KR20190096228A - Organic light emitting device - Google Patents

Abstract

The present invention relates to an organic light emitting device having improved efficiency, low driving voltage and/or service life characteristics. The organic light emitting device comprises: a positive electrode; a negative electrode provided to face the positive electrode; and one or more organic material layers provided between the positive electrode and the negative electrode.

Description

Organic light emitting element {ORGANIC LIGHT EMITTING DEVICE}

The present invention relates to an organic light emitting device.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

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

There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices.

The present invention provides an organic light emitting device.

The present invention is an anode; A cathode provided to face the anode; And at least one organic material layer provided between the anode and the cathode, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by the following Chemical Formula 1; It provides an organic light emitting device comprising a hole transport layer containing a compound represented by the formula (2).

[Formula 1]

In Chemical Formula 1,

X ₁ is O or S,

L ₁ and L ₂ are each independently a single bond or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,

Y ₁ to Y ₃ are each independently N or CR ′, at least one is N, R ′ is hydrogen or substituted or unsubstituted alkyl having 1 to 40 carbon atoms,

Ar ₁ to Ar ₃ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms, or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms containing at least one of O, N, Si and S,

m is an integer of 1 to 2,

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₁₇ are each independently hydrogen; Substituted or unsubstituted alkyl having 2 to 60 carbon atoms; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; Or heteroaryl having 2 to 60 carbon atoms including one or more of substituted or unsubstituted O, N, Si, and S, or groups adjacent to each other may be bonded to form an aliphatic or hetero condensed ring,

L ₃ is each independently a single bond; Or substituted or unsubstituted arylene having 6 to 60 carbon atoms,

Ar ₄ and Ar ₅ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or heteroaryl having 2 to 60 carbon atoms including at least one of substituted or unsubstituted O, N, Si, and S.

Improvement of efficiency, low driving voltage and / or lifespan characteristics in an organic light emitting device by using the compound represented by Chemical Formula 1 as a host material of the light emitting layer and the compound represented by Chemical Formula 2 as the material of the hole transport layer. Can improve.

1 shows a substrate 1, an anode 2; A hole transport layer 3; A hole regulation layer 4; Light emitting layer 5; Electron transport layer 6; And an example of an organic light-emitting device composed of a cathode 7.

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

The present invention provides an organic light emitting device including a compound including a compound represented by the formula (1), the light emitting layer comprising a hole transport layer comprising a compound represented by the formula (2) between the anode and the light emitting layer.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, O and S atoms, or two or more substituents in the above-described substituents connected or substituted. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group and can be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

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

In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group, and the like.

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

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary 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 and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be 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,

And so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group 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, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia There may be a sleepy group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example 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 aforementioned heterocyclic group 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 aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

The present invention, an anode; A cathode provided to face the anode; And at least one organic material layer provided between the anode and the cathode, wherein the organic material layer includes a light emitting layer including a compound represented by the following Chemical Formula 1, and includes a compound represented by the following Chemical Formula 2 between the anode and the light emitting layer. It provides an organic light emitting device comprising a hole transport layer.

The organic light emitting device according to the present invention uses the compound represented by Chemical Formula 1 as a host material of the light emitting layer and the compound represented by Chemical Formula 2 as the material of the hole transport layer, thereby improving efficiency in the organic light emitting device, Low drive voltage and / or lifetime characteristics can be improved.

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

Anode and cathode

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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), indium zinc oxide (IZO); Combinations of oxides with metals 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, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

In addition, a hole injection layer may be further included on the anode. The hole injection layer is made of a hole injection material, has a capability of transporting holes as a hole injection material has a hole injection effect at the anode, an excellent hole injection effect to the light emitting layer or the light emitting material, and The compound which prevents the movement to an electron injection layer or an electron injection material, and is excellent in thin film formation ability is preferable.

Preferably, 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 porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene Organic, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

Light emitting layer

The light emitting material included in the light emitting layer is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole control layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. .

The light emitting layer may include a host material and a dopant material, and in particular, in the present invention, the compound includes the compound represented by Chemical Formula 1 as the host material.

