KR102521480B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device with improved driving voltage, efficiency and lifetime.

Description

Organic light emitting device {Organic light emitting device}

The present invention relates to an organic light emitting diode having improved driving voltage, efficiency and lifetime.

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

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, 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 are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

In the organic light emitting device as described above, the development of an organic light emitting device with improved driving voltage, efficiency, and lifespan is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting diode having improved driving voltage, efficiency and lifetime.

The present invention provides the following organic light emitting device:

anode; cathode; And a light emitting layer between the anode and the cathode,

The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.

Organic Light-Emitting Elements:

[Formula 1]

In Formula 1,

X is O or S;

Ar ₁ is a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

[Formula 2]

In Formula 1,

Ar ₄ is phenanthrenyl or triphenylenyl;

Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C _6-60 aryl;

L ₁ to L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.

The organic light emitting device described above may improve efficiency, low driving voltage, and/or lifetime characteristics of the organic light emitting device by including the compound represented by Formula 1 and the compound represented by Formula 2 in the light emitting layer.

1 shows an example of an organic light emitting device composed 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, a light emitting layer 3, a hole blocking layer 7, an electron transport layer 8, and a cathode 4. It shows an example of an organic light emitting device made of.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl 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 a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

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

In this specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms 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, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl 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, and the like, but is not limited thereto.

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

etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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

Hereinafter, the present invention will be described in detail for each configuration.

anode and cathode

An anode and a cathode used in the present invention refer to electrodes used in an organic light emitting device.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode 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, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

hole injection layer

The organic light emitting device according to the present invention may further include a hole injection layer on the anode, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. In addition, 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 layer.

Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

hole transport layer

The organic light emitting device according to the present invention may include a hole transport layer on the anode (or on the hole injection layer if the hole injection layer exists), if necessary.

The hole transport layer is a layer that receives holes from the anode or the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, it is a material that receives holes from the anode or the hole injection layer and transfers them to the light emitting layer, and has hole mobility. Larger materials are suitable.

Specific examples of the hole transport material include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

light emitting layer

The light emitting layer used in the present invention means a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by Formula 1 and the compound represented by Formula 2 are included as hosts.

Preferably, Ar ₁ is a substituted or unsubstituted C _6-60 aryl, and Ar ₂ and Ar ₃ may each independently represent a substituted or unsubstituted C _6-60 aryl.

Preferably, Ar ₁ can be substituted or unsubstituted C _6-20 aryl, more preferably, Ar ₁ can be phenyl or naphthyl.

Preferably, Ar ₂ and Ar ₃ may each independently be a substituted or unsubstituted C _6-20 aryl, more preferably, Ar ₂ and Ar ₃ may each independently be phenyl, biphenylyl, naphthyl ethyl, or phenanthrenyl.

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

.

.

The compound represented by Chemical Formula 1 can be prepared by, for example, a manufacturing method such as the following Reaction Scheme 1, and other compounds can be prepared similarly.

[Scheme 1]

In Reaction Scheme 1, X and Ar ₁ to Ar ₃ are as defined in Formula 1, X ₁ is halogen, and preferably X ₁ is chloro or bromo.

Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction may be modified as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, the compound represented by Formula 2 may be represented by Formula 2-1 or Formula 2-2 below.

[Formula 2-1]

[Formula 2-2]

In Formula 2-1 or Formula 2-2,

Ar ₅ , Ar ₆ and L ₁ to L ₃ are as defined in Formula 2 above.

Preferably, Ar ₅ and Ar ₆ may each independently be a substituted or unsubstituted C _6-20 aryl, more preferably, Ar ₅ and Ar ₆ may each independently be phenyl, biphenylyl, ter phenylyl, naphthyl, or phenanthrenyl.

Preferably, Ar ₅ is biphenylyl, and Ar ₆ can be phenyl, biphenylyl, terphenylyl, naphthyl, or phenanthrenyl.

, 또는

일 수 있다.Preferably, L ₁ to L ₃ are each independently a single bond; Or it may be a substituted or unsubstituted C _6-20 arylene, more preferably, L ₁ to L ₃ may each independently be a single bond, phenylene, or naphthylene, and most preferably, L ₁ to L ₃ are each independently a single bond;

, or

can be

Preferably, L ₁ is phenylene, and L ₂ and L ₃ each independently may be a single bond, phenylene, or naphthylene.

Representative examples of the compound represented by Formula 2 are as follows:

.

.

The compound represented by Chemical Formula 2 can be prepared by, for example, a manufacturing method such as the following Reaction Scheme 2, and other compounds can be prepared similarly.

[Scheme 2]

In Scheme 2, Ar ₄ to Ar ₆ and L ₁ to L ₃ are as defined in Formula 2, X ₂ is halogen, and preferably X ₂ is chloro or bromo.

Reaction Scheme 2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, the weight ratio of the compound represented by Formula 1 and the compound represented by Formula 2 in the light emitting layer is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30 or 40:60 to 60:40.

