KR102592035B1 - 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 using 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 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. 10-2013-073537

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

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

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, and they may combine with each other to form a ring,

R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 containing one or more heteroatoms selected from the group consisting of N, O and S. It is heteroaryl,

m and n are each independently integers from 0 to 3.

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 the compound of the present invention described above.

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 material for the electron suppression layer.

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.
2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppressing layer (7), a light emitting layer (3), an electron transport layer (8), and an electron injection layer (9). and a cathode (4).

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

In this specification, means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile 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 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, it may be a compound with 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 compound 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, it may be a compound with 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, and cyclooctyl.

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, biphenyl group, or terphenyl 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.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups 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, and 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, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but is not limited to these.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In 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 the heterocyclic group 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 the heterocyclic group 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 the heterocyclic group described above can be applied, except that the heterocycle is not a monovalent group and is formed by combining two substituents.

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

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, and they may combine with each other to form a ring,

R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl, which may combine with adjacent substituents to form a ring,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 containing one or more heteroatoms selected from the group consisting of N, O and S. It is heteroaryl,

m and n are each independently integers from 0 to 3.

Preferably, the compound represented by Formula 1 may be any one selected from compounds represented by Formulas 2 to 10 below:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 2 to 10,

R ₁ , R ₂ , R ₃ , R ₄ , Ar ₁ , Ar ₂ , m and n are as previously defined.

Preferably, R ₁ and R ₂ may each independently be methyl or phenyl.

Preferably, R ₃ and R ₄ may each independently be hydrogen.

Preferably, m and n may each independently be 0 or 1.

Preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

In the above formula, a is an integer from 0 to 5.

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

.

.

The compound represented by Formula 1 can be prepared through Reaction Scheme A below.

[Scheme A]

In Scheme A, except for X ₁ and X ₂ , the remaining variables are as defined in Formula 1, and X ₁ and X ₂ are halogen. The above reaction formula A is a Suzuki coupling reaction and an amine substitution reaction in the presence of a palladium catalyst and a base catalyst to prepare the compound represented by Formula 1 herein. The manufacturing method may be further detailed in the manufacturing examples described later. Additionally, the reactor, catalyst, solvent, etc. used can be changed to suit the desired product.

Additionally, 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. do.

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 suppression 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 addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, the hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 Contains the indicated compounds.

Additionally, the organic material layer may include an electron blocking layer, and the electron blocking layer includes the compound represented by Chemical Formula 1.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer includes the compound represented by Chemical Formula 1.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or a layer that simultaneously performs electron transport and electron injection, and the electron transport layer, the electron injection layer, or a layer that performs both electron transport and electron injection has the formula above: Includes compounds indicated by 1.

In addition, the organic material layer includes a hole injection layer, a hole transport layer, an electron suppression layer, and a light-emitting layer, and at least one selected from the group consisting of the hole injection layer, a hole transport layer, and an electron suppression layer is a compound represented by Formula 1. may include.

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 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.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppressing layer (7), a light emitting layer (3), an electron transport layer (8), and an electron injection layer (9). and a cathode (4). In this structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, hole transport layer, electron suppression layer, light emitting layer, electron transport layer, and electron injection 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, 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. 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 a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and passing to the hole transport layer. It is also called a layer or an electron blocking layer. A material with lower electron affinity than the electron transport layer is preferred for the electron suppressing layer.

The light-emitting material is a material that can emit 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 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 electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable. do. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light-emitting layer or a light-emitting material, and hole injection of excitons generated in the light-emitting layer. A compound that prevents movement to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metals. Complex compounds and nitrogen-containing five-membered ring derivatives are included, but are not limited thereto.

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 front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

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

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

Preparation of intermediate compounds

(1) Preparation of intermediate compound A-1

[Scheme A-1]

Compounds a-1 (46.7g, 131.91mmol) and b-1 (50.0g, 125.63mmol) were completely dissolved in 400ml of tetrahydrofuran in a 1000ml round bottom flask under a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (200ml) was added. Tetrakis-(triphenylphosphine)palladium (4.36 g, 3.77 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 520 ml of ethyl acetate to prepare Compound A-1 (44.76 g, 72%).

MS[M+H] ⁺ = 499

(2) Preparation of intermediate compound A-2

[Scheme A-2]

Compounds a-2 (46.7g, 131.91mmol) and b-1 (50.0g, 125.63mmol) were completely dissolved in 400ml of tetrahydrofuran in a 1000ml round bottom flask under a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (200ml) was added. Tetrakis-(triphenylphosphine)palladium (4.36 g, 3.77 mmol) was added, followed by heating and stirring for 7 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 440 ml of ethyl acetate to prepare Compound A-2 (35.11 g, 56%).

MS[M+H] ⁺ = 499

(3) Preparation of intermediate compound A-3

[Scheme A-3]

In the synthesis of intermediate compound A-1, intermediate compound A-3 was synthesized in the same manner except that compound b-2 was used instead of compound b-1.

