KR102645708B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same}

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

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.

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,

L ₁ to L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms among N, O and S,

Ar ₁ is substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S,

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted benzonaphthofuranyl; Substituted or unsubstituted benzonaphthothiophenyl; or substituted or unsubstituted benzocarbazolyl,

R ₁ is hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S,

R ₂ is hydrogen; or deuterium,

a is an integer from 0 to 8,

b is an integer from 0 to 6,

When a and b are 2 or more, the substituents in parentheses are the same or different from each other.

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-described 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.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6.
2 shows a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), an electron injection and transport layer (5), and a cathode (6). It shows an example of an organic light emitting device made of.

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

(Definition of Terms)

는 다른 치환기에 연결되는 결합을 의미한다.In this specification, and

means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; 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 heteroaryl containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

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 following structure, 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.

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

In the present 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 fluorine, chlorine, bromine, or iodine.

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, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

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 to these.

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

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 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 biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthryl 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.

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a heteroelement, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, phenothiazinyl group, and dibenzofuranyl group, but are not limited to these.

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.

(compound)

Meanwhile, the present invention provides a compound represented by Formula 1 above.

Specifically, the compound represented by Formula 1 is a compound in which the 9th position of fluorene and the amino group are linked by a naphthalene linker, and the substituents of the amino group are an aryl group, benzonaphthofuranyl group, benzonaphthothiophenyl group, and benzocarboxylic group. Its characteristic is that it is selected from the group consisting of jol-ilgi. The organic light-emitting device employing the compound represented by Formula 1 is compared to the organic light-emitting device employing a compound containing an amino group with another substituent and a compound in which the 9th position of fluorene and the amino group are linked by a phenylene linker, It can exhibit characteristics such as high efficiency, low driving voltage, and long lifespan.

Meanwhile, the compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-4 depending on the connection position of the naphthalene linker:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

L ₁ to L ₃ , Ar ₁ to Ar ₃ , R ₁ and R ₂ are as defined in Formula 1 above.

More specifically, the compound represented by Formula 1 has the following formulas 1-1-1 to 1-1-3, 1-2-1 to 1-2-4, 1-3-1 to 1-3-4 and 1-4-1 to 1-4-4:

In the formulas 1-1-1 to 1-1-3, 1-2-1 to 1-2-4, 1-3-1 to 1-3-4, and 1-4-1 to 1-4-4 ,

이고, Z is

ego,

L ₁ to L ₃ , Ar ₁ to Ar ₃ , R ₁ and R ₂ are as defined in Formula 1 above.

Additionally, in Formula 1, L ₁ to L ₃ are each independently a single bond; Alternatively, it may be unsubstituted or C 6-20 arylene substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl _{, and C 6-20 aryl} .

Specifically, L ₁ to L ₃ are each independently a single bond; Unsubstituted or deuterium-substituted phenylene; Alternatively, it may be unsubstituted or deuterium-substituted naphthylene.

More specifically, L ₁ is a single bond,

L ₂ and L ₃ may each independently be a single bond or any one selected from the group consisting of:

.

.

Or, L ₁ to L ₃ are all single bonds; or

L ₁ is a single bond, one of L ₂ and L ₃ is a single bond, and the other one may be any one selected from the group consisting of:

.

.

Additionally, in Formula 1, Ar ₁ is unsubstituted or C _6-20 aryl substituted with one or more substituents selected from the group consisting of deuterium, halogen, C _1-10 alkyl, and C _6-20 aryl. You can.

More specifically, Ar ₁ may be unsubstituted or phenyl substituted with deuterium.

Additionally, in Formula 1, Ar ₂ and Ar ₃ are each independently C _6-30 aryl, benzonaphthofuranyl, benzonaphthothiophenyl, or benzocarbazolyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl, and C _6-20 aryl.

Specifically, Ar ₂ and Ar ₃ are each independently selected from phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, or benzoyl. It's carbazol,

Here, Ar ₂ and Ar ₃ are unsubstituted or have one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl, for example, deuterium, methyl, ethyl, propyl, It may be substituted with one or more substituents selected from the group consisting of isopropyl, butyl, tert-butyl and phenyl.