Meanwhile, the light emitting layer may further include a dopant in addition to a host. The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. For example, there are aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

hole blocking layer

The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer in order to prevent holes injected from the anode from passing to the electron transport layer without recombination in the light emitting layer, and is also called a hole blocking layer. A material having high ionization energy is preferred for the hole blocking layer.

electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer on the light emitting layer, if necessary.

The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode. As a material that can be received and transferred to the light emitting layer, a material having high electron mobility is suitable.

Specific examples of the electron transport material include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto. 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 having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer on the light emitting layer (or on the electron transport layer when the electron transport layer is present), if necessary.

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. It is preferable to use a compound that prevents migration to a layer and has excellent thin film forming ability.

Specific examples of materials that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preore nylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc., but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2 . 1 shows an example of an organic light emitting device composed 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, a light emitting layer 3, a hole blocking layer 7, an electron transport layer 8, and a cathode 4. It shows an example of an organic light emitting device made of.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-described layers thereon, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate and an anode material in the reverse order of the above configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

[Production Example]

Preparation Example 1-1: Preparation of Compound 1-1

Step 1) Preparation of Compound A-1

1,3-dibromo-5-iodobenzene (100 g, 277.9 mmol), phenylboronic acid (1 eq), Pd(P(t-Bu) ₃ ) ₂ (0.005 eq) and potassium carbonate (3 eq) was dissolved in a mixture of THF (1000 ml) and distilled water (500 ml) and refluxed for 1 hour. After the reaction was completed, distilled water was removed, and the organic layer was extracted and dried over magnesium sulfate. After distillation under reduced pressure, silica was purified using column chromatography to obtain Compound A-1 (43 g, yield: 50%).

MS:[M+H] ⁺ = 312

Step 2) Preparation of Compound A-2

Compound A-1 (43 g, 138.7 mmol), dibenzo [b, d] furan-1-yl boronic acid (1 eq), Pd (P (t-Bu) ₃ ) ₂ (0.005 eq) and potassium carbonate (3 eq) was dissolved in a mixture of THF (500 ml) and distilled water (250 ml) and refluxed for 1 hour. After the reaction was completed, distilled water was added, and the organic layer was extracted and dried over magnesium sulfate. Purification was performed using column chromatography to obtain compound A-2 (28.7 g, yield: 52%).

MS:[M+H] ⁺ = 398

Step 3) Preparation of Compound A-3

Compound A-2 (28.7 g, 72.1 mmol), pinacolatodiboron (1.1 eq), Pd(dppf)Cl ₂ (0.02 eq) and potassium acetate (3 eq) were dissolved in 300 ml of 1,4-dioxane Refluxed for 3 hours. After the reaction was completed, distilled water was added, and the organic layer was extracted and dried over magnesium sulfate. Purification was performed using column chromatography to obtain compound A-3 (23.1 g, yield: 72%).

MS:[M+H] ⁺ = 446

Step 3) Preparation of Compound 1-1

Compound A-3 (23.1 g, 51.8 mmol), 2-chloro-4,6- (naphthalen-2-yl) -1,3,5-triazine (1 eq), Pd (P (t-Bu) ₃ ) ₂ (0.005 eq) and potassium carbonate (3 eq) were dissolved in a mixture of THF (300 ml) and distilled water (150 ml) and refluxed for 1 hour. After the reaction was completed, distilled water was removed, and the organic layer was extracted and dried over magnesium sulfate. After distillation under reduced pressure, silica was purified using column chromatography to obtain compound 1-1 (20.9 g, yield: 62%).

MS: [M+H] ⁺ = 651

Preparation Example 1-2: Preparation of Compound 1-2

In step 2 of Preparation Example 1, except that dibenzo [b, d] furan-1-yl boronic acid was used instead of dibenzo [b, d] furan-1-yl boronic acid, Preparation Example 1 Compound 2 was prepared in the same manner as above.

Preparation Example 2-1: Preparation of Compound 2-1

Step 1) Preparation of Compound B-1

Phenanthren-9-yl boronic acid (50 g, 225.1 mmol), 1-bromo-4-chlorobenzene (1 eq), Pd(P(t-Bu) ₃ ) ₂ (0.005 eq) and potassium carbonate ( 3 eq) was dissolved in a mixture of THF (500 ml) and distilled water (250 ml) and refluxed for 1 hour. After the reaction was completed, distilled water was removed, and the organic layer was extracted and dried over magnesium sulfate. After distillation under reduced pressure, silica was purified using column chromatography to obtain compound B-1 (40.8 g, yield: 63%).

MS:[M+H] ⁺ = 288

Step 2) Preparation of Compound 2-1

Compound B-1 (40 g, 138.8 mmol), di([1,1'-biphenyl]-4-yl)amine (1 eq), Pd(P(t-Bu) ₃ ) ₂ (0.005 eq) and Sodium tertbutoxide (3 eq) was dissolved in Toluene (500 ml) and refluxed for 1 hour. After the reaction was completed, distilled water was added, and the organic layer was extracted and dried over magnesium sulfate. Purification was performed using column chromatography to obtain Compound 2 (69.3 g, yield: 55%).

