of 98:2 to form a red light-emitting layer with a thickness of 400 Å.

The following HB-1 compound was vacuum deposited on the light emitting layer to a film thickness of 30 Å to form a hole blocking layer. Next, the following ET-1 compound and the following LiQ compound were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic matter was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2*10. An organic light emitting device was manufactured by maintaining ^-7 to 5*10 ^-6 torr.

Examples 2 to 7

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1 as the host compound of the light-emitting layer.

Comparative Examples 1 to 5

An organic light-emitting device was manufactured in the same manner as Example 1, except that Compounds C1 to C5 listed in Table 1 below were used instead of Compound 1 as the host compound of the light-emitting layer. Here, compounds C1 to C5 are as follows.

Experiment example

Current was applied to the organic light-emitting devices manufactured in Examples 1 to 7 and Comparative Examples 1 to 5, and voltage, efficiency, and lifespan were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease from the initial luminance to 95%.

	compound	Voltage (V) (@10mA/cm 2 )	Efficiency (Cd/A) (@10mA/cm 2 )	Lifespan (h) (LT95 at 50mA/cm 2 )
Example 1	Compound 1	4.8	24.1	165
Example 2	compound 2	4.7	24.0	182
Example 3	Compound 3	4.6	23.3	163
Example 4	Compound 4	4.8	23.7	159
Example 5	Compound 5	4.7	23.9	161
Example 6	Compound 6	4.6	24.1	155
Example 7	Compound 7	4.7	24.2	153
Comparative Example 1	C1	5.7	14.3	59
Comparative Example 2	C2	5.0	21.5	121
Comparative Example 3	C3	5.1	20.8	105
Comparative Example 4	C4	5.5	19.7	103
Comparative Example 5	C5	5.4	20.1	101

As shown in Table 1, the organic light emitting device of the example using the compound represented by Formula 1 as the host material of the light emitting layer has superior performance in terms of efficiency and lifespan compared to the organic light emitting device of the comparative example using a compound having a different structure. It was confirmed that it represents .

As described above, it was confirmed that the compounds of the present invention exhibited superior properties in terms of efficiency and lifespan depending on the position and type of the substituent compared to the comparative compounds.

[Explanation of symbols]

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 (10)

1. Compound represented by Formula 1:

   [Formula 1]

   

   In Formula 1,

   X is O or S,

   R ₁ and R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _6-60 aryl,

   L ₁ is a single bond,

   L ₂ is a single bond, or substituted or unsubstituted C _6-60 arylene,

   Ar ₁ is substituted or unsubstituted C _6-60 aryl,

   Y ₁ to Y ₃ are each independently N, CH, or CD,

   Y ₄ to Y ₆ are each independently N or CR ₃ ,

   Y ₇ is CR ₃ ,

   R ₃ is hydrogen, deuterium, or substituted or unsubstituted C _6-60 aryl,

   At least one of Y ₁ to Y ₆ is N.
2. According to paragraph 1,

   R ₁ is each independently hydrogen or deuterium,

   compound.
3. According to paragraph 1,

   R ₂ is hydrogen, deuterium, phenyl, or naphthyl,

   The phenyl and naphthyl are unsubstituted or substituted with one or more hydrogen hydrogens,

   compound.
4. According to paragraph 1,

   L ₂ is a single bond,

   compound.
5. According to paragraph 1,

   Ar ₁ is phenyl, biphenylyl, naphthyl, naphthyl-phenyl, or phenyl-naphthyl,

   Ar ₁ is unsubstituted or substituted with one or more deuterium,

   compound.
6. According to paragraph 1,

   R ₃ is hydrogen, deuterium, or phenyl,

   The phenyl is unsubstituted or substituted with one or more deuterium,

   compound.
7. According to paragraph 1,

   Any one of Y ₁ to Y ₆ is N,

   compound.
8. According to paragraph 1,

   The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,

   compound:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
9. first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising 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 according to any one of claims 1 to 8. organic light-emitting device.
10. In paragraph 9

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

    Organic light emitting device.

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