More specifically, Ar ₂ and Ar ₃ may each independently be any one selected from the group consisting of:

.

.

At this time, Ar ₂ and Ar ₃ may be the same. Alternatively, Ar ₁ and Ar ₂ may be different.

Additionally, both Ar ₂ and Ar ₃ may not be phenyl.

In addition, R ₁ and R ₂ may each independently be hydrogen or deuterium,

At this time, a is 0, 1, 2, 3, 4, 5, 6, 7, or 8, and b is 0, 1, 2, 3, 4, 5, or 6.

Meanwhile, representative examples of the compound represented by Formula 1 are as follows:

.

Meanwhile, the compound represented by Formula 1 can be prepared by a production method as shown in Scheme 1 below, for example, when L ₁ is a single bond.

[Scheme 1]

In Scheme 1,

Specifically, the compound represented by Formula 1 can be prepared through amine substitution reaction of starting materials A1 and A2. This amine substitution reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be appropriately changed. The method for producing the compound represented by Formula 1 may be more detailed in the production examples to be described later.

(Organic light emitting device)

Meanwhile, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. For example, 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 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, 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.

In one embodiment, the organic material layer may include a hole transport layer, a light-emitting layer, and an electron injection and transport layer, and in this case, the organic material layer containing the compound may be a hole transport 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, and an electron injection and transport layer, and in this case, the organic material layer containing the compound may be a hole transport layer or an electron blocking 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, wherein the organic material layer containing the compound is a hole transport layer or an electron blocking layer. You can.

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 is an organic material layer that, in addition to the light-emitting layer, further includes a hole injection layer and a hole transport layer between the first electrode and the light-emitting layer, and an electron transport layer and an electron injection layer between the light-emitting layer and the second electrode. It can have a structure that does. However, the structure of the organic light emitting device is not limited to this and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention is 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 where the first electrode is an anode and the second electrode is a cathode. It may be a device. In addition, the organic light emitting device according to the present invention is an inverted type organic device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate where the first electrode is a cathode and the second electrode is an anode. It may be a light emitting device. 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 hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6. In this structure, the compound represented by Formula 1 may be included in the hole transport layer.

2 shows a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), an electron injection and transport layer (5), and a cathode (6). It shows an example of an organic light emitting device made of. In this structure, the compound represented by Formula 1 may be included in the hole transport layer or the electron blocking 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 Chemical Formula 1. 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.

Additionally, 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, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

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. These include organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, 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. The hole transport material is a material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and has high mobility for holes. The material is suitable. As the hole transport material, a compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having both a conjugated and non-conjugated portion may be used, but is not limited thereto. .

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 the compound represented by Chemical Formula 1, or an arylamine-based organic material, but are not limited thereto.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, 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 thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material may include a compound represented by Formula 1 above, or may further include a condensed aromatic ring derivative or a heterocycle-containing compound. 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. Specific 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 to these. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene 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, preorenylidene methane, anthrone, etc. 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-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

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 represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

Meanwhile, the compound represented by Chemical Formula 1 can be prepared, for example, by a production method as shown in Scheme 1 below.

Synthesis Example A: Synthesis of Intermediate M-1

Step 1) Synthesis of intermediate M-a

2,6-dibromonaphthalene (20.0 g, 69.9 mmol) was dissolved in 200 mL of diethylether in a dried round bottom flask, cooled to -78°C, and stirred under a nitrogen atmosphere. 30.8 mL (76.9 mmol) of n-butyllithium 2.5M n-hexane solution was slowly added here, and then stirred for 2 hours at -78°C under a nitrogen atmosphere. 9H-fluoren-9-one (13.9 g, 76.9 mmol) dissolved in 40 mL of THF was slowly added thereto and stirred for 8 hours at room temperature under a nitrogen atmosphere. The reaction solution was cooled to 0°C, 100 mL of 1.0M aqueous ammonium chloride solution was added thereto, 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 23.0 g of intermediate Ma. (Yield 85%, MS: [M+H] ⁺ = 388)