In Formula 1 X ₁ may be O or S, can be more specifically O.

In Formula 1, L ₁ and L ₂ may be each independently a single bond, phenylene, or biphenylene.

Y ₁ to Y ₃ in Formula 1 are each independently N or CH, at least one may be N.

Ar ₁ and Ar ₂ in Formula 1 may be each independently a substituent selected from the group consisting of:

Ar ₃ in Formula 1 may be a substituent selected from the group consisting of:

The compound represented by Chemical Formula 1 may be a compound selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 and 1-2.

[Formula 1-1]

In Chemical Formula 1-1,

X ₁ , L ₁ , Y ₁ to Y ₃ , Ar ₁ and Ar ₂ are the same as those of Formula 1,

L _2a is a single bond or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,

Ar _3a is substituted or unsubstituted aryl having 6 to 60 carbon atoms, or heteroaryl having 2 to 60 carbon atoms containing at least one of substituted or unsubstituted O, N, Si, and S,

[Formula 1-2]

In Chemical Formula 1-2,

X ₁ , L ₁ , Y ₁ to Y ₃ , Ar ₁ and Ar ₂ are the same as those of Formula 1,

L _2b and L _2c are each independently a single bond or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,

Ar _3b and Ar _3c are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms, or heteroaryl having 2 to 60 carbon atoms including at least one of substituted or unsubstituted O, N, Si, and S.

As defined above formula 1-1 and 1-2 of X _1, L _1, Y ₁ to about Y _3, Ar ₁ and Ar ₂ is X _1, L _1, Y ₁ to about Y _3, Ar ₁ and Ar ₂ of formula (I) and, L _2a to L _2c correspond to the L ₂ in formula (I), Ar _3a to Ar _3c corresponds to the formula (1) and Ar _3, X _1, L ₁ and L _2, Y ₁ to Y _3, Ar ₁ to Since a specific example of Ar ₃ has been described in detail above, a detailed description thereof will be omitted.

The compound represented by Chemical Formula 1 may be selected from the group consisting of the following compounds.

The compound represented by Chemical Formula 1 may be prepared by the same method as in Scheme 1 below. The manufacturing method may be more specific in the production examples described later.

Scheme 1

In Scheme 1, X ₁ , L ₂ , Ar ₁ to Ar ₃ , and Y ₁ to Y ₃ are as defined above.

In addition, as the host material, a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 3 may be used.

[Formula 3]

In Formula 3, Ar ₆ and Ar ₇ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms.

In Formula 3, Ar ₆ and Ar ₇ are each independently benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spiro [flu] Orene-9,9'-fluorene], phenylterphenyl, phenylnaphthalene and phenylphenanthrene.

The compound represented by Chemical Formula 3 may be selected from the group consisting of the following compounds.

The emission layer may further include a host material known in the art to which the present invention pertains, in addition to the compounds represented by Formulas 1 and 3. Specific examples of such host materials include condensed aromatic ring derivatives and hetero ring-containing compounds. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

On the other hand, the dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

Hole transport layer

The hole transport layer used in the present invention is a layer for receiving holes from the hole injection layer formed on the anode or the anode to transport holes to the light emitting layer, and the compound represented by Chemical Formula 2 is used as a material for forming the hole transport layer.

The compound represented by Chemical Formula 2 is suitable for transporting holes from the anode or the hole injection layer to the light emitting layer because of high mobility to the holes.

In Formula 2, L ₃ may be each independently a single bond, phenyl, naphthalene, biphenyl, or fluorene.

In Formula 2, R ₁ to R ₈ and R ₁₁ to R ₁₇ may be hydrogen.

R ₉ and R ₁₀ in Formula 2 may be hydrogen, or may be combined to form an aliphatic or hetero condensed ring.

Ar ₄ and Ar ₅ in Formula 2 may each independently be phenyl, biphenyl, terphenyl, quarterphenyl, fluorene, phenanthrene, triphenylene, dibenzofuran or dibenzothiophene.