MS [M+H] ⁺ = 499

(4) Preparation of intermediate compound A-4

[Scheme A-4]

In the synthesis of intermediate compound A-2, intermediate compound A-4 was synthesized in the same manner except that compound b-2 was used instead of compound b-1.

MS [M+H] ⁺ = 499

(5) Preparation of intermediate compound A-5

[Scheme A-5]

In the synthesis of intermediate compound A-1, intermediate compound A-5 was synthesized in the same manner except that compound b-3 was used instead of compound b-1.

MS [M+H] ⁺ = 499

(6) Preparation of intermediate compound A-6

[Scheme A-6]

In the synthesis of intermediate compound A-2, intermediate compound A-6 was synthesized in the same manner except that compound b-3 was used instead of compound b-1.

MS [M+H] ⁺ = 499

(7) Preparation of intermediate compound A-7

[Scheme A-7]

In the synthesis of intermediate compound A-1, intermediate compound A-7 was synthesized in the same manner except that compound b-4 was used instead of compound b-1.

MS [M+H] ⁺ = 623

Example Preparation of Compounds

(1) Example 1: Preparation of Compound 1

[Scheme 1]

Compound A-1 (8.36 g, 16.78 mmol) and compound a1 (5.66 g, 17.62 mmol) were completely dissolved in 250 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.42 g, 25.18 mmol) was added , Bis(tri- tert -butylphosphine) palladium(0) (0.17 g, 0.34 mmol) was added and then heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare Compound 1 (8.23 g, yield: 66%).

MS[M+H] ⁺ = 740

(2) Example 2: Preparation of Compound 2

[Scheme 2]

Compound A-1 (7.13 g, 14.31 mmol) and compound a2 (5.97 g, 15.03 mmol) were completely dissolved in 220 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.06 g, 21.47 mmol) was added , Bis(tri- tert -butylphosphine) palladium(0) (0.15 g, 0.29 mmol) was added and heated and stirred for 2 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 240 mL of ethyl acetate to prepare Compound 2 (8.46 g, yield: 72%).

MS[M+H] ⁺ = 816

(3) Example 3: Preparation of Compound 3

[Scheme 3]

Compound A-1 (6.48 g, 27.93 mmol) and compound a3 (4.58 g, 13.66 mmol) were completely dissolved in 240 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (1.88 g, 19.51 mmol) was added. , Bis(tri- tert -butylphosphine) palladium(0) (0.13 g, 0.26 mmol) was added and then heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 260 mL of acetate to prepare Compound 3 (5.36 g, yield: 55%).

MS[M+H] ⁺ = 754

(4) Example 4: Preparation of Compound 4

[Scheme 4]

Compound A-1 (8.13 g, 16.32 mmol) and compound a4 (6.70 g, 17.14 mmol) were completely dissolved in 260 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.35 g, 24.48 mmol) was added , Bis(tri- tert -butylphosphine) palladium(0) (0.17 g, 0.33 mmol) was added and heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare compound 4 (7.33 g, yield: 55%).

MS[M+H] ⁺ = 810

(5) Example 5: Preparation of compound 5

[Scheme 5]

Compound A-2 (9.33 g, 18.73 mmol) and compound a5 (6.79 g, 19.67 mmol) were completely dissolved in 260 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.70 g, 28.10 mmol) was added. , Bis(tri-tert-butylphosphine) palladium(0) (0.19 g, 0.37 mmol) was added and heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare compound 5 (9.22 g, yield: 64%).

MS[M+H]+= 764

(6) Example 6: Preparation of compound 6

[Scheme 6]

Compound A-3 (8.44 g, 16.94 mmol) and compound a6 (6.14 g, 17.79 mmol) were completely dissolved in 280 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and then NaOtBu (2.44 g, 25.42 mmol) was added. , Bis(tri- tert -butylphosphine) palladium(0) (0.17 g, 0.34 mmol) was added and then heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 250 mL of ethyl acetate to prepare compound 6 (8.09 g, yield: 62%).

MS[M+H] ⁺ = 764

(7) Example 7: Preparation of compound 7

[Scheme 7]

Compound A-4 (8.88 g, 17.83 mmol) and compound a7 (6.94 g, 18.72 mmol) were completely dissolved in 220 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.57 g, 26.74 mmol) was added. , Bis(tri-tert-butylphosphine) palladium(0) (0.18 g, 0.36 mmol) was added and heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 260 mL of ethyl acetate to prepare compound 7 (9.46 g, yield: 67%).

MS[M+H]+= 790

(8) Example 8: Preparation of compound 8

[Scheme 8]

Compound A-5 (8.37 g, 16.80 mmol) and compound a8 (6.55 g, 17.64 mmol) were completely dissolved in 250 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.42 g, 25.21 mmol) was added. , Bis(tri- tert -butylphosphine) palladium(0) (0.17 g, 0.34 mmol) was added and then heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 250 mL of ethyl acetate to prepare compound 8 (7.79 g, yield: 59%).