Step 2) Synthesis of intermediate M-1

Intermediate Ma (20.0 g, 51.6 mmol) was added to a round bottom flask and dissolved by adding 138.5 mL of benzene. Trifluoromethanesulfonic acid (8.5 g, 56.8 mmol) was slowly added here, and then refluxed and stirred for 24 hours under a nitrogen atmosphere. After completion of the reaction, 70 mL of 1.0M sodium bicarbonate aqueous solution was slowly added to the reaction solution, the organic layer was separated using ethyl acetate and water, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of intermediate M-1. (Yield 43%, MS: [M+H] ⁺ = 448)

Synthesis Example B: Synthesis of Intermediate M-2

In Synthesis Example A, Intermediate M-2 was prepared in the same manner as that of Intermediate M-1, except that 2,6-dibromonaphthalene was changed to 2,7-dibromonaphthalene. (MS: [M+H] ⁺ = 448)

Synthesis Example C: Synthesis of Intermediate M-3

In Synthesis Example A, Intermediate M-3 was prepared in the same manner as that of Intermediate M-1, except that 2,6-dibromonaphthalene was changed to 1,5-dibromonaphthalene. (MS: [M+H] ⁺ = 448)

Synthesis Example D: Synthesis of intermediate M-4

In Synthesis Example A, Intermediate M-4 was prepared using the same manufacturing method as that of Intermediate M-1, except that 2,6-dibromonaphthalene was changed to 1,4-dibromonaphthalene. (MS: [M+H] ⁺ = 448)

Synthesis Example 1: Synthesis of Compound 1

In a nitrogen atmosphere, intermediate M-1 (15.0 g, 33.5 mmol) and compound a (9.1 g, 36.9 mmol) were added to 300 mL of toluene, stirred, and refluxed. Afterwards, sodium tert-butoxide (4.8 g, 50.3 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 mmol) were added. After reaction for 12 hours, it 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, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, and then 14.2 g of Compound 1 was prepared through sublimation purification. (Yield 69%, MS: [M+H] ⁺ = 613)

Synthesis Example 2: Synthesis of Compound 2

In Synthesis Example 1, Compound 2 was prepared using the same method as that of Compound 1, except that Compound a was changed to Compound b. (MS: [M+H] ⁺ = 663)

Synthesis Example 3: Synthesis of Compound 3

In Synthesis Example 1, Compound 3 was prepared in the same manner as that of Compound 1, except that Intermediate M-1 was changed to Intermediate M-2 and Compound a was changed to Compound c. (MS: [M+H] ⁺ = 663)

Synthesis Example 4: Synthesis of Compound 4

In Synthesis Example 1, Compound 4 was prepared in the same manner as that of Compound 1, except that Intermediate M-1 was changed to Intermediate M-2 and Compound a was changed to Compound d. (MS: [M+H] ⁺ = 677)

Synthesis Example 5: Synthesis of Compound 5

In Synthesis Example 1, Compound 5 was prepared using the same method as that of Compound 1, except that Intermediate M-1 was changed to Intermediate M-3 and Compound a was changed to Compound e. (MS: [M+H] ⁺ = 739)

Synthesis Example 6: Synthesis of Compound 6

In Synthesis Example 1, Compound 6 was prepared by the same method as that of Compound 1, except that Intermediate M-1 was changed to Intermediate M-3 and Compound a was changed to Compound f. (MS: [M+H] ⁺ = 653)

Synthesis Example 7: Synthesis of Compound 7

In Synthesis Example 1, Compound 7 was prepared in the same manner as that of Compound 1, except that Intermediate M-1 was changed to Intermediate M-4. (MS: [M+H] ⁺ = 613)

Synthesis Example 8: Synthesis of Compound 8

In Synthesis Example 1, Compound 8 was prepared by the same method as that of Compound 1, except that Intermediate M-1 was changed to Intermediate M-4 and Compound a was changed to Compound g. (MS: [M+H] ⁺ = 713)

[Example]

Comparative Example 1

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) with a thickness of 1,400 Å was placed in distilled water dissolved in detergent and washed with ultrasonic waves. At this time, Decon™ CON705 from Fischer Co. was used as a detergent, and distilled water filtered secondarily through a 0.22㎛ sterilizing filter from 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 for 10 minutes each, dried, and then transported to a plasma cleaner. Additionally, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, HI-A and LG-101 below were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. On top of this, HT-A below was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and then EB-A below was vacuum-deposited to a thickness of 600 Å as an electron blocking layer.