The compound represented by Chemical Formula 2 may be selected from the group consisting of the following compounds.

The compound represented by Formula 2 may be prepared by the same method as in Scheme 2 below. The manufacturing method may be more specific in the production examples described later.

Scheme 2

In Scheme 2, the definitions of Ar ₄ and Ar ₅ are as mentioned above.

Meanwhile, the hole transport layer may further include a hole transport material known in the art to which the present invention pertains, in addition to the compound represented by Chemical Formula 2. Specific examples of such hole transport materials include, but are not limited to, arylamine-based organics, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.

Hole control layer

The hole control layer refers to a layer that controls the mobility of holes according to the energy level of the light emitting layer in the organic light emitting device.

Electron transport layer

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including 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 in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

Electron injection layer

The organic light emitting device according to the present invention may include an electron injection layer between the electron transport layer and the cathode as necessary. The electron injection layer is a layer for injecting electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from the cathode, an excellent electron injection effect to the light emitting layer or the light emitting material, and the hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, 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) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

Organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1. 1 shows a substrate 1, an anode 2; A hole transport layer 3; A hole regulation layer 4; Light emitting layer 5; Electron transport layer 6; And an example of an organic light-emitting device composed of a cathode 7.

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

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

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 according to a material used.

Fabrication of the above-described organic light emitting device will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1-1 Preparation of Compound 1-1

In a 500 ml round-bottom flask in a nitrogen atmosphere, compound 1-a (13.52 g, 22.61 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (5.25 g, 19.66 mmol) were added to 240 ml tetrahydrofuran. After completely dissolved, 2 M aqueous potassium carbonate solution (120 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.68 g, 0.59 mmol) was added thereto, followed by stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 ml of tetrahydrofuran to prepare compound 1-1 (11.05 g, 76%).

MS: [M + H] ⁺ = 704

Preparation Example 1-2 Preparation of Compound 1-2

In a 500 ml round-bottom flask in a nitrogen atmosphere, compound 1-b (16.60 g, 26.36 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (6.12 g, 22.92 mmol) were added to 240 ml tetrahydrofuran. After completely dissolved, 2M aqueous potassium carbonate solution (120 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.79 g, 0.69 mmol) was added thereto, followed by stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of tetrahydrofuran to prepare compound 1-2 (10.17 g, 67%).

MS: [M + H] ⁺ = 660

Preparation Example 1-3 Preparation of Compound 1-3

Compound 1-c (10.24g, 19.61mmol), 2-([1,1'-biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5 in 500ml round bottom flask in nitrogen atmosphere -Triazine (5.85g, 17.06mmol) was completely dissolved in 220ml of tetrahydrofuran, then 2M potassium carbonate solution (110ml) was added, followed by tetrakis- (triphenylphosphine) palladium (0.59g, 0.51mmol). Heat stirring for hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 180 ml of tetrahydrofuran to prepare compound 1-3 (8.47 g, 71%).

MS: [M + H] ⁺ = 704

Preparation Example 1-4: Preparation of Compound 1-4

Compound 1-d (9.33g, 21.86mmol), 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5 in 500ml round bottom flask in nitrogen atmosphere -Triazine (6.52g, 19.01mmol) is completely dissolved in 200ml of tetrahydrofuran, then 2M potassium carbonate solution (100ml) is added, and tetrakis- (triphenylphosphine) palladium (0.86g, 0.74mmol) is added 4 Heat stirring for hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 160 ml of tetrahydrofuran to prepare compound 1-4 (6.65 g, 57%).

MS: [M + H] ⁺ = 609

Preparation Example 2-1 Preparation of Compound 2-1

Dissolve compound 2-a (9.5 g, 19.59 mmol) and di ([1,1'-biphenyl] -4-yl) amine (7.25 g, 22.53 mmol) in 220 ml of Xylene in a 500 ml round-bottom flask in a nitrogen atmosphere. Sodium tert-butoxide (2.45g, 25.46mmol) was added, Pd (t-Bu3P) ₂ (0.10g, 0.20mmol) was added thereto, and the mixture was heated and stirred for 4 hours. After the temperature was lowered to room temperature and the base was filtered to remove the base, xylene was concentrated under reduced pressure and recrystallized twice with 250 ml of ethyl acetate to obtain Compound 2-1 (11.65 g, yield: 82%).