MS[M+H] ⁺ = 790

(9) Example 9: Preparation of Compound 9

[Scheme 9]

Compound A-6 (7.85 g, 15.76 mmol) and compound a9 (5.31 g, 16.55 mmol) were completely dissolved in 240 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.27 g, 23.64 mmol) was added. , Bis(tri- tert -butylphosphine) palladium(0) (0.16 g, 0.32 mmol) was added and heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of acetone to prepare compound 9 (8.43 g, yield: 72%).

MS[M+H] ⁺ = 624

(10) Example 10: Preparation of compound 10

[Scheme 10]

Compound A-7 (8.95 g, 17.97 mmol) and compound a10 (6.06 g, 18.87 mmol) were completely dissolved in 260 mL of Xylene in a 500 mL round bottom flask under a nitrogen atmosphere, and NaOtBu (2.59 g, 26.95 mmol) was added. , Bis(tri- tert -butylphosphine) palladium(0) (0.18 g, 0.36 mmol) was added and heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare compound 10 (10.75 g, yield: 69%).

MS[M+H] ⁺ = 864

Experiment example

(1) Experimental 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, which is the anode prepared in this way, the compounds of the following compound HI1 and the following compound HI2 were thermally vacuum deposited to a thickness of 100 Å at a ratio of 98:2 (molar ratio) to form a hole injection layer. A hole transport layer was formed by vacuum depositing a compound (1150 Å) represented by the following chemical formula HT1 on the hole injection layer. Next, Compound 1 of Example 1 was vacuum deposited on the hole transport layer to a film thickness of 50 Å to form an electron blocking layer. Subsequently, a compound represented by the following formula BH and a compound represented by the following formula BD were vacuum deposited on the electron blocking layer at a film thickness of 200 Å at a weight ratio of 25:1 to form a light emitting layer. A hole blocking layer was formed by vacuum depositing a compound represented by the following chemical formula HB1 with a film thickness of 50 Å on the light emitting layer. Next, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 310 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 0.4~0.7Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3Å/sec, and the deposition rate of aluminum was maintained at 2Å/sec, and the vacuum degree during deposition was 2x10 ^-7 ~ An organic light emitting device was manufactured by maintaining 5×10 ^-6 torr.

(2) Experimental Examples 2 to 10

In Experimental Example 1, an organic light-emitting device was manufactured in the same manner as Experimental Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1 of Example 1.

(3) Comparative Experimental Examples 1 to 4

In Experimental Example 1, an organic light-emitting device was manufactured in the same manner as Experimental Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1 of Example 1. The compounds EB2, EB3, EB4, and EB5 used in Table 1 below are as follows.

When current was applied to the organic light emitting device manufactured above, the voltage, efficiency, color coordinate, 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 (1600 nit) to 95%.

division compound
(electron suppression layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Experimental Example 1 Example 1 4.48 6.45 (0.145, 0.046) 260 Experimental Example 2 Example 2 4.42 6.43 (0.144, 0.045) 265 Experimental Example 3 Example 3 4.34 6.56 (0.144, 0.047) 280 Experimental Example 4 Example 4 4.31 6.57 (0.144, 0.045) 280 Experimental Example 5 Example 5 4.53 6.32 (0.145, 0.044) 275 Experimental Example 6 Example 6 4.56 6.38 (0.145, 0.045) 250 Experimental Example 7 Example 7 4.58 6.37 (0.144, 0.045) 255 Experimental Example 8 Example 8 4.52 6.36 (0.144, 0.046) 25 Experimental Example 9 Example 9 4.51 6.38 (0.145, 0.047) 275 Experimental Example 10 Example 10 4.47 6.36 (0.144, 0.045) 265 Comparative Experiment Example 1 EB2 5.32 5.85 (0.144, 0.046) 125 Comparative Experiment Example 2 EB3 4.91 5.36 (0.143, 0.044) 140 Comparative Experiment Example 3 EB4 5.53 5.47 (0.145, 0.045) 115 Comparative Experiment Example 4 EB5 4.83 5.82 (0.146, 0.046) 180

As shown in Table 1, the organic light-emitting device using the compound of the present invention as an electron blocking layer showed excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.

1: Substrate 2: Anode
3: Organic layer 4: Cathode
5: hole injection layer 6: hole transport layer
7: electron suppressing layer 8: light emitting layer
9: electron transport layer 10: electron injection layer

Claims (9)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently methyl or phenyl,
R ₃ and R ₄ are each independently hydrogen,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of:


In the above formula, a is an integer from 0 to 5,
m and n are each independently integers from 0 to 3.
According to clause 1,
The compound represented by Formula 1 is any one selected from compounds represented by Formulas 2 to 10 below:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Formulas 2 to 10,
R ₁ , R ₂ , R ₃ , R ₄ , Ar ₁ , Ar ₂ , m and n are as defined in claim 1.
delete delete delete According to clause 1,
m and n are each independently 0 or 1.
According to clause 1,
The compound represented by Formula 1 is any one selected from the group consisting of:











.
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 of the organic material layers is any of claims 1, 2, 6, and 7. An organic light-emitting device comprising the compound according to one clause.
According to clause 8,
An organic light emitting device wherein the organic material layer is an electron suppression layer.