On the electron blocking layer, the light emitting layer host RH-A and the light emitting layer dopant RD-A were vacuum deposited to a thickness of 400 Å at a weight ratio of 98:2 to form a light emitting layer.

Next, ET-A and Liq below were thermally vacuum deposited to a thickness of 360 Å at a ratio of 1:1 as an electron transport and injection layer on the emitting layer, and then Liq was vacuum deposited to a thickness of 5 Å.

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

Examples 1 to 8 Comparative Examples 2 to 4

Organic light-emitting devices of Examples 1 to 8 and Comparative Examples 2 to 4 were prepared using the same method as Comparative Example 1, except that Compound 1 was changed as shown in Table 1 in Comparative Example 1. were produced respectively.

Meanwhile, the structures of Compounds 1 to 8 used in Examples 1 to 8 and Compounds EB-B, EB-C and EB-D used in Comparative Examples 2 to 4, respectively, are as follows.

Experiment example

Current was applied to the organic light-emitting devices manufactured in Examples 1 to 8 and Comparative Examples 1 to 4, and the voltage, efficiency, and lifespan were measured, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm ² , and LT97 refers to the time until the initial luminance decreases to 97% at a current density of 20 mA/cm ² .

compound
(Electronic blocking layer) Voltage
(V
@10mA/cm ² ) efficiency
(cd/A
@10mA/cm ² ) LT97
(hr
@20mA/cm ² ) Example 1 Compound 1 4.51 20.1 93 Example 2 compound 2 4.60 21.3 91 Example 3 Compound 3 4.53 20.8 97 Example 4 Compound 4 4.45 21.9 90 Example 5 Compound 5 4.50 21.0 109 Example 6 Compound 6 4.52 21.1 91 Example 7 Compound 7 4.59 19.9 90 Example 8 Compound 8 4.54 19.5 92 Comparative Example 1 Compound EB-A 5.49 10.3 31 Comparative Example 2 Compound EB-B 5.32 10.7 59 Comparative Example 3 Compound EB-C 5.16 12.4 43 Comparative Example 4 Compound EB-D 5.06 13.2 46

As shown in Table 1, the organic light-emitting device of the example using the compound represented by Chemical Formula 1 as the material for the electron blocking layer has a lower driving voltage than the organic light-emitting device of the comparative example using a compound not included in Chemical Formula 1. , it can be seen that it exhibits excellent luminous efficiency and significantly improved lifespan characteristics.

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

Claims (10)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
L ₁ is a single bond,
L ₂ and L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms among N, O and S,
Ar ₁ is unsubstituted or phenyl substituted with deuterium,
Ar ₂ and Ar ₃ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, or benzocarbazolyl; ,
Here, Ar ₂ and Ar ₃ are unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl, and C _6-20 aryl,
R ₁ and R ₂ are each independently hydrogen; or deuterium,
a is an integer from 0 to 8,
b is an integer from 0 to 6.
According to paragraph 1,
The compound is represented by any one of the following formulas 1-1 to 1-4,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
L ₁ to L ₃ , Ar ₁ to Ar ₃ , R ₁ and R ₂ are as defined in claim 1.
According to paragraph 1,
L ₂ and L ₃ are each independently a single bond; Unsubstituted or deuterium-substituted phenylene; or naphthylene which is unsubstituted or substituted with deuterium,
compound.
delete delete According to paragraph 1,
Ar ₂ and Ar ₃ are each independently selected from the group consisting of:
compound:

.
delete According to paragraph 1,
The compound is any one selected from the group consisting of the following compounds:

.
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 is any of claims 1 to 3, 6, and 8. An organic light-emitting device comprising the compound according to one clause.
According to clause 9,
The organic material layer containing the compound is a hole transport layer or an electron blocking layer,
Organic light emitting device.