MS: [M + H] ⁺ = 727

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

N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 ''-terphenyl]-instead of di ([1,1'-biphenyl] -4-yl) amine Except that 4-amine was used, Compound 2-2 was prepared by the same method as the method for preparing Compound 2-1.

MS: [M + H] ⁺ = 803

Preparation Example 2-3 Preparation of Compound 2-3

N- (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1'-biphenyl] -4- instead of di ([1,1'-biphenyl] -4-yl) amine Except for using amine, Compound 2-3 was prepared by the same method as the method for preparing Compound 2-1.

MS: [M + H] ⁺ = 637

Preparation Example 2-4: Preparation of Compound 2-4

Compound 2-a (7.50 g, 15.46 mmol), (4- (di ([1,1'-biphenyl] -4-yl) amino) phenyl) boronic acid (7.84g, 17.78) in a 500 ml round bottom flask in a nitrogen atmosphere mmol) was completely dissolved in 260 ml of tetrahydrofuran, 2 M aqueous potassium carbonate solution (130 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.54 g, 0.46 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of tetrahydrofuran to prepare compound 2-4 (11.36 g, 69%).

MS: [M + H] ⁺ = 663

Example 1 Fabrication of Organic Light-Emitting Device

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. was used as a detergent, and distilled water was filtered secondly as a filter of Millipore Co. as a distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The HI1 compound was formed to a thickness of 1100 kV as a hole injection layer on the prepared ITO transparent electrode, but p-doping the following A-1 compound at a concentration of 2%. Compound 2-1 was vacuum deposited on the hole injection layer to form a hole transport layer having a film thickness of 350 GPa. Subsequently, the following EB1 compound was vacuum deposited on the hole transport layer with a film thickness of 150 Pa to form an electron suppressing layer.

Subsequently, on the electron suppressing layer, the host composition in which Compound 1-1 and the following YGH-2 compound were mixed at a weight ratio of 4: 6, and the following YGD-1 compound, which is a phosphorescent dopant at 6% by weight, were vacuum deposited together. To form a green light emitting layer having a thickness of 350 kHz.

A hole blocking layer was formed by vacuum depositing the following HB1 compound on the light emitting layer with a film thickness of 50 GPa. Subsequently, the following ET1 compound and the following LiQ compound were vacuum deposited on the hole blocking layer in a weight ratio of 2: 1 to form an electron injection and transport layer at a thickness of 300 Pa. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited in a thickness of 12 Å in order to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å / sec, the lithium fluoride of the cathode was maintained at 0.3Å / sec, the deposition rate of aluminum was 2Å / sec, the vacuum degree during deposition was 2ⅹ10 ^-7 ~ The organic light emitting device was manufactured by maintaining ⁵ × 10 ⁻⁶ torr.

Examples 2 to 16 and Comparative Examples 1 to 11: Preparation of organic light emitting device

Examples 2 to 16 and Comparative Examples were carried out in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of the compound 2-1 of the hole transport layer and the compound 1-1 of the green light emitting layer, respectively. The organic light emitting device of 1 to 11 was produced. In this case, HT2, HT3 and YGH-1 described in Table 1 below are the compounds shown below.

Experimental Example: Performance Evaluation of Organic Light-Emitting Device

Example 1 to 16 and Comparative Example 1, the organic light emitting device manufactured in to 11 10mA / voltage and efficiency measured at a current density of cm ² and, 20 mA / the initial luminance at a current density of cm ² (6000 nit) compared to 95 Life time (LT ₉₅ ), which is the time taken to decrease by%, was measured and the results are shown in Table 1 below.