MS: [M+H] ⁺ = 573

Preparation Example 2-2: Preparation of Compound 2-2

In step 2 of Preparation Example 2-1, N-(4-(naphthalen-2-yl)phenyl)-[1,1'-bi instead of di([1,1'-biphenyl]-4-yl)amine Compound 2-2 was prepared in the same manner as in Preparation Example 2-1, except that phenyl] -4-amine was used.

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1300 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

A hole injection layer was formed by thermal vacuum deposition of the compound HAT-CN to a thickness of 500 Å on the ITO transparent electrode prepared as described above. On the hole injection layer, the following compound HT1 was thermally vacuum deposited to a thickness of 800 Å, and the following compound HT2 was sequentially vacuum deposited to a thickness of 500 Å to form a hole transport layer. On the hole transport layer, as a host, Compound 1-1 and Compound 2-1 previously prepared (including Compound 1-1 and Compound 2-1 in a weight ratio of 6:4) and the following compound Dp-7 as a dopant (host and compound 2-1) A light emitting layer was formed by vacuum-evaporation of 3% by weight of dopants with respect to the total amount of dopants) to a thickness of 300 Å. On the light emitting layer, the following compound ET1 was vacuum-deposited to a thickness of 50 Å to form a hole blocking layer, and the following compound ET2 and lithium quinolate (LiQ) were deposited at a weight ratio of 1:1 to a thickness of 250 Å on the hole blocking layer. An electron transport layer was formed by vacuum deposition. Lithium fluoride (LiF) was sequentially deposited to a thickness of 10 Å on the electron transport layer, and aluminum was deposited to a thickness of 1000 Å thereon to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride on the anode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 1 * 10 ^-7 ~ 5 * 10 ^-8 torr was maintained

Example 2

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compounds 1-1 and 2-1.

Comparative Example 1 and Comparative Example 2

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1.

In Table 1 below, compounds CE1 and CE2 are respectively as follows.

Experimental example

When a current of 10 mA/cm ² was applied to the organic light emitting devices prepared in Examples and Comparative Examples, driving voltage, luminous efficiency, lifetime, and luminous color were measured, and the results are shown in Table 1 below. The driving voltage, luminous efficiency, and luminous color are data at 5000 nit luminance, and the lifetime (T98) means the time required to decrease from the initial luminance (5000 nit) to 98%.

division host substance driving voltage
(V) efficiency
(cd/A) life span
T98 (hr) luminescent color Example 1 compound 1-1 compound 2-1 4.0 36.3 51 Red Example 2 compound 1-1 compound 2-1 3.9 35.8 40 Red Example 3 compound 1-2 compound 2-2 4.1 32.0 38 Red Comparative Example 1 compound CE1 4.4 24.6 17 Red Comparative Example 2 compound CE2 4.7 28.1 28 Red

As shown in Table 1, the organic light emitting device including the two compounds of the present invention exhibited excellent characteristics in terms of efficiency, driving voltage, and lifetime of the organic light emitting device.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: hole blocking layer 8: electron transport layer

Claims (12)

anode;
cathode; and
Including a light emitting layer between the anode and the cathode,
The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.
Organic Light-Emitting Elements:
[Formula 1]

In Formula 1,
X is O or S;
Ar ₁ is a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
Ar ₂ is naphthyl;
Ar ₃ is a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
[Formula 2]

In Formula 2,
Ar ₄ is phenanthrenyl or triphenylenyl;
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C _6-60 aryl;
L ₁ to L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
Ar ₁ is a substituted or unsubstituted C _6-60 aryl;
Ar ₃ is a substituted or unsubstituted C _6-60 aryl;
organic light emitting device.
According to claim 1,
Ar ₁ is phenyl or naphthyl;
organic light emitting device.
According to claim 1,
Ar ₃ is phenyl, biphenylyl, naphthyl, or phenanthrenyl;
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:

.
According to claim 1,
The compound represented by Formula 2 is represented by Formula 2-1 or Formula 2-2 below,
Organic Light-Emitting Elements:
[Formula 2-1]

[Formula 2-2]

In Formula 2-1 or Formula 2-2,
Ar ₅ , Ar ₆ and L ₁ to L ₃ are as defined in claim 1.
According to claim 1,
Ar ₅ and Ar ₆ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, or phenanthrenyl;
organic light emitting device.
According to claim 1,
Ar ₅ is biphenylyl, Ar ₆ is phenyl, biphenylyl, terphenylyl, naphthyl, or phenanthrenyl;
organic light emitting device.
According to claim 1,
L ₁ to L ₃ are each independently a single bond, phenylene, or naphthylene;
organic light emitting device.
According to claim 1,
L ₁ to L ₃ are each independently a single bond;

, or

person,
organic light emitting device.
According to claim 1,
L ₁ is phenylene, L ₂ and L ₃ are each independently a single bond, phenylene, or naphthylene;
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements:

.

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