Hole
Transport layer Light emitting layer
(4: 6) Voltage
(V) Luminous efficiency
(cd / A) LT ₉₅
(hr) Example 1 2-1 1-1, YGH-2 3.53 6.32 290 Example 2 2-1 1-2, YGH-2 3.56 6.37 290 Example 3 2-1 1-3, YGH-2 3.55 6.36 280 Example 4 2-1 1-4, YGH-2 3.54 6.36 315 Example 5 2-2 1-1, YGH-2 3.71 6.56 290 Example 6 2-2 1-2, YGH-2 3.72 6.52 290 Example 7 2-2 1-3, YGH-2 3.75 6.53 270 Example 8 2-2 1-4, YGH-2 3.75 6.51 320 Example 9 2-3 1-1, YGH-2 3.61 6.35 295 Example 10 2-3 1-2, YGH-2 3.62 6.36 285 Example 11 2-3 1-3, YGH-2 3.63 6.37 270 Example 12 2-3 1-4, YGH-2 3.64 6.39 330 Example 13 2-4 1-1, YGH-2 3.75 6.33 305 Example 14 2-4 1-2, YGH-2 3.76 6.32 315 Example 15 2-4 1-3, YGH-2 3.75 6.37 315 Example 16 2-4 1-4, YGH-2 3.74 6.30 330 Comparative Example 1 HT-2 YGH-1, YGH-2 4.21 5.95 215 Comparative Example 2 HT-3 YGH-1, YGH-2 4.25 6.12 235 Comparative Example 3 HT-2 YGH-1, YGH-1 4.84 5.53 180 Comparative Example 4 2-1 YGH-1, YGH-2 4.01 6.46 250 Comparative Example 5 2-2 YGH-1, YGH-2 3.98 6.44 265 Comparative Example 6 2-3 YGH-1, YGH-2 4.06 6.46 255 Comparative Example 7 2-4 YGH-1, YGH-2 4.05 6.33 250 Comparative Example 8 HT-2 1-1, YGH-2 4.13 6.06 270 Comparative Example 9 HT-2 1-2, YGH-2 4.11 6.08 275 Comparative Example 10 HT-2 1-3, YGH-2 4.15 6.03 280 Comparative Example 11 HT-2 1-4, YGH-2 4.24 6.02 295

In Table 1, the organic light emitting device using the conventional compound (Comparative Examples 1 to 3), the compound represented by the formula (2) as the hole transport layer, but the organic light emitting device using the conventional compound as the green light emitting layer material Examples 4 to 7) and the compound represented by the formula (1) as the light emitting layer material, but the basic characteristics of the organic light emitting device (comparative examples 8 to 11) using the conventional compound as the hole transport layer material is shown.

Comparing the examples and comparative examples, when the compound represented by the formula (1) and (2), respectively, is used as a material of the green light emitting layer and the hole transport layer, compared to the conventional organic light emitting device, a low driving voltage, high efficiency and long lifespan It is confirmed to indicate. In particular, when the compound 2-1 was used as the hole transport layer material, the driving voltage was the lowest and the efficiency was the highest. When 1-4 was used as the light emitting layer material, the longest life was obtained.

On the other hand, comparing Comparative Examples 1 to 11, in Comparative Examples 4 to 7 in which the hole transport layer material is changed to the compound represented by Formula 2, the driving voltage is lowered and the luminous efficiency is improved, and the green light emitting layer material is represented by Formula 1 In Comparative Examples 8 to 11 changed to the compound represented, the service life was improved. However, it did not show the efficiency and lifetime of the example level.

Thus, the organic light emitting device of the present invention includes a compound having an arylamine substituted structure including a benzidine-type linker at position 9 of carbazole, as shown in Formula 2, between the anode and the light emitting layer to exhibit a low driving voltage. As shown in Chemical Formula 1, the compound having the structure of replacing the 4 position of dibenzofuran having electron stability with triazine having excellent electron injection ability and thermal stability is included in the green light emitting layer, thereby exhibiting low driving voltage and improved efficiency and long life. It is confirmed to indicate.

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

Claims (15)

anode; A cathode provided to face the anode; And one or more organic material layers provided between the anode and the cathode.
The organic material layer includes a light emitting layer,
The emission layer includes a compound represented by the following formula (1),
An organic light emitting device comprising a hole transport layer comprising a compound represented by Formula 2 between the anode and the light emitting layer:
[Formula 1]

In Chemical Formula 1,
X ₁ is O or S,
L ₁ and L ₂ are each independently a single bond or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,
Y ₁ to Y ₃ are each independently N or CR ′, at least one is N, R ′ is hydrogen or substituted or unsubstituted alkyl having 1 to 40 carbon atoms,
Ar ₁ to Ar ₃ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms, or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms containing at least one of O, N, Si and S,
m is an integer of 1 to 2,
[Formula 2]

In Chemical Formula 2,
R ₁ to R ₁₇ are each independently hydrogen; Substituted or unsubstituted alkyl having 2 to 60 carbon atoms; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; Or heteroaryl having 2 to 60 carbon atoms including one or more of substituted or unsubstituted O, N, Si, and S, or groups adjacent to each other may be bonded to form an aliphatic or hetero condensed ring,
L ₃ is each independently a single bond; Or substituted or unsubstituted arylene having 6 to 60 carbon atoms,
Ar ₄ and Ar ₅ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or heteroaryl having 2 to 60 carbon atoms including at least one of substituted or unsubstituted O, N, Si, and S.
The organic light emitting device of claim 1, wherein L ₁ and L ₂ are each independently a single bond, phenylene, or biphenylene.
The organic light emitting device of claim 1, wherein X ₁ is O.
The organic light emitting device of claim 1, wherein Y ₁ to Y ₃ are each independently N or CH, and at least one is N.
The organic light emitting device of claim 1, wherein Ar ₁ and Ar ₂ are each independently a substituent selected from the group consisting of:

The organic light emitting device of claim 1, wherein Ar ₃ is a substituent selected from the group consisting of:

The organic light emitting device of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of compounds represented by Chemical Formulas 1-1 and 1-2:
[Formula 1-1]

In Chemical Formula 1-1,
X ₁ , L ₁ , Y ₁ to Y ₃ , Ar ₁ and Ar ₂ are the same as those of Formula 1,
L _2a is a single bond or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,
Ar _3a is substituted or unsubstituted aryl having 6 to 60 carbon atoms, or heteroaryl having 2 to 60 carbon atoms containing at least one of substituted or unsubstituted O, N, Si, and S,
[Formula 1-2]

In Chemical Formula 1-2,
X ₁ , L ₁ , Y ₁ to Y ₃ , Ar ₁ and Ar ₂ are the same as those of Formula 1,
L _2b and L _2c are each independently a single bond or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,
Ar _3b and Ar _3c are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms, or heteroaryl having 2 to 60 carbon atoms including at least one of substituted or unsubstituted O, N, Si, and S.
The organic light emitting device of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of the following compounds:

The organic light emitting device of claim 1, wherein each L ₃ is independently a single bond, phenyl, naphthalene, biphenyl, or fluorene.
The organic light emitting device of claim 1, wherein R ₁ to R ₈ and R ₁₁ to R ₁₇ are hydrogen.
The organic light emitting device of claim 1, wherein R ₉ and R ₁₀ are hydrogen or combine to form an aliphatic or hetero condensed ring.
The organic light emitting device of claim 1, wherein Ar ₄ and Ar ₅ are each independently phenyl, biphenyl, terphenyl, quarterphenyl, fluorene, phenanthrene, triphenylene, dibenzofuran, or dibenzothiophene.
The organic light emitting device of claim 1, wherein the compound represented by Chemical Formula 2 is selected from the group consisting of the following compounds:

The organic light emitting device of claim 1, wherein the light emitting layer further comprises a compound represented by the following Chemical Formula 3:
[Formula 3]

In Chemical Formula 3,
Ar ₆ and Ar ₇ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms.
The organic light-emitting device of claim 14, wherein the compound represented by Chemical Formula 3 is selected from the group consisting of the following compounds: